JP7371634B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained using the same, and a liquid crystal display element equipped with the obtained liquid crystal aligning film. More specifically, the present invention relates to a liquid crystal aligning agent that can provide a liquid crystal aligning film that has good liquid crystal alignment, excellent pretilt angle expression ability, and high reliability, and a liquid crystal display element that has excellent display quality.

In a liquid crystal display element, a liquid crystal alignment film plays the role of aligning liquid crystal in a certain direction. Currently, the main liquid crystal alignment films used industrially are polyimide precursors such as polyamic acid (also called polyamic acid), polyamic acid esters, and polyimide-based liquid crystal alignment agents made of polyimide solutions, which are applied to a substrate. It is manufactured by coating and forming a film.
In addition, when the liquid crystal is aligned parallel or oblique to the substrate surface, a surface stretching process by rubbing is further performed after the film is formed.

On the other hand, when aligning liquid crystal perpendicularly to the substrate (referred to as vertical alignment (VA) method), long-chain alkyls, cyclic groups, or combinations of cyclic groups and alkyl groups (for example, see Patent Document 1), steroid skeletons ( For example, a liquid crystal alignment film is used in which a hydrophobic group such as (see Patent Document 2) is introduced into the side chain of polyimide. In this case, when applying a voltage between the substrates and tilting the liquid crystal molecules in a direction parallel to the substrates, it is necessary to make sure that the liquid crystal molecules tilt from the normal direction of the substrates to one direction within the plane of the substrates. . Methods for this purpose include, for example, providing protrusions on the substrate, providing slits in the display electrodes, and rubbing to slightly tilt the liquid crystal molecules from the normal direction of the substrate toward one direction within the substrate surface. Furthermore, the liquid crystal can be pretilted by adding a photopolymerizable compound to the liquid crystal composition in advance, using it together with a vertical alignment film such as polyimide, and irradiating the liquid crystal cell with ultraviolet rays while applying a voltage. A method (for example, see Patent Document 3) has been proposed.

In recent years, as an alternative to the formation of protrusions and slits in VA liquid crystal alignment control, and the PSA technique, methods (photoalignment methods) that utilize anisotropic photochemical reactions such as polarized ultraviolet irradiation have also been proposed. In other words, it is known that by irradiating a photoreactive, vertically aligned polyimide film with polarized ultraviolet rays to impart alignment regulation ability and pretilt angle development ability, it is possible to uniformly control the tilt direction of liquid crystal molecules when voltage is applied. (See Patent Document 4).

VA type liquid crystal display elements are used in TVs and car displays because of their high contrast and wide viewing angle. LCD display elements for TVs use backlights that generate a large amount of heat in order to achieve high brightness, and LCD display elements used in automobiles, such as car navigation systems and instrument panels, cannot be used in high-temperature environments for long periods of time. It may be used or left alone. Under such severe conditions, if the pretilt angle changes gradually, problems such as initial display characteristics not being obtained or display unevenness occur. Furthermore, when driving the liquid crystal, the voltage retention characteristics and charge accumulation characteristics are also affected by the liquid crystal alignment film, and if the voltage retention rate is low, the contrast of the display screen will decrease, and if the charge accumulation with respect to the DC voltage is large. The phenomenon of burn-in of the display screen occurs.

Japanese Patent Application Publication No. 3-179323 Japanese Patent Application Publication No. 4-281427 Patent No. 4504626 Patent No. 4995267

The present invention was developed in view of the above circumstances, and its objectives are to provide excellent display reliability with little change in pretilt angle even after long-term driving, high voltage holding characteristics, and reduced charge accumulation. An object of the present invention is to provide a liquid crystal aligning film that can be used, a liquid crystal display element having the same, and a liquid crystal aligning agent that provides the same.

The present inventors have discovered the invention whose gist is <X> below.
<X> A polymer having a photo-alignable group represented by the following formula (pa-1) and a thermally crosslinkable group A as the component (A), a polymer selected from polyimide and its precursor as the component (B) contains at least one group selected from a vertical alignment group and a tert-butoxycarbonyl group, or is chemically imidized, and a solvent, and also satisfies the following requirements Z1 and Liquid crystal aligning agent that satisfies at least one of Z2:
Z1: The polymer that is component (A) further has a thermally crosslinkable group B.
Z2: Further contains a compound having two or more thermally crosslinkable groups B in the molecule as component (C).

In the formula, A is optionally a group selected from fluorine, chlorine, cyano, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (which can optionally be one pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, substituted with a cyano group or one or more halogen atoms); Represents 1,4- or 2,6-naphthylene or phenylene, R ₁ is a single bond, oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group group, a divalent heterocyclic group, or a divalent fused cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a straight chain having 1 to 40 carbon atoms. or a monovalent organic group having 3 to 40 carbon atoms containing a branched alkyl group or alicyclic group, and D is an oxygen atom, a sulfur atom, or -NR _d - (where R _d is a hydrogen atom or represents an alkyl having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents a bonding position.
Thermal crosslinkable group A and thermally crosslinkable group B each independently include a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy site-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a block. An organic group selected from the group consisting of isocyanate groups, which is selected such that thermally crosslinkable group A and thermally crosslinkable group B undergo a crosslinking reaction with heat, provided that thermally crosslinkable group A and thermally crosslinkable group The groups B may be the same.

The present invention provides good liquid crystal alignment, excellent pre-tilt angle development ability, little change in pre-tilt angle even after long-term driving, excellent display reliability, high voltage holding characteristics, and low charge accumulation. It is possible to provide a liquid crystal alignment film and a liquid crystal alignment agent that can reduce the amount of liquid crystal alignment.
Furthermore, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics.

The liquid crystal aligning agent of the present invention includes a polymer having a photoalignable group represented by the following formula (pa-1) and a thermally crosslinkable group A as the component (A), and a polyimide and its precursor as the component (B). A polymer selected from polyimide and its precursor, which has at least one group selected from a vertical alignment group and a tert-butoxycarbonyl group, or has been chemically imidized. A liquid crystal aligning agent that contains at least one of a polymer and a solvent and satisfies at least one of the following requirements Z1 and Z2:
Z1: The polymer that is component (A) further has a thermally crosslinkable group B.
Z2: Further contains a compound having two or more thermally crosslinkable groups B in the molecule as component (C).

In the formula, A is optionally a group selected from fluorine, chlorine, cyano, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (which can optionally be one pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, substituted with a cyano group or one or more halogen atoms); Represents 1,4- or 2,6-naphthylene or phenylene, R ₁ is a single bond, oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group group, a divalent heterocyclic group, or a divalent fused cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a straight chain having 1 to 40 carbon atoms. or a monovalent organic group having 3 to 40 carbon atoms containing a branched alkyl group or alicyclic group, and D is an oxygen atom, a sulfur atom, or -NR _d - (where R _d is a hydrogen atom or represents an alkyl having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents a bonding position.
Thermal crosslinkable group A and thermally crosslinkable group B each independently include a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy site-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a block. An organic group selected from the group consisting of isocyanate groups, which is selected such that thermally crosslinkable group A and thermally crosslinkable group B undergo a crosslinking reaction with heat, provided that thermally crosslinkable group A and thermally crosslinkable group The groups B may be the same.

Here, "two or more groups in the molecule" refers to cases in which the molecule contains two or more groups of the same type, such as two or more epoxy groups, as well as cases in which the molecule contains two or more groups of the same type, such as a combination of an epoxy group and a thiirane group. This also includes cases where the molecule contains a total of two or more different groups. "Two or more groups in the molecule" preferably means that the molecule contains two or more groups of the same type.

Since the polymer that is component (A) contained in the liquid crystal aligning agent of the present invention has high sensitivity to light, it can exhibit alignment control ability even when irradiated with polarized ultraviolet light at a low exposure dose.
In addition, since the polymer that is the component (A) contains the thermally crosslinkable group A and further contains the thermally crosslinkable group B in the component, the component (A) can be used even when the baking time of the liquid crystal aligning agent is short. It becomes possible to carry out crosslinking reactions involving polymers that are This makes it easier for the anisotropy to remain (memory) in the liquid crystal alignment film when the photoalignment site develops anisotropy due to a photoreaction, thereby increasing the liquid crystal alignment and developing the pretilt angle of the liquid crystal. It becomes possible to do so.

Furthermore, by containing the polymer as component (B), the liquid crystal aligning agent of the present invention can improve electrical properties such as improving voltage holding rate and suppressing residual charge accumulation.

In addition, since the photo-alignable group, thermally crosslinkable group A and thermally crosslinkable group B represented by the above formula (pa-1) can all become side chains in the polymer, they may be added as necessary. It can also be called a "side chain."
Each component of the present invention will be explained in detail below.

<(A) component: specific polymer>
[Photoalignable group represented by formula (pa-1)]
In the present invention, the site in the molecule having the photo-alignment property represented by the above formula (pa-1) can be represented by, for example, the following formula (a-1). Further, the site may include, but is not limited to, a structure derived from a monomer represented by the following formula (a-1-m). In the formula, Ia is a monovalent organic group represented by the following formula (pa-1).

In formula (pa-1), A is optionally a group selected from fluorine, chlorine, cyano, an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (this is pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, optionally substituted with one cyano group or one or more halogen atoms) , 5-furanylene, 1,4- or 2,6-naphthylene or phenylene, R ₁ is a single bond, oxygen atom, -COO- or -OCO-, R ₂ is a divalent aromatic group, 2 a valent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ has a carbon number of 1 -40 linear or branched alkyl group or alicyclic group, and D is a monovalent organic group having 3 to 40 carbon atoms, and D is an oxygen atom, a sulfur atom, or -NR _d - (here, R _d represents a hydrogen atom or an alkyl having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents the bonding position with _Sa.

In the above formula (a-1) or (a-1-m), S _a represents a spacer unit, and the bonding group on the left of S _a is bonded to the main chain of the specific polymer, optionally via a spacer. Show that.
S _a can be represented, for example, by the structure of the following formula (Sp).

In the formula (Sp),
The left bond of W ₁ represents the bond to M _b ,
The bond to the right of W ₃ represents the bond to I _a ,
W ₁ , W ₂ and W ₃ each independently represent a single bond, a divalent heterocycle, -(CH ₂ ) _n - (in the formula, n represents 1 to 20), -OCH ₂ -, - Represents CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ - or -C≡C- However, in these substituents, one or more non-adjacent CH ₂ groups are independently -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 Substitution with =CH-, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or a straight or branched alkyl group having 1 to 5 carbon atoms) is possible,
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, chlorine atom, cyano group, methyl group or methoxy group.

In formula (a-1-m), M _a represents a polymerizable group. Examples of the polymerizable group include radically polymerizable groups of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, (meth)acrylamide and its derivatives, and siloxane. can. Preferred are (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and acrylamide.
r is an integer satisfying 1≦r≦3.
M _b is selected from a single bond, a (r+1)-valent heterocycle, a linear or branched alkyl group having 1 to 10 carbon atoms, an (r+1)-valent aromatic group, and an (r+1)-valent alicyclic 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 aromatic group for A ₁ , A _{2 ,} and M _b include aromatic hydrocarbons having 6 to 18 carbon atoms such as benzene, biphenyl, and naphthalene. Examples of the alicyclic group for A ₁ , A ₂ and M _b include alicyclic hydrocarbons having 6 to 12 carbon atoms such as cyclohexane and bicyclohexane. Examples of the heterocycle in A ₁ , A _{2 ,} and M _b include nitrogen-containing heterocycles such as pyridine, piperidine, and piperazine. Examples of the alkyl group for A ₁ and A ₂ include linear or branched alkyl groups having 1 to 10 carbon atoms.

From the viewpoint of achieving good vertical alignment control ability and a stable pretilt angle, the group represented by (pa-1) above is preferably a group represented by (pa-1-a) below. Further, the site may include, but is not limited to, a structure derived from a monomer represented by the following formula (pa-1-ma).

In formula (pa-1-a) or (pa-1-ma), M _a , M _b , and S _a have the same definitions as above.
Further, Z is an oxygen atom or a sulfur atom.
X _a and X _b 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-.
R ₂ is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group.
R ₃ is a single bond, an oxygen atom, -COO- or -OCO-.
R ₄ is a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group having 1 to 40 carbon atoms or an alicyclic 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 from 0 to 3, and b is an integer from 0 to 4.

In formula (pa-1-a) or (pa-1-ma), as the straight chain or branched alkylene group having 1 to 10 carbon atoms in S _a , straight chain or branched alkylene having 1 to 8 carbon atoms; It is preferably a group, 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, or an n-octylene group. .
Examples of the divalent aromatic group of S _a include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetra Examples include fluoro-1,4-phenylene group.

In formula (pa-1-a) or (pa-1-ma), the divalent alicyclic group of S _a is, for example, trans-1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, Examples include silene and the like.
Examples of the divalent heterocyclic group of S _a include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furanylene group, 1,4-piperazine group, 1,4-piperidine group, etc. be able to.
S _a is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

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 include fluoro-1,4-phenylene group and naphthylene group.
Examples of the divalent alicyclic group for R ₂ include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.
Examples of the divalent heterocyclic group for R ₂ include 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furanylene group, 1,4-piperazine group, 1,4-piperidine group, etc. be able to.
R ₂ is preferably a 1,4-phenylene group, trans-1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

Examples of the straight-chain or branched alkyl group having 1 to 40 carbon atoms for R ₄ include straight-chain or branched alkyl groups having 1 to 20 carbon atoms, and some of the hydrogen atoms of this alkyl group Alternatively, all of them may be substituted with fluorine atoms. Examples of such alkyl groups include methyl group, ethyl group, 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-heptafluoro Hexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- Examples include (perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, and 2-(perfluorodecyl)ethyl group.

Examples of the monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group for R ₄ include a cholestenyl group, a cholestanyl group, an adamantyl group, and the following formula (Alc-1) or (Alc-2) (in the formula, R ₇ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms may be substituted with a fluorine atom, and * indicates the bonding position). The groups represented can be mentioned.

Examples of the monomer represented by the above formula (pa-1-ma) include, but are not limited to, structures represented by formulas (paa-1-ma1) to (paa-1-ma18). In the formula, "E" represents the E form, and "t" represents the trans form of the cyclohexyl group.

[Thermal crosslinkable group A and thermally crosslinkable group B]
Thermal crosslinkable group A and thermally crosslinkable group B each independently include a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy site-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a block. An organic group selected from the group consisting of isocyanate groups, which is selected such that thermally crosslinkable group A and thermally crosslinkable group B undergo a crosslinking reaction with heat, provided that thermally crosslinkable group A and thermally crosslinkable group The groups B may be the same.

Combinations of such thermally crosslinkable group A and thermally crosslinkable group B include combinations in which one is a carboxyl group and the other is an epoxy group, oxetanyl group, or thiiranyl group, and combinations in which one is a hydroxy group and the other is a blocked isocyanate group, one is a phenolic hydroxy group and the other is an epoxy group, oxetanyl group, or thiiranyl group, one is a carboxyl group and the other is a blocked isocyanate group, one is an amino group, and the other is a blocked isocyanate group, and both are N-alkoxymethylamide groups. More preferred combinations include a carboxyl group and an epoxy group, a hydroxy group and a blocked isocyanate group, and the like.

In order to introduce such a thermally crosslinkable group A into the polymer serving as component (A), a monomer having a thermally crosslinkable group A may be copolymerized.

In addition, when the liquid crystal aligning agent of the present invention satisfies requirement Z1, when producing the polymer as component (A), both the monomer having a thermally crosslinkable group A and the monomer having a thermally crosslinkable group B are added. Copolymerization is sufficient.

Examples of monomers having a thermally crosslinkable group include:
Acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl) methacrylate A monomer having a carboxyl group such as amide and N-(carboxyphenyl)acrylamide;

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl Methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy) ethyl ester, caprolactone 2-(methacryloyloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5- Monomers having a hydroxy group such as acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone;

Monomers having a phenolic hydroxy group such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide;

Monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate;

N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, etc. ) acrylamide compound;

Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propylacrylate glycidyl, α-n-butyl glycidyl acrylate, 3,4-acrylate Epoxybutyl, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5- Monomers having epoxy moiety-containing groups such as hexene and 1,7-octadiene monoepoxide;

3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl) -2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-acryloyloxyethyl)oxetane, 3-(2-acryloyloxyethyl) )-2-ethyloxetane, 3-(2-acryloyloxyethyl)-3-ethyloxetane, 3-(2-acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloyloxyethyl)-2 -Pentafluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluorooxetane, 3-(2-acryloyloxyethyl)-2, Acrylic acid esters such as 2,4-trifluorooxetane, 3-(2-acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl) )-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyl oxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane, 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl) )-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl) -2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, 3-(2-methacryloyloxy Monomers having an oxetanyl group such as ethyl)-2,2,4,4-tetrafluorooxetane;

2,3-epithiopropyl acrylate or methacrylate, and 2- or 3- or 4-(β-epithiopropylthiomethyl) styrene, 2- or 3- or 4-(β-epithiopropyloxymethyl) styrene, Monomers having a thiiranyl group such as 2- or 3- or 4-(β-epithiopropylthio)styrene, 2- or 3- or 4-(β-epithiopropyloxy)styrene;

2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1'-methyl methacrylate) Examples include monomers having a blocked isocyanate group such as propylideneamino)carboxyamino)ethyl and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate. Note that (meth)acrylamide means both acrylamide and methacrylamide.

In addition, in the present invention, when obtaining a specific copolymer, a monomer having a photoalignable group represented by the above formula (a-1-m) and a thermally crosslinkable group A and, if necessary, a thermally crosslinkable In addition to the monomer having group B, other monomers that can be copolymerized with these monomers can also be used.

Specific examples of such other monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, N-methoxymethyl (meth)acrylamide, N-butoxymethyl Examples include acrylamide compounds such as (meth)acrylamide and acrylamide, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.

Examples of acrylic ester compounds 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. 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- Examples include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, and 2,2,2-trimethacrylate. Fluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl- Examples include 2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

Examples of the (meth)acrylamide compound include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinyl carbazole, allyl glycidyl ether, and 3-ethenyl-7-oxabicyclo[4.1.0]heptane.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The nitrogen-containing aromatic heterocycle has a structure selected from the group consisting of the following formulas [N-a] to [N-b] (wherein Z ₂ is a straight chain or branched alkyl group having 1 to 5 carbon atoms) It is preferable that the aromatic cyclic hydrocarbon contains at least one, preferably one to four.

Specifically, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, quinoline ring, 1-pyrazoline ring, isoquinoline ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazine ring, phenanthroline ring, quinoxaline ring, benzothiazole ring, Examples include an oxadiazole ring and an acridine ring. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom. Among these, for example, a pyridine ring can be mentioned.

Examples of monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth)acrylate, 2 -(4-pyridylcarbonyloxy)ethyl (meth)acrylate, and the like.

The other monomers used in the present invention may be used alone, or two or more monomers may be used in combination.

The photoreactive moiety represented by the above formula (pa-1) contained in the polymer as component (A) of the liquid crystal aligning agent of the present invention may be used alone, or two or more types of moieties may be used. may be used in combination.

The photoreactive site represented by the above formula (pa-1) is contained in a proportion of 5 to 95 mol%, 10 to 60 mol%, or 15 to 50 mol% of the total repeating units of the polymer that is component (A). It is preferable that

As the site having a thermally crosslinkable group to be contained in the polymer of the present invention, thermally crosslinkable group A may be used alone, or two or more types of sites containing thermally crosslinkable group A and thermally crosslinkable group B may be used in combination. It may also be used.
The amount of the site having a thermally crosslinkable group introduced is preferably 5 to 95 mol%, 40 to 90 mol%, or 50 to 85 mol% of the total repeating units of the polymer as component (A).

The content of the structure derived from the other monomers is preferably 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of the total repeating units of the polymer as component (A).

<Method for producing specific polymer>
The specific polymer of component (A) contained in the liquid crystal aligning agent of the present invention is a monomer having a photoalignable group represented by the above formula (pa-1), a monomer having the above thermally crosslinkable group A, , and, if desired, by copolymerizing a monomer having the above thermally crosslinkable group B. Moreover, it can be copolymerized with the other monomers mentioned above.

The method for producing the specific polymer of component (A) in the present invention is not particularly limited, and any industrially used general-purpose method can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using vinyl groups of monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.
As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

A radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) ), alkyl peresters (peroxyneodecanoic acid tert-butyl ester, peroxypivalic acid tert-butyl ester, peroxy 2-ethylcyclohexanoic acid tert-amyl ester, etc.), persulfates (potassium persulfate, (sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.).

Such radical thermal polymerization initiators can be used alone 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 known compounds such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. These compounds may be used alone or in combination of two or more.
The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc. can be used.

The solvent used in the polymerization reaction of the specific polymer of component (A) is not particularly limited as long as it dissolves the produced polymer. Specific examples include the solvents described in the <Solvent> section below, such as N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, and the formula (Sv-1). Examples include the compound represented by the formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethylsulfone, dimethylsulfoxide, and the like.
These solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the produced polymer may be mixed with the above-mentioned solvent and used as long as the produced polymer does not precipitate.
Further, in radical polymerization, oxygen in the solvent becomes a cause of inhibiting the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.

The polymerization temperature during radical polymerization can be selected from any temperature in the range of 30 to 150°C, but is preferably in the range of 50 to 100°C. Further, the reaction can be carried out at any concentration, but the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent can be added.
In the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer will be small, and if it is small, the molecular weight of the obtained polymer will be large. The amount is preferably 0.1 to 10 mol% based on the monomer to be polymerized. Furthermore, various monomer components, solvents, initiators, etc. can be added during polymerization.

[Recovery of polymer]
When recovering produced polymers from the reaction solution obtained by the above-described reaction, the reaction solution may be poured into a poor solvent to precipitate the polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, and the like. The polymer precipitated in a poor solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating. Furthermore, by repeating the procedure of redissolving the precipitated and collected polymer in an organic solvent and re-precipitating and collecting it 2 to 10 times, the amount of impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more types of poor solvents selected from these, since the efficiency of purification will further increase.

The molecular weight of the specific polymer of component (A) is the weight average measured by GPC (Gel Permeation Chromatography) method, considering the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film. The molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

<(B) component>
Component (B) contained in the liquid crystal aligning agent of the present invention is a polymer selected from polyimide and its precursor, and has at least one group selected from a vertical alignment group and a tert-butoxycarbonyl group, or It is a polymer that has been chemically imidized.

The polymer of component (B) is a polyimide and its precursor (hereinafter also referred to as polyimide component), and has a surface energy close to that of the polymer of component (A). Acrylic components such as component (A) basically have low polarity and low surface energy. On the other hand, polyimide components have high polarity and high surface energy. However, if the difference in surface energy between these two components is too large, they will not mix well and agglomeration will occur, resulting in an uneven film, repelling, and unevenness, which will narrow the process margin. Problems such as this may occur. Therefore, by lowering the polarity of the polyimide component, the surface energy can be controlled to a value that is higher than that of the acrylic component but has a small difference. Methods for lowering the polarity of the polyimide component include a method of chemically imidizing it and then mixing it with component (A), and a method of introducing a side chain.

Such polymers include polymers obtained by chemically imidizing a tetracarboxylic acid derivative such as a known tetracarboxylic dianhydride and a known diamine, and a diamine having a side chain. Examples thereof include the resulting polyimide precursor, a polyimide obtained by imidizing the same, a polyimide precursor obtained using a diamine having a tert-butoxycarbonyloxy group, and a polyimide obtained by imidizing the same. Due to such side chains and chemical imidization, the surface energy can be brought close to that of the acrylic polymer, which is component (A), so when a liquid crystal aligning agent is applied and baked to form a cured film, agglomeration etc. This does not occur and a flat cured film can be provided. Examples of diamines having side chains include diamines represented by formulas (2), (3), (4), and (5) described in paragraphs [0023] to [0039] of International Patent Application Publication WO2016/125870; Specific examples include diamines represented by formulas [A-1] to [A-32]. Examples of diamines having a tertiary-butoxycarbonyloxy group include formulas [A-1], [A-2], and [A-3] described in paragraphs [0011] to [0034] of International Patent Application Publication WO2017/119461. Diamines having this structure and specific examples thereof include the diamines exemplified.

The content ratio of the polymer that is the (A) component and the polymer that is the (B) component in the liquid crystal aligning agent of the present invention is such that the mass ratio of the (A) component:(B) component is 5:95 to 95:5. The ratio is preferably 10:90 to 90:10, and even more preferably 20:80 to 60:40.

<(C) component>
When the liquid crystal aligning agent used in the present invention satisfies requirement Z2, it contains a crosslinking agent as the component (C). Component (C) includes a crosslinking agent having two or more thermally crosslinkable groups B.

As the crosslinking agent which is component (C), low molecular weight compounds such as epoxy compounds, compounds having two or more amino groups, methylol compounds, isocyanate compounds, phenoplast compounds, blocked isocyanate compounds, and polymers of N-alkoxymethyl acrylamide are used. , a polymer of a compound having an epoxy group, a polymer of a compound having an isocyanate group, and the like.

Specific examples of the above-mentioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N', N',-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane etc.

Examples of compounds having two or more amino groups include diamines such as alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophorone. Examples include diamine.

Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino Examples include -2-methoxybenzene, 2,5-diamino-p-xylene, and 1,3-diamino-4-chlorobenzene.

Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl) Aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methyl) aminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-( Examples include 6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, and 3-(6-aminonaphthyl)ethylamine.

Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,7-diaminoheptane. , 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane and the like.

Specific examples of methylol compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 , 6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include compounds such as glycoluril compounds (product names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resins (product name: UFR (registered trademark) 65). ), butylated urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Corporation (high condensation type, product name: Beckamine ( Examples include registered trademarks) J-300S, P-955, N), etc.

Specific examples of alkoxymethylated benzoguanamine include, for example, tetramethoxymethylbenzoguanamine. Commercially available products include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, and BL-). 60, BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds (trade name: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark)) manufactured by Mitsui Cytec Co., Ltd. ) 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical (trade name: Nikalak (registered trademark) MW-30, Nikalak MW-22, Nikalak MW-11, Nikalak MS-001, Nikalak MX-002, Nikalak (registered trademark) MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nikalac (registered trademark) MX-45, MX-410, MX-302), and the like.

It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310. Examples of commercial products of the melamine compound include the trade name Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include the trade name Cymel (registered trademark) 1123 (trade name). (manufactured by Mitsui Cytec Co., Ltd.), etc.

Specific examples of isocyanate compounds include VESTANAT B1358/100, VESTAGON BF 1540 (all of the above are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, VESTAGON B-7075 ( Examples include isocyanurate-type modified polyisocyanate (manufactured by Mitsui Chemicals, Inc.).

Specific examples of the phenoplast compound include the following compounds, but the phenoplast compound is not limited to the following compound examples.

Specific examples of the compound having two or more hydroxyalkylamide groups at the end of the molecule include the following compounds, Primid XL-552, and Primid SF-4510.

Examples of the blocked isocyanate compound include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, Examples include B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.).

Furthermore, examples of the above-mentioned polymers of N-alkoxymethyl acrylamide include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide. ) Polymers produced using acrylamide or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as acrylamide.

Specific examples of such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-butoxymethylacrylamide. Examples include a copolymer of -ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, still more preferably 3,000 to 50,000.

Examples of polymers of compounds having epoxy groups include polymers produced using compounds having epoxy groups such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate. It will be done.

Specific examples of such polymers include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), copolymers of glycidyl methacrylate and methyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Examples include copolymers with methyl methacrylate and copolymers with glycidyl methacrylate and styrene. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, still more preferably 3,000 to 50,000.

Examples of polymers of the above-mentioned compounds having isocyanate groups include 2-isocyanatoethyl methacrylate (Karens MOI [registered trademark], manufactured by Showa Denko KK), 2-isocyanatoethyl acrylate (Karens AOI [registered trademark]) , manufactured by Showa Denko K.K.), or 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM [registered trademark], Showa Denko K.K.) ), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.) and other compounds having blocked isocyanate groups. Examples include polymers that can be used.

Specific examples of such polymers include, for example, poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate), 2-isocyanatoethyl Examples include a copolymer of methacrylate and styrene, a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate, and the like. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, still more preferably 3,000 to 50,000.

These crosslinking agents can be used alone or in combination of two or more.

When the liquid crystal aligning agent used in the present invention contains the crosslinking agent (C), the content is preferably 1 part by mass to 100 parts by mass based on 100 parts by mass of the resin (A). , more preferably 1 part by mass to 80 parts by mass.

[Preparation of liquid crystal alignment agent]
The liquid crystal alignment agent used in the present invention is preferably prepared as a coating liquid so that it is suitable for forming a liquid crystal alignment film. That is, the liquid crystal aligning agent of 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 the specific polymer which is the component (A) and the polymer which is the component (B), which have already been explained. At that time, the total content of the specific polymer as component (A) and the content of the polymer as component (B) is preferably 0.5 to 20% by mass, more preferably, based on the entire liquid crystal aligning agent. is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 1 to 10% by weight.

<Solvent>
The solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as it is a solvent that can dissolve component (A), component (B), and optionally component (C). The number of solvents contained in the liquid crystal aligning agent may be one, or a mixture of two or more may be used. Furthermore, the solvent does not have to be a solvent that dissolves the component (A) and the component (B), but can be used in combination with a solvent that dissolves the component (A) and the component (B). In this case, if the surface energy of the solvent that does not dissolve component (A) or (B) is lower than that of the solvent that dissolves component (A) or (B), the coating properties of the liquid crystal aligning agent on the substrate will be improved. This is preferable because it can be done.

Specific examples include water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylcaprolactam. , tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazo Dialkyl imidazolidinones such as lysinone, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, propanol, isopropanol, 3-methyl- Ketones such as 3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone compounds represented by the following formula (Sv-1) and compounds represented by the following formula (Sv-2), 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, Examples include 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, diisopentyl ether, and the like.

In formulas (Sv-1) to (Sv-2), Y ₁ and Y ₂ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X ₁ is an oxygen atom or -COO- , X2 is a single bond or a carbonyl group, and R ₁ is an alkanediyl group having 2 to 4 carbon atoms. n ₁ is an integer from 1 to 3. When n ₁ is 2 or 3, a plurality of R ₁ may be the same or different. Z ₁ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Y ₃ and Y ₄ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

In formula (Sv-1), the monovalent hydrocarbon group having 1 to 6 carbon atoms in Y ₁ and Y ₂ may be, for example, a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples include a monovalent alicyclic hydrocarbon group and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms. The alkanediyl group for R ₁ may be linear or branched.

In formula (Sv-2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms in Z ₁ include alkanediyl groups having 1 to 6 carbon atoms.
The monovalent hydrocarbon group having 1 to 6 carbon atoms for Y ₃ and Y ₄ includes a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, and a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms. and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms.

Specific examples of the solvent represented by formula (Sv-1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether ( butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene Glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, etc.;
Specific examples of the solvent represented by (Sv-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3 -methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and the like.

The solvent preferably has a boiling point of 80 to 200°C. More preferably, the temperature is 80°C to 180°C, and preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, propanol, isopropanol, and 3-methyl-3-methoxy. Butanol, ethyl amyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, diisopentyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol -i-Propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutyl acetate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, Examples include ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, and the like.
It is preferable that the boiling point is in this range, especially when the liquid crystal aligning agent containing the solvent is coated on a plastic substrate to be described later.

<Other ingredients>
The liquid crystal aligning agent used in the present invention may contain components other than the above-mentioned (A) component, (B) component, and, if necessary, the above-mentioned (C) component. Examples of such other components include a crosslinking catalyst, a compound that improves film thickness uniformity and surface smoothness when the liquid crystal alignment agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, etc. Examples include, but are not limited to.

<Crosslinking catalyst>
A crosslinking catalyst may be added to the liquid crystal aligning agent used in the present invention for the purpose of promoting the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. Such crosslinking catalysts include p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m- Xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1- Examples include sulfonic acids such as sulfonic acid and dodecylbenzenesulfonic acid, or hydrates and salts thereof. Examples of compounds that generate acid when heated include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3- Phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate , N-ethyl-p-toluenesulfonamide and the like.

[Compound that improves film thickness uniformity and surface smoothness]
Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorosurfactants, silicone surfactants, and nonionic surfactants.
Specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florado FC430, FC431 ( (manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical), etc. .
The proportion of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, based on 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

[Compound that improves adhesion between liquid crystal alignment film and substrate]
Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane , N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl- 1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxy Examples include amino-based silane-containing compounds such as silane and N-bis(oxyethylene)-3-aminopropyltriethoxysilane.
When using a compound that improves adhesion to the substrate, the amount used is preferably 0.1 parts by mass to 30 parts by mass based on 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 part by mass to 20 parts by mass.

In some embodiments, a photosensitizer can also be used as an additive to improve the photoreactivity of the photoalignable group. Specific examples include aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal aligning agent of the present invention can be applied to a substrate, baked, and then subjected to alignment treatment such as rubbing or light irradiation, or in some vertical alignment applications, can be made into a liquid crystal alignment film without alignment treatment. can. Examples of substrates include glasses such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyether sulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, and polyether ether. Transparent substrates made of plastics such as ketone (PEEK) resin films, polysulfone (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, and triacetyl cellulose can be used.
The transparent conductive film provided on one surface of the substrate includes a NESA film (registered trademark of PPG, Inc., USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. Can be used.

<Coating film formation process>
The method for applying the liquid crystal aligning agent of the present invention is not particularly limited, but includes screen printing, flexo printing, offset printing, inkjet, dip coating, roll coating, slit coating, spin coating, etc., and these may be used depending on the purpose. good. After coating onto a substrate using these methods, the solvent can be evaporated using heating means such as a hot plate to form a coating film.

The baking after applying the liquid crystal aligning agent can be carried out at any temperature from 40 to 300°C, preferably from 40 to 250°C, more preferably from 40 to 230°C.
The thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, more preferably 10 to 500 nm or 10 to 300 nm. This firing can be performed using a hot plate, hot air circulation furnace, infrared furnace, etc.
Rayon cloth, nylon cloth, cotton cloth, etc. can be used for the rubbing treatment.

<Light irradiation process>
In some embodiments, an alignment treatment by light irradiation may be performed, for example, a step of applying the above-mentioned liquid crystal aligning agent onto a substrate to form a coating film, and a step of applying the above-mentioned liquid crystal aligning agent onto a substrate, and a step of forming the coating film in a state where the coating film is not in contact with the liquid crystal layer, or The method may also include a step of irradiating the coating film with light while in contact with a liquid crystal layer.

Examples of the light irradiated in the alignment treatment by light irradiation include ultraviolet rays containing light with a wavelength of 150 to 800 nm, visible light, and the like. Among these, ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The irradiation light may be polarized or non-polarized. As the polarized light, it is preferable to use light containing linearly polarized light.

When the light used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these may be performed. When irradiating non-polarized light, it is preferable to irradiate from a direction oblique to the substrate surface.
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 . preferable.

The liquid crystal display element of the present invention can be manufactured by a conventional method, and the manufacturing method is not particularly limited. It is preferable that the pair of substrates face each other with an appropriate gap therebetween, and that a spacer is disposed between the substrates in order to make the thickness of the liquid crystal sandwiched between the substrates uniform. As this spacer, known spacer materials such as a conventional scattering type spacer and a spacer formed from a photosensitive spacer forming composition can be used, as well as unevenness formed on a layer made of a cured liquid crystal material. It is also possible to use it as a spacer.

<Liquid crystal clamping process>
For constructing a liquid crystal cell by sandwiching a liquid crystal between substrates, there are, for example, the following two methods. The first method is to place a pair of substrates facing each other with a gap (cell gap) in between so that the respective liquid crystal alignment films face each other, and then bond the peripheral parts of the pair of substrates together using a sealant. A method for producing a liquid crystal cell can be mentioned by injecting liquid crystal into a cell gap defined by a suitable sealant and then sealing the injection hole.

As a second method, for example, an ultraviolet light-curable sealing material is applied to a predetermined location on one of the two substrates on which a liquid crystal alignment film is formed, and then a sealing material that is cured by ultraviolet light is applied to several predetermined locations on the surface of the liquid crystal alignment film. After dropping the liquid crystal onto the substrate, the other substrate is attached so that the liquid crystal alignment films face each other, 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 harden the sealant. A method for manufacturing cells (ODF (One Drop Fill) method) can be mentioned.

Examples of liquid crystals include fluorine-based liquid crystals and cyano-based liquid crystals that have positive or negative dielectric anisotropy depending on the application, and liquid crystal compounds or liquid crystal compositions that are polymerized by at least one of heating and light irradiation. (hereinafter also referred to as a polymerizable liquid crystal or a curable liquid crystal composition) may be used.
In an embodiment, the step of forming the coating film of the liquid crystal aligning agent may be performed by a roll-to-roll method. If the roll-to-roll method is used, it becomes possible to simplify the manufacturing process of the liquid crystal display element and reduce the manufacturing cost.
A liquid crystal display element can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

The polarizing plate used on the outside of the liquid crystal cell is either a polarizing plate in which a polarizing film called "H film", which is made by stretching and aligning polyvinyl alcohol and absorbing iodine, is sandwiched between cellulose acetate protective films, or the H film itself. Examples include polarizing plates.
The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention as described above has good liquid crystal alignment, excellent pretilt angle expression ability, and high reliability. Furthermore, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics.

The abbreviations used in the examples are as follows.
<Methacrylic monomer>
(Photoalignable monomer)
“MA1” was synthesized by the synthesis method described in patent document (WO2017/115791).
"MA2" was synthesized by the synthesis method described in patent document (WO2017/115791).

(polar monomer)
MAA: methacrylic acid

(Crosslinkable monomer)
GMA: glycidyl methacrylate

(Isocyanate monomer)
MOI-BP: 2-[(3,5-dimethyl-1-pyrazolyl)carbonylamino]ethyl methacrylate

<Tetracarboxylic dianhydride monomer>
A1: Tetracarboxylic dianhydride represented by the following formula [A1] A2: Tetracarboxylic dianhydride represented by the following formula [A2] A3: Tetracarboxylic dianhydride represented by the following formula [A3] Product A4: Tetracarboxylic dianhydride represented by the following formula [A4] A5: Tetracarboxylic dianhydride represented by the following formula [A5] A6: Tetracarboxylic dianhydride represented by the following formula [A6] Anhydride A7: Tetracarboxylic dianhydride represented by the following formula [A7] A8: Tetracarboxylic dianhydride represented by the following formula [A8]

<Side chain diamine monomer>
B1: Side chain diamine monomer represented by the following formula [B1] B2: Side chain diamine monomer represented by the following formula [B2] B3: Side chain diamine monomer represented by the following formula [B3] B4: The following formula Side chain diamine monomer B5 represented by the following formula [B4]: Side chain diamine monomer B6 represented by the following formula [B6]: Side chain diamine monomer B7 represented by the following formula [B6]: Represented by the following formula [B7] Side chain diamine monomer B8: Side chain diamine monomer represented by the following formula [B8] B9: Side chain diamine monomer represented by the following formula [B9] B10: Side chain diamine monomer represented by the following formula [B10] B11: Side chain diamine monomer represented by the following formula [B11] B12: Side chain diamine monomer represented by the following formula [B12] B13: Side chain diamine monomer represented by the following formula [B13] B14: The following Side chain diamine monomer represented by formula [B14]

<Other diamine monomers>
C1: Other diamine monomers represented by the following formula [C1] C2: Other diamine monomers represented by the following formula [C2] C3: Other diamine monomers represented by the following formula [C3] C4: Other diamine monomers represented by the following formula [C4] Other diamine monomer C5 represented by the following formula [C5]: Other diamine monomer C6 represented by the following formula [C6]: Other diamine monomer C7 represented by the following formula [C7]: Other diamine monomer C8 represented by the following formula [C7]: Other diamine monomers represented by the following formula [C8] C9: Other diamine monomers represented by the following formula [C9] C10: Other diamine monomers represented by the following formula [C10] C11: Represented by the following formula [C11] Other diamine monomers C12: Other diamine monomers represented by the following formula [C12] C13: Other diamine monomers represented by the following formula [C13] C14: Other diamine monomers represented by the following formula [C14] C15: Other diamine monomers represented by the following formula [C14] Other diamine monomers represented by formula [C15] C16: Other diamine monomers represented by formula [C16] below C17: Other diamine monomers represented by formula [C17] below C18: Other diamine monomers represented by formula [C18] below Diamine monomer C19: Other diamine monomers represented by the following formula [C19] C20: Other diamine monomers represented by the following formula [C20]

(Crosslinking agent component)
D-1: Crosslinking agent component represented by the following formula [D1] D-2: Crosslinking agent component represented by the following formula [D2] D-3: Crosslinking agent component represented by the following formula [D3]

In addition, the abbreviations of reagents used in this example are shown below.
(Polymerization initiator)
AIBN: Azobisisobutyronitrile (solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: Tetrahydrofuran DMF: N,N-dimethylformamide

(molecular weight measurement)
The molecular weight of the polymer in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) device (SSC-7200 manufactured by Senshu Kagaku Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd.).
Column temperature: 50°C, eluent: DMF (as additives, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30 mmol/L, THF was 10 ml/L), flow rate: 1.0 ml/min.
Standard samples for creating a calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight approximately 9000,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer Laboratory (molecular weight approximately 12,000, 4 ,000, 1,000).

(Imidization rate measurement)
The imidization rate in the synthesis example was measured as follows. Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard φ5, manufactured by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture), and apply ultrasound. completely dissolved. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring device (JNW-ECA500) manufactured by JEOL Datum. The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and by calculating the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears around 9.5 to 10.0 ppm. It was calculated using the following formula using the integrated value. In the formula below, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated peak value of the standard proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidization rate is 0%). This is the ratio of the number of reference protons to one proton.
Imidization rate (%) = (1-α・x/y)×100

<Methacrylate polymer synthesis example 1>
MA1 (1.65 g, 4.00 mmol) and MAA (1.38 g, 16.00 mmol) were dissolved in NMP (18.1 g), degassed with a diaphragm pump, and then AIBN (0 .16 g, 0.5 mmol) was added, and the mixture was degassed again. Thereafter, the mixture was reacted at 60° C. for 13 hours to obtain a polymer solution.
Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP1).
This polymer had a number average molecular weight of 34,200 and a weight average molecular weight of 116,000.

<Methacrylate polymer synthesis example 2>
MA1 (3.30 g, 8.00 mmol), GMA (0.56 g, 4.00 mmol) and MAA (0.69 g, 8.00 mmol) were dissolved in NMP (26.8 g) and degassed with a diaphragm pump. After that, AIBN (0.16 g, 0.5 mmol) was added as a polymerization initiator, and deaeration was performed again. Thereafter, the mixture was reacted at 60° C. for 13 hours to obtain a polymer solution.
Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP2).
This polymer had a number average molecular weight of 45,000 and a weight average molecular weight of 150,000.

<Methacrylate polymer synthesis example 3>
MA1 (2.48 g, 6.00 mmol) and MOI-BP (3.52 g, 14.00 mmol) were dissolved in NMP (34.9 g), and after degassing with a diaphragm pump, AIBN was added as a polymerization initiator. (0.16 g, 0.5 mmol) was added and degassed again. Thereafter, the mixture was reacted at 60° C. for 13 hours to obtain a polymer solution.
Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP3).
This polymer had a number average molecular weight of 48,000 and a weight average molecular weight of 148,000.

<Polyamic acid polymer synthesis example 4>
B1 (2.28 g, 3.00 mmol), C2 (1.22 g, 4.00 mmol), C7 (1.45 g, 3.00 mmol) and A1 (2.23 g, 6.00 mmol) in NMP (27.2 g) After reacting at 60°C for 5 hours, A2 (1.00g, 2.00mmol) and A4 (0.87g, 2.00mmol) and NMP (9.1g) were added and reacted at 40°C for 10 hours. A polyamic acid polymer solution (MP4) was obtained by reacting for a period of time.

<Polyamic acid polymer synthesis examples 5 to 20>
Polyamic acid polymer solutions MP5 to MP20 were synthesized with the compositions shown in Table 1 using the same method as in Polymer Synthesis Example 1.

<Amic acid polymer synthesis example 21>
C8 (5.17 g, 5.00 mmol) and A4 (2.18 g, 10.00 mmol) were dissolved in NMP (26.6 g) and reacted at 60°C for 5 hours, and then C17 (5.17 g, 5 .00 mmol) and NMP (9.5 g) were added and reacted at 40° C. for 10 hours to obtain a polyamic acid polymer solution (MP21).

<Amic acid polymer synthesis example 22>
C2 (0.61 g, 2.00 mmol), C11 (3.19 g, 8.00 mmol) and A2 (2.50 g, 5.00 mmol) were dissolved in NMP (24.78 g) and reacted at 60°C for 5 hours. After that, A1 (1.96 g, 5.00 mmol) and NMP (8.26 g) were added and reacted at 40° C. for 10 hours to obtain a polyamic acid polymer solution (MP22).

<Polyimide polymer synthesis example 23>
After adding NMP to a polyamic acid polymer solution (MP4) (50 g) and diluting it to 6.5% by mass, acetic anhydride (8.8 g) and pyridine (2.7 g) were added as an imidization catalyst, and 2. The reaction was allowed to proceed for 5 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide polymer powder (E). The imidization rate of this polyimide polymer was 71%, the number average molecular weight was 13,000, and the weight average molecular weight was 42,000.

NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g) and dissolved by stirring at 70° C. for 20 hours. NMP (10.0 g) and BCS (40.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain a polyimide polymer solution (MP23).

<Polyimide polymer synthesis examples 24, 25>
Using the polymer solutions obtained in Polymer Synthesis Examples 21 and 22, polyimide polymer solutions (MP24) and (MP25) were synthesized using the same method as in Polymer Synthesis Example 23.

<Methacrylate polymer synthesis example 26>
MA2 (3.04 g, 6.00 mmol), GMA (0.71 g, 5.00 mmol) and MAA (0.77 g, 9.00 mmol) were dissolved in NMP (18.8 g) and degassed with a diaphragm pump. After that, AIBN (0.16 g, 0.5 mmol) was added as a polymerization initiator, and deaeration was performed again. Thereafter, the mixture was reacted at 60° C. for 13 hours to obtain a polymer solution.
Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP26).
This polymer had a number average molecular weight of 44,000 and a weight average molecular weight of 143,000.

(Example 1)
To the polymer solution (MP2) (3.0 g) obtained in methacrylate polymer synthesis example 2, added the polymer solution (MP4) (7.0 g) obtained in polyimide polymer synthesis example 4, and further added D2 (0.06 g). was added and stirred at room temperature to obtain a liquid crystal aligning agent (PM1).

(Examples 2 to 24)
Using the same method as in Example 1, liquid crystal aligning agents (PM2) to (PM24) were obtained with the compositions shown in Table 2.

(Comparative example 1)
A liquid crystal aligning agent (RPM1) was obtained by adding D1 (0.06 g) to the polymer solution (MP1) (4.0 g) obtained in methacrylate polymer synthesis example 1 and stirring at room temperature.

(Comparative example 2)
A liquid crystal aligning agent (RPM2) was obtained by adding D2 (0.06 g) to the polymer solution (MP1) (4.0 g) obtained in methacrylate polymer synthesis example 1 and stirring at room temperature.

(Comparative example 3)
A liquid crystal aligning agent (RPM3) was obtained by adding D2 (0.06 g) to the polymer solution (MP2) (4.0 g) obtained in methacrylate polymer synthesis example 2 and stirring at room temperature.

(Comparative example 4)
To the polymer solution (MP2) (3.0 g) obtained in methacrylate polymer synthesis example 2, added the polymer solution (MP21) (7.0 g) obtained in amic acid polymer synthesis example 21, and further added D2 (0.06 g). ) was added and stirred at room temperature to obtain a liquid crystal aligning agent (RPM4).

(Comparative example 5)
To the polymer solution (MP2) (3.0 g) obtained in methacrylate polymer synthesis example 2, added the polymer solution (MP22) (7.0 g) obtained in amic acid polymer synthesis example 22, and further added D2 (0.06 g). ) was added and stirred at room temperature to obtain a liquid crystal aligning agent (RPM5).

(Comparative example 6)
A liquid crystal aligning agent (RPM6) was obtained by adding D3 (0.06 g) to the polymer solution (MP26) (4.0 g) obtained in methacrylate polymer synthesis example 26 and stirring at room temperature.

<Production of liquid crystal display element>
The liquid crystal aligning agents (PM1) to (PM22) obtained in the examples and the liquid crystal aligning agents (RPM1) to (RPM5) obtained in the comparative examples were filtered under pressure using a membrane filter with a pore diameter of 1 μm.
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 70°C for 90 seconds, and then baked on a hot plate at 200°C for 30 minutes to form a film with a thickness of 100 nm. A liquid crystal alignment film was formed.
Next, the coating surface was irradiated with 50 mJ/ ^cm2 of linearly polarized ultraviolet rays of 313 nm with an irradiation intensity of 4.3 mW/cm2 from an angle inclined at 40 degrees from the normal direction of the substrate through a polarizing plate to form a substrate with a liquid crystal alignment film ^. I got it. Linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a 313-nm band-pass filter and then passing it through a 313-nm polarizing plate.
Two of the above substrates were prepared, and after 4 μm bead spacers were sprinkled on the liquid crystal alignment film of one substrate, a sealant (XN-1500T, manufactured by Mitsui Chemicals) was applied. Next, the other substrate was bonded together so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 180°, and then the sealant was thermally cured at 120° C. for 90 minutes to prepare an empty cell. A liquid crystal (MLC-3022, manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method to obtain a liquid crystal display element.

<Evaluation of applicability>
The liquid crystal display element obtained above was spin-coated on the ITO electrode surface of a glass substrate with an ITO electrode made of an ITO film, dried on a hot plate at 70° C. for 90 seconds, and the coated surface was observed. The coating properties of the liquid crystal display element were evaluated as "poor" when unevenness or repelling occurred on the coated surface, and as "good" when there was no repelling or unevenness and uniformity. The evaluation results are shown in Table 3.

<Evaluation>
(Liquid crystal orientation)
The liquid crystal display element obtained above was subjected to isotropic phase treatment at 120° C. for 1 hour, and then the cell was observed using a polarizing microscope. A case where there was no alignment defect such as light leakage or domain generation, or a case where uniform liquid crystal driving was obtained when a voltage was applied to the liquid crystal cell was considered good. The evaluation results are shown in Table 4.

(pretilt angle)
The pretilt angle of the liquid crystal cell of the liquid crystal display element produced above was measured by the Mueller matrix method using AxoScan manufactured by Axo Metrix. The evaluation results are shown in Table 4.

(Voltage holding rate (VHR) evaluation)
For VHR evaluation, a voltage of 1V was applied to the liquid crystal cell prepared above for 60μs at a temperature of 60°C, the voltage after 1667ms was measured, and the voltage retention rate was calculated as how long the voltage could be maintained. .
Note that a voltage holding rate measuring device VHR-1 manufactured by Toyo Technica Co., Ltd. was used to measure the voltage holding rate. The evaluation results are shown in Table 4.

(Evaluation of residual DC)
An AC voltage of 6.8 Vpp and a DC voltage of 1 V were applied to the liquid crystal cell prepared above for 48 hours, and the voltage (residual DC) generated within the liquid crystal cell was determined by the flicker elimination method immediately after the DC voltage was removed. This value serves as an index of afterimage characteristics, and a case where this value was ±30 mV or less was considered good. The evaluation results are shown in Table 4.

(Evaluation of tilt angle change)
After measuring the pretilt angle, a DC voltage of 15 V was applied to the liquid crystal cell, and the tilt angle was measured again 36 hours later to calculate how much the tilt angle had changed. The evaluation results are shown in Table 4.

As can be seen from the results in Table 3, from the comparison between Examples 1 to 24 and Comparative Examples 4 and 5, the blend of the polymethacrylate solution and the polyamic acid solution containing no side chain diamine did not have excellent coating properties. A liquid crystal alignment film with excellent coating properties was obtained by blending a polyimide solution containing no side chains, a polyamic acid containing side chains, and a polyimide solution.
In addition, as can be seen from the results in Table 4, from the comparison between Examples 1 to 24 and Comparative Examples 1 to 6, the polymethacrylate solution can be blended with polyamic acid and polyimide solution to improve tilt angle change, VHR, and residual A liquid crystal alignment film with excellent DC was obtained.

The liquid crystal aligning agent of the present invention and a liquid crystal display element using a liquid crystal aligning film obtained from the liquid crystal aligning agent can be suitably used for a liquid crystal display element that requires durability, such as for use in a vehicle.

Claims (7)

(A) The following formula (a-1-m)
(In the formula, Ia is a monovalent organic group represented by the following formula (pa-1),
S _a represents a spacer unit,
M _b is selected from a single bond, a (r+1)-valent heterocycle, a linear or branched alkyl group having 1 to 10 carbon atoms, an (r+1)-valent aromatic group, and an (r+1)-valent alicyclic group. It is the basis of
M _a represents a polymerizable group selected from the group consisting of (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and acrylamide;
r is an integer satisfying 1≦r≦3. )
The following formula (pa-1) derived from the monomer represented by
(In the formula, A is optionally a group selected from fluorine, chlorine, cyano, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (this can optionally be one pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-diyl, which may be substituted with a cyano group or one or more halogen atoms) -furanylene, 1,4- or 2,6-naphthylene, or phenylene, R ₁ is a single bond, oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent aromatic group, It is an alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ has 1 to 40 carbon atoms. is a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group or alicyclic group, and D is an oxygen atom, a sulfur atom, or -NR _d - (where R _d is , represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), X and Y 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, and a is an integer from 0 to 3, and * represents the bonding position.)
A polymer having a photo-alignable group and a thermally crosslinkable group A;
(B) A polymer selected from polyimide and its precursor, which has at least one group selected from a vertical alignment group and a tertiary butoxycarbonyl group, or is chemically imidized. Polymer; and Solvent;
A liquid crystal aligning agent containing,
The liquid crystal aligning agent is
Z1: The (A) polymer further has a thermally crosslinkable group B, and/or Z2: (C) The polymer further contains a compound having two or more thermally crosslinkable groups B in the molecule (thermally crosslinkable Group A and thermally crosslinkable group B each independently include a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, which may be the same or different from each other. , a group selected from the group consisting of a thiiranyl group, an isocyanate group, and a blocked isocyanate group, in which the thermally crosslinkable group A and the thermally crosslinkable group B are selected so as to undergo a crosslinking reaction with heat), liquid crystal alignment. agent.

The liquid crystal aligning agent according to claim 1, wherein the component (B) is a polymer having a vertical alignment group. The liquid crystal aligning agent according to claim 1, wherein the component (B) is a polymer having a tert-butoxycarbonyl group. The liquid crystal aligning agent according to claim 1, wherein component (B) is a chemically imidized polymer. A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of claims 1 to 4. A step of applying the liquid crystal aligning agent according to any one of claims 1 to 4 on a substrate to form a coating film, and a step of forming a coating film in a state where the coating film is not in contact with the liquid crystal layer or with the liquid crystal layer. A method for producing a liquid crystal alignment film, comprising the step of irradiating the coating film with light while in contact with the coating film. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5 or the liquid crystal alignment film obtained by the manufacturing method according to claim 6.