KR20210047864A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment film having a small change in pretilt angle and excellent display reliability even after driving for a long time, high voltage retention characteristics, and capable of reducing charge accumulation, a liquid crystal display element having the same, and a liquid crystal providing the same. Provides an alignment agent. In the present invention, as the component (A), the following formula (pa-1) (in the formula, A represents phenylene, etc., R ₁ is a single bond, an oxygen atom, etc., R ₂ is a divalent aromatic group, etc., and R ₃ is A single bond, an oxygen atom, etc., R ₄ is a C 3 to C 40 monovalent organic group including a C 1 to C 40 linear or branched alkyl group or an alicyclic group, D is an oxygen atom, a sulfur atom or -NR _d -Represents, a is an integer of 0-3, and * represents a bonding position.
The thermally crosslinkable group A and the thermally crosslinkable group B are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B react by heat for crosslinking reaction.) A liquid crystal aligning agent that satisfies at least one of the following requirements Z1 and Z2 is provided, while containing a polymer and a solvent selected from mid and its precursors:
Z1: (A) The polymer which is a component further has a thermal crosslinkable group B.
Z2: As component (C), it further contains a compound having two or more thermally crosslinkable groups B in the molecule.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

The present invention relates to a liquid crystal display device comprising a liquid crystal aligning agent, a liquid crystal aligning film obtained thereby, and a liquid crystal aligning film obtained by the liquid crystal aligning agent. More specifically, it relates to a liquid crystal aligning agent capable of providing a liquid crystal aligning film having good liquid crystal alignment, excellent pretilt angle expression ability, and obtaining high reliability, and a liquid crystal display device having excellent display quality.

In a liquid crystal display device, the liquid crystal alignment layer plays a role of aligning the liquid crystal in a certain direction. Currently, the main liquid crystal aligning film used industrially is a polyimide liquid crystal aligning agent composed of a polyamic acid (also referred to as polyamic acid), a polyamic acid ester, or a solution of polyimide, which is a polyimide precursor, to a substrate. It is manufactured by coating and forming a film.

In addition, when the liquid crystal is aligned in parallel or obliquely aligned with respect to the substrate surface, after film formation, a surface stretching treatment by rubbing is further performed.

On the other hand, in the case of aligning the liquid crystal vertically with respect to the substrate (referred to as a vertical alignment (VA) method), a long chain alkyl, a cyclic group, or a combination of a cyclic group and an alkyl group (see, for example, Patent Document 1), a steroid skeleton ( For example, a liquid crystal alignment film in which a hydrophobic group such as (refer to Patent Document 2) was introduced into the side chain of a polyimide is used. In this case, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in a direction parallel to the substrate, it is necessary to make the liquid crystal molecules tilt from the substrate normal direction toward one direction in the substrate surface. As a means for this, for example, a method of forming a protrusion on a substrate, a method of forming a slit in a display electrode, a method of slightly inclining the liquid crystal molecules from the normal direction of the substrate toward one direction in the surface of the substrate by rubbing (pretilt Method), and furthermore, a method of pretilting a liquid crystal by adding a photopolymerizable compound to the liquid crystal composition in advance, using it with a vertical alignment film such as polyimide, and irradiating ultraviolet rays while applying a voltage to the liquid crystal cell (Example For example, see Patent Document 3) and the like have been proposed.

In recent years, a method of using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays or the like as an alternative to formation of projections and slits in VA system liquid crystal alignment control, and PSA technology (photoalignment method) has also been proposed. That is, it is known that the tilt direction of the liquid crystal molecules at the time of application of voltage can be uniformly controlled by irradiating polarized ultraviolet rays to a polyimide film having a vertical orientation having photoreactivity and giving the ability to regulate the orientation and the expression of the pretilt angle. Yes (refer to Patent Document 4).

VA type liquid crystal display elements are used in TVs and on-vehicle displays because of their features of high contrast and wide viewing angles. In order to obtain high luminance, a liquid crystal display device for TV uses a backlight with a high calorific value, or a liquid crystal display device used for automotive applications, for example, in a car navigation system or a meter panel, when used or left unattended in a high-temperature environment for a long time. There is. Under such severe conditions, when the pretilt angle gradually changes, problems such as initial display characteristics are not obtained or non-uniformity occurs in display. In addition, when the liquid crystal is driven, the voltage retention characteristics and charge accumulation characteristics are also affected by the liquid crystal alignment layer. There is a phenomenon that the screen is burned in.

Japanese Laid-Open Patent Publication No. Hei 3-179323 Japanese Patent Laid-Open Publication No. Hei 4-281427 Japanese Patent Publication No. 4504626 Japanese Patent Publication No. 4995267

The present invention has been made in view of the above circumstances, and the subject is a liquid crystal that has a small change in pretilt angle and excellent display reliability even after driving for a long time, has high voltage retention characteristics, and can reduce charge accumulation. It is in providing an alignment film, a liquid crystal display element having the same, and a liquid crystal aligning agent providing the same.

The inventors of the present invention have found out the invention with the following <X> as a summary.

<X> As a polymer having a photoalignable group represented by the following formula (pa-1) as a component (A) and a thermal crosslinkable group A, as a component (B), a polymer selected from polyimide and a precursor thereof, including a vertically oriented group and tertiary A liquid crystal aligning agent that has at least one group selected from a butoxycarbonyl group, is chemically imidized, or contains a polymer and a solvent that is at least one of, and satisfies at least one of the following requirements Z1 and Z2:

Z1: The polymer which is the component (A) further has a thermal crosslinkable group B.

Z2: As component (C), it further contains a compound having two or more thermally crosslinkable groups B in the molecule.

[Formula 1]

In the formula, A is depending on a group selected from fluorine, chlorine, and cyano as the case may be, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl moiety (this is optionally one cyano group Or substituted with one or more halogen atoms), substituted with pyrimidine-2,5-diyl, pyridin-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4 -Or 2,6-naphthylene or phenylene, R ₁ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group Or a divalent condensed cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a C 1 to C 40 linear or branched alkyl group or an alicyclic group containing 3 to carbon atoms 40 is a monovalent organic group, D represents 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), and a is an integer of 0 to 3 And * represents a bonding position.

The thermally crosslinkable group A and the thermally crosslinkable group B are each independently a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiranyl group, an isocyanate group, and a block isocyanate. As an organic group selected from the group consisting of groups, the thermally crosslinkable group A and the thermally crosslinkable group B are selected to undergo a crosslinking reaction by heat, provided that the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.

According to the present invention, the liquid crystal alignment property is good, the pretilt angle expression ability is excellent, the change in the pretilt angle is small even after driving for a long time, the display reliability is excellent, the voltage retention characteristics are high, and the charge accumulation is reduced. A possible liquid crystal alignment film and a liquid crystal aligning agent can be provided.

Further, the liquid crystal display device manufactured by the method of the present invention has excellent display characteristics.

The liquid crystal aligning agent of the present invention is a polymer selected from a polymer having a photoalignable group represented by the following formula (pa-1) as a component (A) and a thermal crosslinkable group A, and a polyimide and a precursor thereof as a component (B). As a polymer selected from mids and their precursors, the following requirement Z1, having at least one group selected from a vertically aligning group and tertiarybutoxycarbonyl group, chemically imidized, or containing a polymer and a solvent that is at least one of: And a liquid crystal aligning agent satisfying at least one of Z2:

Z1: The polymer which is the component (A) further has a thermal crosslinkable group B.

Z2: As component (C), it further contains a compound having two or more thermally crosslinkable groups B in the molecule.

[Formula 2]

In the formula, A is depending on a group selected from fluorine, chlorine, and cyano as the case may be, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl moiety (this is optionally one cyano group Or substituted with one or more halogen atoms), substituted with pyrimidine-2,5-diyl, pyridin-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4 -Or 2,6-naphthylene or phenylene, R ₁ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group Or a divalent condensed cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a C 1 to C 40 linear or branched alkyl group or an alicyclic group containing 3 to carbon atoms 40 is a monovalent organic group, D represents 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), and a is an integer of 0 to 3 And * represents a bonding position.

The thermally crosslinkable group A and the thermally crosslinkable group B are each independently a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiranyl group, an isocyanate group, and a block isocyanate. As an organic group selected from the group consisting of groups, the thermally crosslinkable group A and the thermally crosslinkable group B are selected to undergo a crosslinking reaction by heat, provided that the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.

Here, ``two or more in a molecule'' means, for example, in the case of containing two or more groups of the same type, such as two or more epoxy groups, in the molecule, for example, a combination of an epoxy group and a thirane group, such as a heterogeneous ( It means to include the case of containing two or more groups in total in the molecule of (異種). "Two or more in a molecule" preferably contains two or more groups of the same kind in a molecule.

Since the polymer which is the component (A) contained in the liquid crystal aligning agent of the present invention has high sensitivity to light, the orientation control ability can be expressed even in polarized ultraviolet irradiation at a low exposure amount.

In addition, when the polymer as the component (A) contains a thermal crosslinkable group A and further contains a thermal crosslinkable group B in the component, even when the sintering time of the liquid crystal aligning agent is short, the polymer as the component (A) is included. Crosslinking reaction becomes possible. Accordingly, when the photo-alignment site exhibits anisotropy by photoreaction, since anisotropy remains (memory) in the liquid crystal alignment film easily, it becomes possible to increase the liquid crystal alignment and further express the pretilt angle of the liquid crystal.

Moreover, the liquid crystal aligning agent of this invention can aim at the improvement of electrical characteristics, such as improvement of voltage retention and suppression of residual charge accumulation, by containing the polymer which is (B) component.

In addition, since the photoalignable group, the thermal crosslinkable group A, and the thermal crosslinkable group B represented by the above formula (pa-1) can all be side chains in the polymer, they are changed to ``side chains'' if necessary. I can say.

Hereinafter, each constitutional requirement of the present invention will be described in detail.

<(A) component: Specific polymer>

[Photo-aligning group represented by formula (pa-1)]

In the present invention, the moiety in the molecule having photoalignment represented by the above formula (pa-1) can be represented by, for example, the following formula (a-1). Moreover, although the structure derived from a monomer represented by the following formula (a-1-m) is mentioned as the site|part, it is not limited to this. In the formula, Ia is a monovalent organic group represented by the following formula (pa-1).

[Formula 3]

In the formula (pa-1), A is optionally according to a group selected from fluorine, chlorine, and cyano, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (this is Thus substituted with one cyano group or one or more halogen atoms), substituted with pyrimidine-2,5-diyl, pyridin-2,5-diyl, 2,5-thiophenylene, 2,5-fura Represents nylene, 1,4- or 2,6-naphthylene or phenylene, R ₁ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group, Is a divalent heterocyclic group or a divalent condensed cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a linear or branched alkyl group or alicyclic group having 1 to 40 carbon atoms Is a monovalent organic group containing 3 to 40 carbon atoms, D represents 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), and a represents It is an integer of 0-3, and * represents the bonding position with _{S a.}

In the formula (a-1) or (a-1-m), S _a represents a spacer unit, and _{the linking group on the left side of S a} represents that the main chain of a specific polymer is optionally bonded via a spacer. .

S _a can be represented by the structure of the following formula (Sp), for example.

[Formula 4]

In formula (Sp),

The bond on the left side of W ₁ represents the bond to _{M b,}

The bond on the right side of W ₃ represents the bond to _{I a,}

W ₁ , W ₂ and W ₃ are each independently a single bond, a divalent heterocycle, -(CH ₂ ) _n- (wherein n represents 1 to 20), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF _{2 O-, -OCF 2} -, -CF ₂ CF ₂ -or -C≡C-, In these substituents, at least one of the non-adjacent CH ₂ groups is independently -O-, -CO-, -CO-O-, -O-CO-, -Si(CH ₃ ) ₂ -O-Si( CH ₃ ) ₂ -NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- ( In the formula, R may independently be substituted with hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms),

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, and each group is unsubstituted or one or more The hydrogen atom may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

In formula (a-1-m), M _a represents a polymerizable group. As the polymerizable group, radical polymerizable groups of (meth)acrylate, fumarate, maleate, α-methylene-γ butyrolactone, styrene, vinyl, maleimide, norbornene, (meth)acrylamide and derivatives thereof, And siloxane. Preferably, they are (meth)acrylate, α-methylene-γ butyrolactone, styrene, vinyl, maleimide, and acrylamide.

r is an integer satisfying 1≦r≦3.

M _b is a group selected from a single bond, a (r+1) valent heterocycle, a C1-C10 linear or branched alkyl group, a (r+1) valent aromatic group, and a (r+1) valent alicyclic group, and each group is non- It may be substituted, 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.

As _{the aromatic group for A 1} , A ₂ , and M _b , for example, an aromatic hydrocarbon having 6 to 18 carbon atoms such as benzene, biphenyl, and naphthalene can be mentioned. As _{the alicyclic group in A 1} , A ₂ , and M _b , for example, alicyclic hydrocarbons having 6 to 12 carbon atoms such as cyclohexane and bicyclohexane are mentioned. Examples of the heterocycle in A ₁ , A ₂ , and M _b include nitrogen-containing hetero rings such as pyridine, piperidine, and piperazine. Examples of the alkyl group for A ₁ and A ₂ include a linear or branched alkyl group having 1 to 10 carbon atoms.

From the viewpoint of being able to express a good vertical orientation control ability and a stable pretilt angle, the group represented by the above (pa-1) is preferably a group represented by the following (pa-1-a). Moreover, although the structure derived from the monomer represented by the following formula (pa-1-ma) is mentioned as the site|part, it is not limited to this.

[Formula 5]

In formula (pa-1-a) or (pa-1-ma), M _a , M _b , and S _a are the same definitions as described above.

In addition, 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 C 3 to C 40 monovalent organic group including a C 1 to C 40 linear or branched alkyl group or an alicyclic group.

R ₅ is a C 1 to C 3 alkyl group, a C 1 to C 3 alkoxy group, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom.

a is an integer of 0-3, and b is an integer of 0-4.

In formula (pa-1-a) or (pa-1-ma), S _a is a linear or branched alkylene group having 1 to 10 carbon atoms, which is a linear or branched alkylene group having 1 to 8 carbon atoms. It is preferable and, for example, methylene group, ethylene group, n-propylene group, n-butylene group, t-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group are preferable. Do.

As the divalent aromatic group of S _a , for example, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6 -A tetrafluoro-1,4-phenylene group, etc. are mentioned.

In formula (pa-1-a) or (pa-1-ma), _{as a divalent alicyclic group of S a} , for example, trans-1,4-cyclohexylene, trans-trans-1,4-bicyclo Hexylene, etc. are mentioned.

As the _{divalent heterocyclic group of S a} , for example, 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furanylene group, 1,4-piperazine group, 1,4-p Peridingi, etc. are mentioned.

S _a is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms.

As the divalent aromatic group of R ₂ , for example, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6 -A tetrafluoro-1,4-phenylene group, a naphthylene group, etc. are mentioned.

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

As the _{divalent heterocyclic group of R 2} , for example, 1,4-pyridylene group, 2,5-pyridylene group, 1,4-furanylene group, 1,4-piperazine group, 1,4-pi Peridingi, etc. are mentioned.

R ₂ is preferably a 1,4-phenylene group, trans1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

As _{a C1-C40 linear or branched alkyl group of R 4} , for example, a C1-C20 linear or branched alkyl group may be exemplified, and some or all of the hydrogen atoms of this alkyl group are fluorine atoms. You may be substituted by. Examples of such an alkyl group include, for example, methyl group, ethyl group, n-propyl group, 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 group, 4,4,5, 5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3 ,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, 2-(perfluorodecyl)ethyl group, and the like.

As _{a C3-C40 monovalent organic group containing an alicyclic group of R 4} , for example, a cholesteryl group, a cholestanyl group, an adamantyl group, 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, respectively, the alkyl group having 1 to 20 carbon atoms may be substituted with a fluorine atom, and * represents a bonding position). .

[Formula 6]

Examples of the monomer represented by the above formula (pa-1-ma) include structures represented by the formulas (paa-1-ma1) to (paa-1-ma18), but are not limited thereto. In addition, in the formula, "E" represents an E chain, and "t" represents that a cyclohexyl group is trans-type.

[Formula 7]

[Formula 8]

[Thermal crosslinking machine A and the thermal crosslinking machine B]

The thermally crosslinkable group A and the thermally crosslinkable group B are each independently a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiranyl group, an isocyanate group, and a block isocyanate. As an organic group selected from the group consisting of groups, the thermally crosslinkable group A and the thermally crosslinkable group B are selected to undergo a crosslinking reaction by heat, provided that the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.

As such a combination of the thermally crosslinkable group A and the thermally crosslinkable group B, one is a carboxyl group, the other is an epoxy group, an oxetanyl group, or a thiranyl group, a combination wherein one is a hydroxy group, and the other is a block isocyanate group, A combination in which one is a phenolic hydroxy group, the other is an epoxy group, an oxetanyl group, or a thiranyl group, a combination in which one is a carboxyl group and the other is a block isocyanate group, a combination in which one is an amino group, and the other is a block isocyanate group, both together And combinations that are N-alkoxymethylamides. A more preferable combination is a carboxyl group and an epoxy group, a hydroxy group and a block isocyanate group.

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

Moreover, when the liquid crystal aligning agent of this invention satisfies the requirement Z1, when manufacturing the polymer which is (A) component, it is just necessary to copolymerize both the monomer which has a thermally crosslinkable group A and the monomer which has a thermally crosslinkable group B.

As a monomer having a thermally crosslinkable group, for example,

Acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N Monomers having a carboxyl group such as -(carboxyphenyl)methacrylamide 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-acryloyloxy-6-hydroxynorbor Monomers having a hydroxyl group such as ene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone;

Phenolic hydrodes such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide A monomer having a oxy group;

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

Hydroxymethyl group or alkoxy such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide (Meth)acrylamide compound substituted with a methyl group;

Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, α-ethylglycidyl acrylate, α-n-propyl glycidyl acrylate, α-n- Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylic acid, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic acid-6,7 -Epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexylmethyl, 3-ethenyl-7- Monomers having an epoxy moiety-containing group such as oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide;

3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyl Oxymethyl)-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-penta Fluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluorooxetane, 3-(2 Acrylic acid esters such as -acryloyloxyethyl)-2,2,4-trifluorooxetane and 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- (Methacryloyloxymethyl)-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-methacryloyloxyethyl)- Monomers having an oxetanyl group such as 2,2,4,4-tetrafluorooxetane;

2,3-epithiopropylacrylate or methacrylate, and 2- or 3- or 4-(β-epithiopropylthiomethyl)styrene, 2- or 3- or 4-(β-epithiopropyloxymethyl ) A monomer having a thiranyl group such as styrene, 2- or 3- or 4-(β-epithiopropylthio) styrene, and 2- or 3- or 4-(β-epithiopropyloxy) styrene;

Acrylic acid 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl, acrylic acid 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl, methacrylic acid 2-(0-(1'-) Monomers having a block isocyanate group such as methylpropylideneamino)carboxyamino)ethyl and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate; And the like. In addition, (meth)acrylamide means both acrylamide and methacrylamide.

In addition, in the present invention, when obtaining a specific copolymer, in addition to the monomer having a photoalignable group represented by the formula (a-1-m) and a monomer having a thermal crosslinkable group A and optionally a thermal crosslinkable group B, these monomers Other monomers that can be copolymerized with may be used in combination.

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

As an acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 ,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecylacrylic Rate, and 8-ethyl-8-tricyclodecylacrylate, etc. are mentioned.

As a methacrylic acid ester compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate , Anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate Acrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl -2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate And the like.

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

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

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 at least one structure selected from the group consisting of the following formulas [Na] to [Nb] (in the formula, Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms), preferably It is preferable that it is an aromatic cyclic hydrocarbon containing 1-4 pieces.

[Formula 9]

Specifically, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, quinoline ring, 1-pyrazoline ring, isoquinoline ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazine ring, phenanthrol And a lean ring, a quinoxaline ring, a benzothiazole ring, an oxadiazole ring, an acridine ring, and the like. Further, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a hetero atom. Among these, a pyridine ring is mentioned, for example.

As a monomer having a nitrogen-containing aromatic heterocyclic group and a polymerizable group, for example, 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth) Acrylate, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, and the like.

Other monomers used in the present invention may be used singly or in combination of two or more kinds of monomers.

The photoreactive moiety represented by the formula (pa-1) to be contained in the polymer which is the component (A) of the liquid crystal aligning agent of the present invention may be used singly or in combination of two or more moieties.

The photoreactive moiety represented by the above formula (pa-1) is contained in a ratio of 5 to 95 mol%, 10 to 60 mol%, or 15 to 50 mol% of all repeating units of the polymer as component (A). desirable.

As the moiety having a thermal crosslinkable group to be contained in the polymer of the present invention, the thermal crosslinkable group A may be used alone, or two or more types of moieties including the thermal crosslinkable group A and the thermal crosslinkable group B may be used in combination.

It is preferable that the introduction amount of the moiety having a thermally crosslinkable group is 5 to 95 mol%, 40 to 90 mol%, or 50 to 85 mol% of all repeating units of the polymer which is the component (A).

It is preferable that content of the structure derived from the said other monomer contains 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of all repeating units of the polymer which is a component (A).

<Method for producing a 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 thermal crosslinkable group A, and, if desired, the above It is obtained by copolymerizing a monomer having a thermally crosslinkable group B of. In addition, it can be copolymerized with the above other monomers.

The method for producing the specific polymer of the component (A) in the present invention is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a monomer. Among these, radical polymerization is particularly preferred from the viewpoint of easiness of reaction control and the like.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides. (Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxy ketals (dibutyl Peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), and Sulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.) Can be lifted.

Such radical thermal polymerization initiators may 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 irradiation with light. 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 an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, and the like can be used.

The solvent used in the polymerization reaction of the specific polymer of the component (A) is not particularly limited as long as the resulting polymer is dissolved. As a specific example, the solvent described in the item of <solvent> mentioned later, for example, N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, formula (Sv- The compound represented by 1) and the compound represented by formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, dimethyl sulfoxide, etc. are mentioned.

These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve the produced|generated polymer, you may mix and use with the above-mentioned solvent within the range which the produced|generated polymer does not precipitate.

Further, in radical polymerization, since oxygen in the solvent becomes a cause of inhibiting the polymerization reaction, it is preferable to use the organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from an arbitrary temperature of 30 to 150°C, but is preferably in the range of 50 to 100°C. Moreover, although the reaction can be carried out at an arbitrary concentration, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. It is carried out at a high concentration at the beginning of the reaction, and after that, an organic solvent can be added.

In the above-described radical polymerization reaction, if the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer decreases, and if the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer increases. Therefore, the ratio of the radical initiator is 0.1 to 10 with respect to the monomer to be polymerized. It is preferable that it is mol%. In addition, at the time of polymerization, various monomer components, solvents, initiators, etc. can also be added.

[Recovery of Polymer]

In the case of recovering the produced polymer from the reaction solution obtained by the above-described reaction, the reaction solution may be added to a poor solvent to precipitate these polymers. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer injected into the poor solvent and precipitated can be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, if the polymer recovered by precipitation is re-dissolved in an organic solvent and the operation of reprecipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more poor solvents selected from among them is preferable because the efficiency of purification is further increased.

The molecular weight of the specific polymer of component (A) is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film are considered. This is preferable, and more preferably, it is 5000 to 100000.

<(B) component>

The 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 aligning group and a tertiarybutoxycarbonyl group, or is chemically imidized. It is a polymer which is at least one of them.

The polymer of the component (B) is a polyimide and a precursor thereof (hereinafter, also referred to as a polyimide component), and is a component having a surface energy close to that of the polymer as the component (A). Acrylic components such as component (A) basically have low polarity and low surface energy. On the other hand, the polyimide component has high polarity and high surface energy. However, if the difference between the surface energy of the two components is too large, there is a concern that the process margin is narrowed due to the formation of a film with irregularities due to the occurrence of coagulation due to poor compatibility, or the occurrence of cratering or non-uniformity. . Therefore, by lowering the polarity of the polyimide component, the surface energy is higher than that of the acrylic component, but the difference can be controlled to a small value. As a method of lowering the polarity of the polyimide component, there is a method of mixing with the component (A) after chemical imidization, or a method of introducing a side chain.

As such a polymer, a polymer obtained by polymerizing a known tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a known diamine, followed by chemical imidization, a polyimide precursor obtained using a diamine having a side chain, and A polyimide obtained by imidization, a polyimide precursor obtained using a diamine having a tertiarybutoxycarbonyloxy group, and a polyimide obtained by imidizing it may be mentioned. Since the surface energy can be brought close to the acrylic polymer as the component (A) by such side chain or chemical imidization, when a cured film is formed by applying and firing a liquid crystal aligning agent, no aggregation or the like occurs, and flat curing You can give it a film. As the diamine having a side chain, the diamine represented by formulas (2), (3), (4) and (5) described in paragraphs [0023] to [0039] of WO2016/125870, and specific examples thereof The diamine represented by formula [A-1]-[A-32] is mentioned. As the diamine having a tertiarybutoxycarbonyloxy group, the formulas [A-1], [A-2], and [A-3] described in paragraphs [0011] to [0034] of WO2017/119461 The diamine having a structure and the diamine exemplified as a specific example thereof can be mentioned.

The content ratio of the polymer as the component (A) and the polymer as the component (B) in the liquid crystal aligning agent of the present invention is preferably a mass ratio of the component (A): the component (B) from 5:95 to 95:5, And 10:90 to 90:10 are more preferable, and 20:80 to 60:40 are still more preferable.

<(C) component>

When the liquid crystal aligning agent used for this invention satisfies the requirement Z2, it contains a crosslinking agent as (C) component. As (C) component, a crosslinking agent which has two or more thermal crosslinkable groups B is mentioned.

Examples of the crosslinking agent as component (C) include an epoxy compound, a compound having two or more amino groups, a methylol compound, an isocyanate compound, a phenoplast compound, a low molecular weight compound such as a block isocyanate compound, a polymer of N-alkoxymethylacrylamide, and an epoxy group. And polymers such as polymers of compounds having an isocyanate group and polymers of compounds having an isocyanate group.

As specific examples of the above-described epoxy compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglyci Dyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 ,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-di Glycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

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

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3' -Dimethyldicyclohexylamine, isophoronediamine, etc. are mentioned.

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

Examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-amino Phenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3 -Methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4 -(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl) Aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, etc. Can be mentioned.

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

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

Specific examples of the alkoxymethylated glycoluril include, for example, 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)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl) )-4,5-dimethoxy-2-imidazolinone, etc. are mentioned. As a commercial product, Mitsui Cytec Co., Ltd. manufactured glycoluril compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), and other compounds, methylated urea resin (trade name: UFR (registered trademark) 65), butyl Huaurea resin (brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. urea/formaldehyde resin (high condensation type, brand name: Beccamin (registered trademark)) J-300S, same P-955, same N), etc. are mentioned.

As a specific example of alkoxymethylated benzoguanamine, tetramethoxymethylbenzoguanamine etc. are mentioned, for example. As a commercial product, manufactured by Mitsui Cytec Co., Ltd. (brand name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (brand name: Nikarak (registered trademark) BX-4000, BX-37, BL-60, BX-55H), etc. are mentioned.

As a specific example of an alkoxymethylated melamine, hexamethoxymethylmelamine etc. are mentioned, for example. As a commercial product, Mitsui Cytec Co., Ltd. methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, copper 301, copper 303, copper 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) ) 506, copper 508), Sanwa Chemical methoxymethyl type melamine compound (trade name: Nikarak (registered trademark) MW-30, copper MW-22, copper MW-11, copper MS-001, copper MX-002, copper MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nikarak (registered trademark) MX-45, MX-410, MX-302), and the like.

Further, a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group may be used. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in US Patent Publication No. 623310 may be mentioned. As a commercial product of the melamine compound, a brand name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.) may be mentioned, and as a commercial product of the benzoguanamine compound, a brand name: Cymel (registered trademark) 1123 (Mitsui Cytec Co., Ltd. product), etc. are mentioned.

Specific examples of the isocyanate compound include, for example, VESTANAT B1358/100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degusa Japan Co., Ltd.), Takenate (registered trademark) B-882N. , Copper B-7075 (above, isocyanurate-type modified polyisocyanate, manufactured by Mitsui Chemical Co., Ltd.), etc. are mentioned.

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

[Formula 10]

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

[Formula 11]

As a block isocyanate compound, for example, Collonate AP stable M, Collonate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemical Co., Ltd.), etc. are mentioned.

In addition, as the polymer of the N-alkoxymethylacrylamide described above, for example, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, and N-ethoxymethyl (meth) And polymers prepared using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or alkoxymethyl group such as acrylamide and N-butoxymethyl (meth)acrylamide.

Specific examples of such a polymer include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, and of N-hydroxymethylmethacrylamide and methylmethacrylate. Copolymers, copolymers of N-ethoxymethyl methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide and 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, and still more preferably 3,000 to 50,000.

As the polymer of the compound having an epoxy group, for example, a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate And polymers produced by using.

Specific examples of such a polymer include, for example, poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), glycidyl methacrylate and methyl methacrylate. Coalescence, a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, a copolymer of glycidyl methacrylate and styrene, 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, and still more preferably 3,000 to 50,000.

As the polymer of the compound having an isocyanate group described above, for example, 2-isocyanatoethyl methacrylate (Carenz MOI [registered trademark], manufactured by Showa Electric Co., Ltd.), 2-isocyanatoethylacrylic A compound having an isocyanate group, such as a rate (Carenz AOI [registered trademark], manufactured by Showa Electric Co., Ltd.), or 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Carenz MOI-BM [registered trademark], manufactured by Showa Electric Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Carenz MOI-BP [registered trademark], Showa Polymers produced using compounds having a block isocyanate group, such as (manufactured by Major Co., Ltd.) can be mentioned.

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

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

In the case where the crosslinking agent of the component (C) is contained in the liquid crystal aligning agent used in the present invention, the content is preferably 1 part by mass to 100 parts by mass based on 100 parts by mass of the resin as the component (A), more preferably Is from 1 part by mass to 80 parts by mass.

[Preparation of liquid crystal aligning agent]

It is preferable that the liquid crystal aligning agent used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. In other words, it is preferable that the liquid crystal aligning agent of the present invention is prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a specific polymer that is a component (A) and a polymer that is a component (B) described above. In that case, the sum of the content of the specific polymer in the component (A) and the content of the polymer as the component (B) is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, with respect to the entire liquid crystal aligning agent. It is more preferably 1 to 15% by mass, particularly preferably 1 to 10% by mass.

<Solvent>

The solvent contained in the liquid crystal aligning agent used for this invention is not specifically limited if it is a solvent which melt|dissolves the component (A), the component (B), and the component (C) which has if necessary. 1 type may be sufficient as the solvent contained in a liquid crystal aligning agent, and may mix and use 2 or more types. Moreover, even if it is not a solvent which dissolves (A) component or (B) component, it can use together with a solvent which dissolves (A) component or (B) component. In this case, if the surface energy of the solvent that does not dissolve the component (A) or the component (B) is lower than the solvent dissolving the component (A) or the component (B), the coating property of the liquid crystal aligning agent to the substrate is satisfactory. It is desirable because it can be done.

As specific examples, N-alkyl-2-pyrrolidones such as water, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethyl Acetamide, N-methylcaprolactam, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropane Dialkylimidazolidinones such as amide and 1,3-dimethyl-2-imidazolidinone, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, ethylene carbonate, propylene Carbonates such as carbonate, methanol, ethanol, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamylmethyl ketone, methyl isopropyl ketone, diisobutyl ketone , Ketones such as cyclohexanone, cyclopentanone, methyl isobutyl ketone, and 4-hydroxy-4-methyl-2-pentanone, a compound represented by the following formula (Sv-1), and the following formula (Sv-2) The represented compound, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutylcarbinol, di Isopentyl ether and the like.

[Formula 12]

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, X ₁ is an oxygen atom or -COO-, and X ₂ 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 of 1-3. When n ₁ is 2 or 3, a plurality of R ₁ may be the same or different. Z ₁ is a C 1 to C 6 divalent hydrocarbon group, and Y ₃ and Y ₄ are each independently a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group).

In formula (Sv-1), as _{a C 1 to C 6 monovalent hydrocarbon group of Y 1} and Y ₂ , for example, a C 1 to C 6 monovalent chain hydrocarbon group or a C 1 to C 6 monovalent alicyclic hydrocarbon Group and a C1-C6 monovalent aromatic hydrocarbon group, etc. are mentioned. As a C1-C6 monovalent chain hydrocarbon group, a C1-C6 alkyl group etc. are mentioned. The _{alkanediyl group of R 1} may be linear or branched.

In formula (Sv-2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms of _{Z 1 include an alkanediyl group having 1 to 6 carbon atoms.}

As _{the C1-C6 monovalent hydrocarbon group of Y 3} and Y ₄ , a C1-C6 monovalent chain hydrocarbon group, a C1-C6 monovalent alicyclic hydrocarbon group, and a C1-C6 monovalent aromatic hydrocarbon And the like. As a C1-C6 monovalent chain hydrocarbon group, a C1-C6 alkyl group etc. are mentioned.

Specific examples of the solvent represented by formula (Sv-1) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, and 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 mono Butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, and the like;

As a specific example of the solvent represented by (Sv-2), for example, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, Methyl-3-methoxypropionate, 3-methoxy ethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxypropionate butyl, and the like, respectively.

It is preferable that the solvent has a boiling point of 80 to 200°C. More preferably, it is 80 degreeC to 180 degreeC, and as a preferable solvent, N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, propanol, isopropanol, 3-methyl-3 -Methoxybutanol, ethyl amyl ketone, methyl ethyl ketone, isoamylmethyl 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, diisobutylcarbinol, 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, ethyl-3-ethoxypropionate, methyl-3 -Methoxy propionate, 3-methoxy ethyl propionate, etc. are mentioned.

It is particularly preferable that the boiling point is in this range when the liquid crystal aligning agent containing the solvent is applied onto a plastic substrate described later.

<Other ingredients>

The liquid crystal aligning agent used for this invention may contain components other than the said (A) component, the (B) component, and the said (C) component which it has as needed. Examples of such other components include a crosslinking catalyst, a compound that improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal aligning film and the substrate, and the like. It is 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 accelerating the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. As such a crosslinking catalyst, 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-sulfonic acid, And sulfonic acids such as dodecylbenzenesulfonic acid, or hydrates and salts thereof. As a compound that generates an acid by heat, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 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-toluene sulfonic acid isobutyl ester, p-toluene sulfonic acid methyl ester, p-toluene sulfonic acid phenethyl ester, cyanomethyl p-toluene sulfonate, 2,2,2-trifluoroethyl p-toluene sulfonate, 2 -Hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, etc. are mentioned.

[Compound to improve the uniformity of film thickness or surface smoothness]

As a compound which improves the uniformity of film thickness and surface smoothness, a fluorine type surfactant, a silicone type surfactant, a nonion type surfactant, etc. are mentioned.

Specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapac (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (Manufactured by Sumitomo 3M), Asahigard (registered trademark) AG710 (manufactured by Asahi Glass Corporation), Suflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) And the like.

The ratio of these surfactants to be 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 per 100 parts by mass of the resin component contained in the polymer composition.

[Compound to improve adhesion between liquid crystal alignment film and substrate]

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the functional silane-containing compound etc. shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 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-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri And amino-based silane-containing compounds such as ethoxysilane.

When a compound that improves adhesion to a substrate is used, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass per 100 parts by mass of the resin component contained in the polymer composition. It's wealth.

In certain embodiments, a photosensitizer may be used as an additive in order to improve the photoreactivity of the photoalignable group. As a specific example, aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal, etc. are mentioned.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal aligning agent of the present invention can be applied onto a substrate and fired, and then subjected to alignment treatment by rubbing treatment, light irradiation, or the like, or can be used as a liquid crystal alignment film without alignment treatment in some vertical alignment applications. Examples of the substrate include glass such as float glass and soda glass; Polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyethersulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resin film, polysulfone Transparent substrates made of plastics such as (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, and triacetylcellulose can be used.

As a transparent conductive film formed on one side of the substrate, a _{NESA film made of tin oxide (SnO 2} ) (registered trademark of PPG, USA), 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 of applying the liquid crystal aligning agent of the present invention is not particularly limited, and there are screen printing, flexo printing, offset printing, inkjet, dip coating, roll coating, slit coating, spin coating, and the like, and may be used depending on the purpose. After coating on a substrate by these methods, the solvent can be evaporated by heating means such as a hot plate to form a coating film.

The firing after applying the liquid crystal aligning agent can be carried out at an arbitrary temperature of 40 to 300°C, preferably 40°C to 250°C, and more preferably 40°C to 230°C.

The film 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 by a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

For the rubbing treatment, rayon cloth, nylon cloth, cotton cloth, or the like can be used.

<light irradiation process>

In any embodiment, alignment treatment by light irradiation may be performed, for example, a step of forming a coating film by applying the liquid crystal aligning agent on a substrate, and in a state in which the coating film is not in contact with the liquid crystal layer or liquid crystal You may include a step of irradiating light to the coating film in a state in contact with the layer.

As the light to be irradiated in the alignment treatment by light irradiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be exemplified. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. The irradiated light may be polarized or non-polarized. As polarized light, it is preferable to use light containing linearly polarized light.

When the light to be used is polarized light, the irradiation of light may be performed in a direction perpendicular to the substrate surface, may be performed in an oblique direction, or a combination thereof may be performed. In the case of irradiating non-polarization, it is preferable to perform it in a direction oblique to the substrate surface.

The irradiation amount of light 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 still more preferably 2 to 200 mJ/cm 2.

The liquid crystal display device of the present invention can be manufactured by a conventional method, and the manufacturing method is not particularly limited. It is preferable to arrange a spacer between the substrates for the purpose of making the pair of substrates face each other via an appropriate gap, and to make the thickness of the liquid crystal sandwiched between the substrates uniform. As this spacer, a known spacer material such as a conventional scattered spacer and a spacer formed from a photosensitive spacer-forming composition can be used, and as a spacer, irregularities formed on a layer made of a liquid crystal cured product can be used as spacers. It is possible.

<liquid crystal holding process>

In order to configure a liquid crystal cell by sandwiching a liquid crystal between substrates, for example, the following two methods are mentioned. As a first method, a pair of substrates are opposed to each other through a gap (cell gap) so that each liquid crystal aligning film faces, and the periphery of the pair of substrates is bonded using a sealing agent, and the substrate surface And a method of manufacturing a liquid crystal cell by filling and injecting liquid crystal into the cell gap partitioned by an appropriate sealing agent, and then sealing the injection hole.

As a second method, for example, an ultraviolet light-curable sealing material was applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film was formed, and liquid crystal was dripped at several predetermined locations on the surface of the liquid crystal alignment film. Thereafter, a method of manufacturing a liquid crystal cell by bonding the other substrate so that the liquid crystal aligning film is opposed to each other, expanding the liquid crystal to the entire surface of the substrate, and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate (ODF ( One Drop Fill) method).

As a liquid crystal, a fluorine-based liquid crystal or cyano-based liquid crystal having positive or negative dielectric anisotropy depending on the application, and a liquid crystal compound or liquid crystal composition that is polymerized by at least one treatment during heating and light irradiation (hereinafter , Also referred to as a polymerizable liquid crystal or curable liquid crystal composition) may be used.

In any embodiment, the step of forming the coating film of the liquid crystal aligning agent may be performed by a roll-to-roll method. When implemented by a roll-to-roll system, it becomes possible to simplify the manufacturing process of a liquid crystal display element and reduce manufacturing cost.

And a liquid crystal display element can be obtained by attaching a polarizing plate to the outer both surfaces of the said liquid crystal cell.

Examples of the polarizing plate used on the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called ``H film'' absorbed iodine while stretching and aligning polyvinyl alcohol is sandwiched by a cellulose acetate protective film, or a polarizing plate made of the H film itself. I can.

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. Further, the liquid crystal display device manufactured by the method of the present invention has excellent display characteristics.

Example

The abbreviations used in the examples are as follows.

<Methacryl monomer>

(Photo-aligning 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).

[Formula 13]

(Polar monomer)

MAA: methacrylic acid

[Formula 14]

(Crosslinkable monomer)

GMA: Glycidyl methacrylate

[Formula 15]

(Isocyanate monomer)

MOI-BP: 2-[(3,5-dimethyl-1-pyrazolyl)carbonylamino]ethylmethacrylate

[Formula 16]

<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]

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]

A7: Tetracarboxylic dianhydride represented by the following formula [A7]

A8: Tetracarboxylic dianhydride represented by the following formula [A8]

[Formula 17]

<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: Side chain diamine monomer represented by the following formula [B4]

B5: Side chain diamine monomer represented by the following formula [B5]

B6: Side chain diamine monomer represented by the following formula [B6]

B7: Side chain diamine monomer represented by the following formula [B7]

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 side 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: Side chain diamine monomer represented by the following formula [B14]

[Formula 18]

[Formula 19]

<Other diamine monomers>

C1: other diamine monomer represented by the following formula [C1]

C2: other diamine monomer represented by the following formula [C2]

C3: other diamine monomer represented by the following formula [C3]

C4: other diamine monomer represented by the following formula [C4]

C5: Other diamine monomer represented by the following formula [C5]

C6: other diamine monomer represented by the following formula [C6]

C7: other diamine monomer represented by the following formula [C7]

C8: Other diamine monomer represented by the following formula [C8]

C9: other diamine monomer represented by the following formula [C9]

C10: other diamine monomer represented by the following formula [C10]

C11: Other diamine monomer represented by the following formula [C11]

C12: other diamine monomer represented by the following formula [C12]

C13: Other diamine monomer represented by the following formula [C13]

C14: Other diamine monomer represented by the following formula [C14]

C15: other diamine monomer represented by the following formula [C15]

C16: other diamine monomer represented by the following formula [C16]

C17: other diamine monomer represented by the following formula [C17]

C18: other diamine monomer represented by the following formula [C18]

C19: other diamine monomer represented by the following formula [C19]

C20: other diamine monomer represented by the following formula [C20]

[Formula 20]

[Formula 21]

(Crosslinker ingredient)

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]

[Formula 22]

In addition, the symbol of the reagent used in this example is shown below.

(Polymerization initiator)

AIBN: Azobisisobutyronitrile

(menstruum)

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) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column manufactured by Shodex (KD-803, KD-805).

Column temperature: 50°C, eluent: DMF (as an additive, lithium bromide monohydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, THF is 10 Ml/l), flow rate: 1.0 ml/min.

Standard sample for calibration curve preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: about 9000,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratories (molecular weight: about 12,000, 4,000, 1,000).

(Measurement of imidation rate)

The imidation ratio in the synthesis example was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve it. . A 500 MHz proton NMR was measured for this solution with an NMR analyzer (JNW-ECA500) manufactured by Nippon Electronics Datum. For the imidation rate, a proton derived from a structure that does not change before and after imidation is determined as a reference proton, and the integrated peak value of this proton and the integrated proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm are determined. It was calculated|required by the following formula using. In the following formula, x is the integrated proton peak value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidation ratio is 0%). It is the ratio of the number of reference protons to one proton in the group.

Imidation 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) as a polymerization initiator Was added and degassed again. Then, it reacted at 60 degreeC for 13 hours, and obtained the 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).

The number average molecular weight of this polymer was 34200, and the weight average molecular weight was 116000.

<Methacrylate polymer synthesis example 2>

After dissolving MA1 (3.30 g, 8.00 mmol), GMA (0.56 g, 4.00 mmol) and MAA (0.69 g, 8.00 mmol) in NMP (26.8 g), degassing with a diaphragm pump, polymerization initiator As AIBN (0.16 g, 0.5 mmol) was added, and deaeration was performed again. Then, it reacted at 60 degreeC for 13 hours, and obtained the 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).

The number average molecular weight of this polymer was 45000, and the weight average molecular weight was 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 degassed with a diaphragm pump, followed by AIBN (0.16 g, 0.5 m) as a polymerization initiator. Mol) was added and degassed again. Then, it reacted at 60 degreeC for 13 hours, and obtained the 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).

The number average molecular weight of this polymer was 48000, and the weight average molecular weight was 148000.

<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) were dissolved in NMP (27.2 g), and 60 After reacting at °C for 5 hours, A2 (1.00 g, 2.00 mmol) and A4 (0.87 g, 2.00 mmol) and NMP (9.1 g) were added, followed by reacting at 40 °C for 10 hours to obtain a polyamic acid polymer solution (MP4 ) Was obtained.

<Polyamic acid polymer synthesis examples 5 to 20>

With the composition shown in Table 1, using the same method as in Polymer Synthesis Example 1, polyamic acid polymer solutions MP5 to MP20 were synthesized.

<Amic acid polymer synthesis example 21>

After dissolving C8 (5.17 g, 5.00 mmol) and A4 (2.18 g, 10.00 mmol) in NMP (26.6 g) and reacting at 60° C. for 5 hours, C17 (5.17 g, 5.00 mmol) and NMP ( 9.5 g) was added, and it was made to react at 40 degreeC for 10 hours, and obtained the polyamic acid polymer solution (MP21).

<Amic acid polymer synthesis example 22>

After dissolving C2 (0.61 g, 2.00 mmol), C11 (3.19 g, 8.00 mmol) and A2 (2.50 g, 5.00 mmol) in NMP (24.78 g) and reacting at 60° C. for 5 hours, A1 ( 1.96 g, 5.00 mmol) and NMP (8.26 g) were added, and it reacted at 40 degreeC for 10 hours, and obtained the polyamic acid polymer solution (MP22).

<Polyimide Polymer Synthesis Example 23>

After NMP was added to the polyamic acid polymer solution (MP4) (50 g) and diluted to 6.5% by mass, acetic anhydride (8.8 g) and pyridine (2.7 g) were added as an imidation catalyst, followed by reaction at 75°C for 2.5 hours. Made it. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained the polyimide polymer powder (E). The imidation ratio of this polyimide polymer was 71 %, the number average molecular weight was 13000 and the weight average molecular weight was 42000.

NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and it stirred and dissolved at 70 degreeC for 20 hours. A polyimide polymer solution (MP23) was obtained by adding NMP (10.0 g) and BCS (40.0 g) to this solution and stirring at room temperature for 5 hours.

<Polyimide Polymer Synthesis Examples 24 and 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>

After dissolving MA2 (3.04 g, 6.00 mmol), GMA (0.71 g, 5.00 mmol) and MAA (0.77 g, 9.00 mmol) in NMP (18.8 g), degassing with a diaphragm pump, polymerization initiator As AIBN (0.16 g, 0.5 mmol) was added, and deaeration was performed again. Then, it reacted at 60 degreeC for 13 hours, and obtained the 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).

The number average molecular weight of this polymer was 44000, and the weight average molecular weight was 143000.

(Example 1)

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

(Examples 2 to 24)

With the composition shown in Table 2, using the method similar to Example 1, the liquid-crystal aligning agent (PM2)-(PM24) were obtained.

(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 the methacrylate polymer synthesis example 2, the polymer solution (MP21) (7.0 g) obtained in the amic acid polymer synthesis example 21 was added, and further D2 (0.06 g) was added. And, by stirring at room temperature, a liquid crystal aligning agent (RPM4) was obtained.

(Comparative Example 5)

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

(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.

<Manufacture of liquid crystal display device>

The liquid crystal aligning agents (PM1) to (PM22) obtained in Examples and the liquid crystal aligning agents (RPM1) to (RPM5) obtained in Comparative Examples were pressure-filtered with a membrane filter having a pore diameter of 1 μm.

The resulting solution was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, dried for 90 seconds on a hot plate at 70°C, and fired for 30 minutes on a hot plate at 200°C, and a film thickness of 100 A nm liquid crystal alignment film was formed.

Subsequently, a linearly polarized ultraviolet ray having an irradiation intensity of 4.3 mW/cm 2 and a 313 nm of 313 nm was irradiated on the surface of the coating film by 50 mJ/cm 2 from an angle inclined at 40° in the substrate normal direction to obtain a substrate with a liquid crystal aligning film. The linearly polarized ultraviolet rays were prepared by passing a 313 nm band pass filter through the ultraviolet light of a high-pressure mercury lamp, and then passing a 313 nm polarizing plate.

Two of the above substrates were prepared, and a 4 µm bead spacer was dispersed on the liquid crystal alignment film of one substrate, and then a sealing agent (manufactured by Mitsui Chemicals, XN-1500T) was applied. Subsequently, the other substrate was bonded so that the liquid crystal alignment layer faced and the alignment direction was 180°, and then the sealing agent was thermally cured at 120° C. for 90 minutes to prepare an empty cell. A liquid crystal (MLC-3022 manufactured by Merck Corporation) was injected into this empty cell by a reduced pressure injection method to obtain a liquid crystal display element.

<Evaluation of spreadability>

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 for 90 seconds on a hot plate at 70° C., and the coated surface was observed. The case where non-uniformity or cratering occurred on the coated surface was referred to as "defective", and the case where there was no cratering or non-uniformity and was uniform was referred to as "good", and the applicability of the liquid crystal display element was evaluated. Table 3 shows the evaluation results.

<Evaluation>

(Liquid crystal orientation)

After performing the isotropic treatment for 1 hour at 120 degreeC of the liquid crystal display element obtained above, the cell observation was performed with a polarizing microscope. When there was no alignment defect such as light leakage or domain generation, or when voltage was applied to the liquid crystal cell, uniform driving of the liquid crystal was obtained as good. Table 4 shows the evaluation results.

(Pre-tilt angle)

In the liquid crystal display device manufactured above, the measurement of the pretilt angle of the liquid crystal cell was measured by the Muller matrix method using AxoScan manufactured by Axo Metrix. Table 4 shows the evaluation results.

(Voltage retention rate (VHR) evaluation)

In the evaluation of VHR, a voltage of 1 V was applied for 60 μs at a temperature of 60° C. to the liquid crystal cell prepared above, the voltage after 1667 ms was measured, and how much the voltage was maintained was calculated as the voltage retention rate. .

In addition, for the measurement of the voltage retention rate, the voltage retention rate measuring device VHR-1 manufactured by Toyo Technica was used. Table 4 shows the evaluation results.

(Evaluation of residual DC)

To the liquid crystal cell prepared above, an AC voltage of 6.8 Vpp and a DC voltage of 1 V were applied for 48 hours, and the voltage generated in the liquid crystal cell (residual DC) was determined by the flicker elimination method immediately after the DC voltage was released. This value becomes an index of the afterimage characteristic, and the case where this value is ±30 mV or less was made favorable. Table 4 shows the evaluation results.

(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 after 36 hours to calculate how much the tilt angle was changing. Table 4 shows the evaluation results.

As can be seen from the results of Table 3, from the contrast 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 was not excellent in applicability. On the other hand, by blending with a polyimide solution not containing a side chain, a polyamic acid containing a side chain, and a polyimide solution, a liquid crystal alignment film excellent in coatability was obtained.

In addition, as can be seen from the results in Table 4, from the contrast between Examples 1 to 24 and Comparative Examples 1 to 6, the polymethacrylate solution was blended with a polyamic acid or polyimide solution to change the tilt angle, VHR And a liquid crystal alignment film excellent in residual DC was obtained.

Industrial applicability

The liquid crystal aligning agent of this invention and the liquid crystal display element using the liquid crystal aligning film obtained from it can be used suitably for the liquid crystal display element which requires durability, such as for vehicle installation.

Claims (7)

(A) the following formula (pa-1)
(In the formula, A is depending on a group selected from fluorine, chlorine, and cyano as the case may be, or an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl moiety (this is, in some cases, one cyano Pyrimidine-2,5-diyl, pyridin-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1, which may be substituted with a no group or one or more halogen atoms) Represents 4- or 2,6-naphthylene or phenylene, R ₁ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₂ is a divalent aromatic group, a divalent alicyclic group, and a divalent heterocycle A type group or a divalent condensed cyclic group, R ₃ is a single bond, an oxygen atom, -COO- or -OCO-, and R ₄ is a C 1 to C 40 linear or branched alkyl group or an alicyclic group containing 3 carbon atoms It is a monovalent organic group of -40, D represents 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), and a represents 0 to 3 It is an integer, and * represents a bonding position.)
A polymer which has a photoalignable group and a thermal crosslinkable group A represented by;
(B) a polymer selected from polyimide and its precursor, which has at least one group selected from a vertically aligning group and a tertiarybutoxycarbonyl group, is chemically imidized, or is at least one polymer; And
Solvent;
As a liquid crystal aligning agent containing,
The liquid crystal aligning agent,
Z1: The (A) polymer further has a thermal crosslinkable group B, and/or
Z2: (C) further containing a compound having two or more thermal crosslinkable groups B in the molecule
(The thermal crosslinkable group A and the thermal crosslinkable group B are each independently, which may be the same or different from each other, a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, As a group selected from the group consisting of a thiranyl group, an isocyanate group, and a block isocyanate group, it is selected and formed so that the thermally crosslinkable group A and the thermally crosslinkable group B react by heat for a crosslinking reaction.), a liquid crystal aligning agent.

The method of claim 1,
The liquid crystal aligning agent in which the component (B) is a polymer which has a vertical aligning group. The method of claim 1,
The liquid crystal aligning agent in which the component (B) is a polymer having a tertiarybutoxycarbonyl group. The method of claim 1,
The liquid crystal aligning agent in which the component (B) is a chemically imidized polymer. A liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-4. A process of forming a coating film by applying the liquid crystal aligning agent according to any one of claims 1 to 4 on a substrate, and the coating film in a state in which the coating film is not in contact with the liquid crystal layer or in contact with the liquid crystal layer. The manufacturing method of a liquid crystal aligning film including the process of irradiating light to the. A liquid crystal display device comprising the liquid crystal alignment film according to claim 5 or the liquid crystal alignment film obtained by the production method according to claim 6.