JPWO2022220199A5

JPWO2022220199A5 -

Info

Publication number: JPWO2022220199A5
Application number: JP2023514632A
Authority: JP
Filing date: 2022-04-08
Publication date: 2024-01-23
Anticipated expiration: 2042-04-08

Claims

The following formula (D _ＡA ) Contains at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a diamine component containing diamine (0) represented by A liquid crystal aligning agent characterized by:

(Ar _１1 , Ar _２2 each independently represents a divalent aromatic group having a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group may be replaced with a monovalent group. W is *-(CH _２2 ) _ｍm -LA-*(L represents -OC(=O)- or -C(=O)-O-, A is -(CH _２2 ) _ｎn - represents. m is an integer from 1 to 6. n is an integer from 1 to 16. When n is 2 or more, any -CH constituting A _２2 - is -O-, -C(=O)-, -NH-, -O-C(=O)-, -C(=O)-O-, -C=C-, phenylene group, or cyclo It may be substituted with a hexylene group. Moreover, some of the hydrogen atoms that W has may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. ) is a divalent organic group having 4 to 20 carbon atoms. * represents a bond. )

The above formula (D _ＡA ), W in
*-(CH _２2 ) _ｐp -OC(=O)-(CH _２2 ) _ｑq -*,
*-(CH _２2 ) _ｐp -OC(=O)-(CH _２2 ) _ｑq -C(=O)-O-(CH _２2 ) _ｒr -*,
*-(CH _２2 ) _ｐp -C(=O)-O-(CH _２2 ) _ｑq -OC(=O)-(CH _２2 ) _ｒr -*,
*-(CH _２2 ) _ｐp -O-C(=O)-Q-C(=O)-O-(CH _２2 ) _ｑq -*,
or *-(CH _２2 ) _ｐp -C(=O)-O-Q-OC(=O)-(CH _２2 ) _ｑq -*, Q represents a phenylene group or a cyclohexylene group, and p, q, and r are each independently an integer of 1 to 6, the liquid crystal aligning agent according to claim 1.

The liquid crystal aligning agent according to claim 2, wherein the p is an integer of 2 to 6, the q is an integer of 2 to 6, and the r is an integer of 2 to 6.

The above formula (D _ＡA ) in -NH _２2 The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the bonding position is para to the bonding position with the oxygen atom.

Ar _１1 and Ar _２2 The divalent aromatic group represented by is 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1, 4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-tert-butyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy- 1,4-phenylene, 2-propoxy-1,4-phenylene, 2-butoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4- Methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, 4,4'- Biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4,4'-biphenylylene, 2-tert- Butyl-4,4'-biphenylylene, 2-methoxy-4,4'-biphenylylene, 2-ethoxy-4,4'-biphenylylene, 2-fluoro-4,4'-biphenylylene, 3-methyl-4,4' -biphenylylene, 3-ethyl-4,4'-biphenylylene, 3-propyl-4,4'-biphenylylene, 3-butyl-4,4'-biphenylylene, 3-tert-butyl-4,4'-biphenylylene, 3 -Methoxy-4,4'-biphenylylene, 3-ethoxy-4,4'-biphenylylene, 3-fluoro-4,4'-biphenylylene, 2,2'-dimethyl-4,4'-biphenylylene, 3,3' -dimethyl-4,4'-biphenylylene, 3,3'-biphenylylene, 5-methyl-3,3'-biphenylylene, 5,5'-dimethyl-3,3'-biphenylylene, according to claims 1 to 3. The liquid crystal aligning agent according to any one of the items.

The diamine (0) has the following formula (d _ＡA -1) ~ (d _ＡA -5) The liquid crystal aligning agent according to any one of claims 1 to 3, which is any diamine selected from the group consisting of:

The polymer (P) contains the diamine component and an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof. The liquid crystal aligning agent according to any one of claims 1 to 3, which is obtained by a polycondensation reaction with a tetracarboxylic acid component.

The tetracarboxylic acid component is 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 4-(2 , 5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho [1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2- c] Furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2 , 3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellitic dianhydride Anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetra Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyl dianhydride Phthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride, or a derivative thereof, the liquid crystal aligning agent according to claim 7.

The liquid crystal aligning agent according to claim 1 or 2, wherein the proportion of the tetracarboxylic dianhydride or a derivative thereof used is 10 mol% or more based on the total tetracarboxylic acid component used.

The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the amount of the diamine (0) used is 5 mol% or more based on the diamine component.

The diamine component includes diamines other than diamine (0), and the other diamines include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p -phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3 , 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro -4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis (Trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3' - Diaminobiphenyl, the following formula (d _ＡＬAL -1) ~ (d _ＡＬAL -10), 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1, 8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy) Dodecane, 1,12-bis(3-aminophenoxy)dodecane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4-bis(4-aminophenoxy) Biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane , 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 1,4-phenylenebis(4-aminobenzoate), 1, 4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis(3- Aminophenyl) terephthalate, bis(4-aminophenyl) isophthalate, bis(3-aminophenyl) isophthalate; 4,4'-diaminobenzanilide, 1,3-bis(4-aminophenyl)urea, 1,3 -Bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4 -bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4 -(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'- Bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis( 3-amino-4-methylphenyl)propane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis The liquid crystal aligning agent according to any one of claims 1 to 3, which is (4-aminobenzyl)benzene.

Furthermore, it contains at least one polymer (B) selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the diamine (0) and a polyimide that is an imidized product of the polyimide precursor. The liquid crystal aligning agent according to any one of claims 1 to 3 .

The diamine component for obtaining the polymer (B) is a diamine having at least one group selected from the group consisting of a urea bond, an amide bond, a carboxyl group, and a hydroxy group in the molecule, and the following formula (d _ＡＬAL -1) ~ (d _ＡＬAL -10) and at least one diamine having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group. The liquid crystal aligning agent according to claim 12, containing one type of diamine.

The diamine component for obtaining the polymer (B) is 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6- Diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-( 3-(1H-imidazol-1-yl)propyl-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]- Benzeneamine, diamines represented by the following formulas (z-1) to (z-13), 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis (4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'- Dimethyl-1,4-benzenediamine, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4' -Diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4, 4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2 , 2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3 The liquid crystal aligning agent according to claim 12, which contains '-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid. .

The liquid crystal aligning agent according to claim 12, wherein the content ratio of the polymer (B) is 10 to 90 parts by mass based on a total of 100 parts by mass of the polymers contained in the liquid crystal aligning agent.

A liquid crystal aligning film obtained from the liquid crystal aligning agent according to any one of claims 1 to 3 .

A liquid crystal display element comprising the liquid crystal alignment film according to claim 16 .

A method for manufacturing a liquid crystal display element, including the following steps (1) to (3).
Step (1): A step of applying the liquid crystal aligning agent according to any one of claims 1 to 3 onto a substrate. Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film. Step (3) ): A step of orienting the film obtained in step (2).

The method for manufacturing a liquid crystal display element according to claim 18, wherein the alignment treatment is a rubbing treatment method or a photo alignment treatment method.

19. The liquid crystal display element according to claim 18, wherein the photo-alignment treatment method is a method of irradiating radiation polarized in a certain direction, and the radiation uses ultraviolet rays or visible light having a wavelength of 100 to 800 nm. Production method.

21. The method for manufacturing a liquid crystal display element according to claim 20, comprising the step of further heat-treating the liquid crystal alignment film irradiated with the radiation, and the temperature of the heat treatment is 50 to 300°C.

A diamine represented by the following formula (d _A -1) or formula (d _A -3).

A polymer obtained from a diamine component containing the diamine according to claim 22 .

A polyimide which is a polyimide precursor obtained by a polycondensation reaction between a diamine component containing the diamine according to claim 22 and a tetracarboxylic acid component, or an imidized product thereof.

It is characterized by containing a polymer having at least one type of repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1). Liquid crystal alignment agent.

(In formula (1), X ₁ represents a tetravalent organic group. _{Y 1} is a divalent organic group represented by "-Ar ₁ --O-W-O-Ar ₂ --".
Ar ₁ and Ar ₂ each independently represent a divalent aromatic group having a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group is replaced with a monovalent group; You can.
W is *-(CH ₂ ) _m -LA-*(L represents -OC(=O)- or -C(=O)-O-, A is -(CH ₂ ) _n - represents.
m is an integer from 1 to 6. n is an integer from 1 to 16. When n is 2 or more, any -CH ₂ - constituting A is -O-, -C(=O)-, -NH-, -O-C(=O)-, -C(=O ) -O-, -C=C-, a phenylene group, or a cyclohexylene group.
Moreover, some of the hydrogen atoms that W has may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. ) is a divalent organic group having 4 to 20 carbon atoms. * represents a bond.
R and Z each independently represent a hydrogen atom or a monovalent organic group. )

The polymer is at least one selected from the group consisting of a polyimide precursor obtained using a diamine component containing diamine (0) represented by the following formula (D _A ) and a polyimide that is an imidized product of the polyimide precursor. The liquid crystal aligning agent according to claim 25 , which is a seed polymer (P).

(Ar ₁ , Ar ₂ and W are as defined in claim 1.)

W in the formula (D _A ) is *-(CH ₂ ) _p -OC(=O)-(CH ₂ ) _q -*, *-(CH ₂ ) _p -OC(=O)- (CH ₂ ) _q -C(=O)-O-(CH ₂ ) _r -*, *-(CH ₂ ) _p -C(=O)-O-(CH ₂ ) _q -O-C(=O )-(CH ₂ ) _r -*, *-(CH ₂ ) _p -OC(=O)-Q-C(=O)-O-(CH ₂ ) _q -*, or *-(CH ₂ ) _p -C(=O)-O-Q-O-C(=O)-(CH ₂ ) _q -*, Q represents a phenylene group or a cyclohexylene group, and p, q, r are each The liquid crystal aligning agent according to claim 26 , which is independently an integer of 1 to 6.

The liquid crystal aligning agent according to claim 26 or 27 , wherein the diamine (0) is any diamine selected from the group consisting of the following formulas (d _A -1) to (d _A -5).

(The hydrogen atom on the benzene ring in the above formulas (d _A -1) to (d _A -5) may be substituted with a monovalent substituent.)

The polymer (P) contains the diamine component and an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof. The liquid crystal aligning agent according to claim 26 or 27 , which is obtained by a polycondensation reaction with a tetracarboxylic acid component.

The liquid crystal aligning agent according to claim 26 or 27 , wherein the amount of the diamine (0) used is 5 mol% or more based on the diamine component.

Furthermore, it contains at least one polymer (B) selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the diamine (0) and a polyimide that is an imidized product of the polyimide precursor. The liquid crystal aligning agent according to claim 26 or 27 .

Consists of a crosslinkable compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxy group, and an alkoxy group, and a crosslinkable compound having a polymerizable unsaturated group At least one crosslinking compound selected from the group, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, and the dielectric constant and The liquid crystal aligning agent according to claim 26 or 27 , further comprising an additive component selected from compounds for adjusting electrical resistance.

The liquid crystal aligning agent according to claim 26 or 27, further comprising a polymer other than the polymer (P).

The other polymer is at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component not having the diamine (0) and a polyimide that is an imidized product of the polyimide precursor. Siloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether) The liquid crystal aligning agent according to claim 33, which is a polymer selected from the group consisting of a maleic anhydride) copolymer, a poly(styrene-phenylmaleimide) derivative, and a poly(meth)acrylate.

A liquid crystal aligning film obtained from the liquid crystal aligning agent according to claim 25 or 26 .

A liquid crystal display element comprising the liquid crystal alignment film according to claim 35 .

37. The liquid crystal display element according to claim 36 , which is a transverse field liquid crystal display element.

A method for manufacturing a liquid crystal display element, including the following steps (1) to (3).
Step (1): A step of applying the liquid crystal aligning agent according to claim 25 or 26 on a substrate. Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film. Step (3): Step (2) ) A step of orienting the film obtained in