KR20150139426A - Synthesis of photo-reactive diamine monomer for LCD alignment layer - Google Patents
Synthesis of photo-reactive diamine monomer for LCD alignment layer Download PDFInfo
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- KR20150139426A KR20150139426A KR1020150063895A KR20150063895A KR20150139426A KR 20150139426 A KR20150139426 A KR 20150139426A KR 1020150063895 A KR1020150063895 A KR 1020150063895A KR 20150063895 A KR20150063895 A KR 20150063895A KR 20150139426 A KR20150139426 A KR 20150139426A
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/51—Phenylenediamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
Abstract
The present invention relates to a photo-reactive diamine monomer for polymerization of an orientation film capable of inducing a linear gradient of a hose liquid crystal by photo-curing, a liquid crystal alignment film using the same, and an alignment film comprising the same, When the liquid crystal aligning agent is prepared using the photoreactive diamine monomer compound of the present invention, unreacted mesogens can be minimized to improve the reliability of the panel, improve the response speed and the voltage holding ratio, The desired line inclination angle can be formed to suit the application, and the stability of line inclination angle after the photo-crosslinking can be improved and maintained, which can be usefully used in an alignment film of a liquid crystal display element.
Description
The present invention relates to a photo-reactive diamine monomer for polymerization of an orientation film capable of inducing line tilt of a host liquid crystal by photo-curing, a liquid crystal alignment film using the same, and an alignment film comprising the same.
As high-level digitization and informationization are accelerating, many information technology (IT) devices are being used in daily life, and display technology for them is also developing. Among the electronic displays that have been used in the past, CRT (Cathode Ray Tube) monitors, which have been used for TVs and computer monitors, are the most representative. CRT monitors, however, are bulky and heavy in weight, making them difficult to scale and port, have high power consumption, and are gradually replacing other flat panel displays with higher driving voltages.
LCDs (flat panel displays), plasma display panels (PDPs), and organic light emitting diodes (OLEDs) are typical examples of flat panel displays for overcoming the limitations of CRT.
The alignment for determining the initial alignment of the liquid crystal is mainly performed by sweeping the alignment film in a specific direction using a rubbing method. However, since the rubbing method is a mechanical method, it is difficult to precisely control the initial alignment state of the liquid crystal, and there is a problem in that it is difficult to perform different alignment directions for each fine region. On the other hand, since the liquid crystal display device changes its image through the mechanical operation of the liquid crystal, it is pointed out that a dragging of a moving image due to a slow response speed of the liquid crystal is a problem.
In the constituent material of the liquid crystal display, the alignment film is in contact with the liquid crystal molecules and plays a role of arranging them uniformly. The alignment layer is a key material for uniformly controlling the liquid crystal in one direction so that the liquid crystal can perform well as a switcher of the polarized light, and the orientation characteristic and the display quality of the liquid crystal display as the thin film depend on the orientation.
At present, various polymer compounds are known as liquid crystal aligning agents. Among them, typical polymer compounds most frequently used are polymer compositions such as imidized polymers and soluble polyimides which are imidized with polyamic acid.
On the other hand, in a small and medium-sized mobile liquid crystal display device, a PVA (Patterned Vertical Alignment) mode using a micro slit mode or a photoreactive mesogen is disclosed to reduce the slit portion which is an obstacle to an aperture ratio improvement.
In the micro-slit mode, a micro-slit portion is formed only in the lower electrode among the field-generating electrodes facing each other to impart directionality to the liquid crystal, and the upper electrode is formed as a through-hole.
In the VA mode, such as the PVA mode and the micro-slit mode, anisotropy is induced by light irradiation using a polymerizable mesogen compound without rubbing directly on the alignment layer, May be applied.
This is because when a mesogen compound that can be polymerized by ultraviolet rays together with a host liquid crystal or an orientation film in a liquid crystal cell is induced in the direction in which the host liquid crystal lie when the voltage is applied to the electrode and then cured through light irradiation, And the orientation of the host liquid crystal is induced in the direction of the line inclination determined beforehand when voltage is applied, thereby realizing a high-speed response.
However, conventionally known polymerizable mesogenic compounds for liquid crystal displays have a low photoreaction efficiency and are likely to react with the backlight during driving of the liquid crystal display due to unreacted mesogens remaining un polymerized, . Therefore, a large amount of exposure is required to completely remove unreacted mesogens, which causes a disadvantage that organic materials are decomposed. High light irradiation energy has become a limiting factor in mode development and process design utilizing reactive mesogenic compounds. Therefore, it is required to reduce the un-cured reactive mesogens in the liquid crystal layer. Further, there is a demand for an alignment film capable of uniformly orienting liquid crystal molecules in order to improve the visibility and display quality of the liquid crystal display device. In addition, an optimal alignment film production process is required to improve the reliability and characteristics of the alignment film.
In order to solve the above problems, there has been proposed a liquid crystal display device mode of a type in which a photo reactive group is directly introduced into a polymer main chain that forms an alignment film. The pixel electrodes of the array substrate are formed with slits in different directions between a plurality of domains. A lower alignment layer including at least one diamine having at least one photoreactive side chain is formed on the pixel electrode to induce an oblique direction of the liquid crystal. An upper alignment film is formed on the common electrode of the counter substrate. And the liquid crystal is formed to have a pretilt angle in the lower and upper alignment layers through a process of curing the light reacting unit which is the side chain attached to the photoreactive diamine by irradiating light. Therefore, as the amount of the residual reactive mesogen significantly decreases in the liquid crystal display, the generation of the afterimage is reduced, and the display quality is improved. Such a liquid crystal display device using a photoreactive diamine is described in Patent Document 2 (Korean Patent Laid-Open No. 10-2010-0084823).
The inventors of the present invention conducted studies with interest on photoreactive mesogenic compounds, and found that unreacted monomers were not present through polymerization of an orientation film incorporating the photoreactive diamine compound of the present invention, And thus it can be used as an alignment film for a liquid crystal display of a polymer-stabilized alignment type. Thus, the present invention has been completed.
It is an object of the present invention to provide a photoreactive diamine monomer compound.
It is another object of the present invention to provide a process for preparing the photoreactive diamine monomer compound.
It is still another object of the present invention to provide a liquid crystal aligning agent containing a divalent organic group derived from the photoreactive diamine monomer compound.
Another object of the present invention is to provide a liquid crystal alignment layer comprising the liquid crystal aligning agent.
Still another object of the present invention is to provide a liquid crystal display element including the liquid crystal alignment layer.
In order to accomplish the above object, the present invention provides a photoreactive diamine monomer compound represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
L is
X is a single bond, -CH 2 -, -S-, -NH- , or -O-, and;
Y is a single bond, - (CH 2 ) n -, - (CF 2 ) n -, - (CH 2 ) n - (CF 2 ) m - or - (CH 2 CH 2 O) n -
Wherein n and m are integers between 1 and 20;
Z is
The present invention also relates to a process for producing a compound represented by the formula (1)
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
A step of reducing the compound represented by the formula (4) obtained in the step (1) to produce a compound represented by the formula (5) (step 2);
Reacting a compound represented by Chemical Formula 6 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 7 having a peptide protecting group (Step 3);
Reacting a compound represented by the formula (8) with a compound represented by the formula (7) to obtain a compound represented by the formula (9) (step 4); And
And removing the peptide protecting group of the compound represented by the formula (9) obtained in the step 4 to obtain a compound represented by the formula (1) (step 5).
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
L, X, Y, and Z are as defined in Formula 1;
R 1 is
Further, the present invention relates to a process for the preparation of
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
Reacting the compound represented by the formula (4) and the compound represented by the formula (10) obtained in the above step 1 to prepare a compound represented by the formula (11) (step 2);
A step of performing a reduction reaction of the compound represented by the formula (11) obtained in the step 2 to prepare a compound represented by the formula (12) (step 3);
Reacting a compound represented by the formula (6) with the compound represented by the formula (12) obtained in the step 3 to prepare a compound represented by the formula (13) in which a peptide protecting group is formed (step 4);
Reacting a compound represented by the formula (8) with a compound represented by the formula (13) to obtain a compound represented by the formula (14) (step 5); And
And removing the peptide protecting group of the compound represented by the formula (14) obtained in the step 5 to obtain a compound represented by the formula (1) (step 6).
[Reaction Scheme 2]
(In the above Reaction Scheme 2,
L, X, Y, and Z are as defined in Formula 1;
R 1 is
The present invention also provides a liquid crystal aligning agent comprising a polymer compound comprising at least one repeating unit selected from the group consisting of the following formulas (15) and (16).
[Chemical Formula 15]
[Chemical Formula 16]
In the above formulas (15) and (16)
X 1 and X 2 are independently a tetravalent organic group derived from a single species or a combination of two or more species selected from the group consisting of alicyclic dianhydrides and aromatic acid dianhydrides;
Y 1 And Y 2 independently represent a divalent organic group derived from a single diamine monomer compound or a combination of two or more thereof, and the diamine monomer compound necessarily contains the photoreactive diamine monomer compound represented by Formula 1 and; And
The repeating units represented by formulas (15) and (16) independently have a weight average molecular weight (Mw) of 1,000 to 200,000 g / mol.
Further, the present invention provides a liquid crystal alignment film comprising the liquid crystal aligning agent.
The present invention also provides a liquid crystal display element comprising the liquid crystal alignment layer.
When the liquid crystal aligning agent is prepared using the photoreactive diamine monomer compound of the present invention, unreacted mesogens can be minimized to improve the reliability of the panel, improve the response speed and the voltage holding ratio, The desired line inclination angle can be formed to suit the application, and the stability of line inclination angle after the photo-crosslinking can be improved and maintained, which can be usefully used in an alignment film of a liquid crystal display element.
FIG. 1 shows a photograph of a liquid crystal display device manufactured in Comparative Example 6 in which a liquid crystal molecule is finally aligned by applying a driving voltage using a polarizing microscope, a photograph in which the applied driving voltage is removed, It is an image representing a photo in an oriented state.
Fig. 2 is a photograph showing the state in which the liquid crystal molecules are finally aligned by applying a driving voltage to the liquid crystal display device manufactured in Example 25 using a polarization microscope, and a photograph in which the applied driving voltage is removed, It is an image representing a photo in an oriented state.
Hereinafter, the present invention will be described in detail.
The present invention provides a photoreactive diamine monomer compound represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
L is
X is a single bond, -CH 2 -, -S-, -NH- , or -O-, and;
Y is a single bond, - (CH 2 ) n -, - (CF 2 ) n -, - (CH 2 ) n - (CF 2 ) m - or - (CH 2 CH 2 O) n -
Wherein n and m are integers between 1 and 20;
Z is
Preferably,
L is
X is a single bond, -CH 2 -, -NH-, or -O-;
Y is a single bond, - (CH 2 ) n -, - (CF 2 ) n -, - (CH 2 ) n - (CF 2 ) m - or - (CH 2 CH 2 O) n -
Wherein n and m are integers between 1 and 10;
Z is
More preferably,
L is
X is a single bond, or -O-;
Y is a single bond, or - (CH 2 ) n -
Wherein n is an integer between 3 and 6;
Z is
Preferable examples of the compound represented by the formula (1) according to the present invention include the following compounds.
(1) 3,5-diamino-4'-acryloyloxybiphenyl;
(2) 3,5-diamino-4'-methacryloyloxybiphenyl;
(3) 3,5-Diamino-4'-cinnamoyloxybiphenyl;
(4) 3,5-Diamino-4 '- (3-acryloyloxypropyloxy) biphenyl;
(5) 3,5-Diamino-4 '- (3-methacryloyloxypropyloxy) biphenyl;
(6) 3,5-Diamino-4 '- (3-cinnamoyloxypropyloxy) biphenyl;
(7) 3,5-Diamino-4 '- (6-acryloyloxyhexyloxy) biphenyl;
(8) 3,5-Diamino-4 '- (6-methacryloyloxyhexyloxy) biphenyl;
(9) 3,5-Diamino-4 '- (6-cinnamoyloxyhexyloxy) biphenyl;
(10) 3,5-Diamino-4 "-acryloyloxy-1,1 ': 4', 1" -terphenyl;
(11) 3,5-Diamino-4 "-methacryloyloxy-1,1 ': 4', 1" -terphenyl;
(12) 3,5-Diamino-4 "-cinnamoyloxy-1,1 ': 4', 1" -terphenyl;
(13) 3,5-Diamino-4 '' - (3-acryloyloxypropyloxy) -1,1 ': 4', 1 "-terphenyl;
(14) 3,5-Diamino-4 "- (3-methacryloyloxypropyloxy) -1,1 ': 4', 1" -terphenyl;
(15) 3,5-Diamino-4 '' - (3-cinnamoyloxypropyloxy) -1,1 ': 4', 1 "-terphenyl;
(16) 3,5-Diamino-4 "- (6-acryloyloxyhexyloxy) -1,1 ': 4', 1" -terphenyl;
(17) 3,5-Diamino-4 '' - (6-methacryloyloxyhexyloxy) -1,1 ': 4', 1 "-terphenyl; And
(18) 3,5-Diamino-4 '' - (6-cinnamoyloxyhexyloxy) -1,1 ': 4', 1 "-terphenyl.
The present invention also relates to a process for producing a compound represented by the formula (1)
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
A step of reducing the compound represented by the formula (4) obtained in the step (1) to produce a compound represented by the formula (5) (step 2);
Reacting a compound represented by Chemical Formula 6 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 7 having a peptide protecting group (Step 3);
Reacting a compound represented by the formula (8) with a compound represented by the formula (7) to obtain a compound represented by the formula (9) (step 4); And
And removing the peptide protecting group of the compound represented by the formula (9) obtained in the step 4 to obtain a compound represented by the formula (1) (step 5).
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
L, X, Y, and Z are as defined in Formula 1;
R 1 is
Hereinafter, the method for preparing the compound represented by the formula (1) according to the present invention will be described in detail.
In the method for preparing the compound represented by the formula (1) according to the present invention, the above step 1 is a step for preparing the compound represented by the formula (4) by reacting the compound represented by the formula (2) with the compound represented by the formula , The compound represented by the general formula (2) is dissolved in an organic solvent, and the compound represented by the general formula ( 3 ) and an aqueous solution of calcium carbonate (K 2 CO 3 ) are added and reacted. After degassing for 30 minutes, And performing a coupling reaction to prepare a compound represented by the formula (4).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. , A solution prepared by mixing dimethoxyethane (DME): methanol (3: 1) may be used.
Further, the catalyst may be a Pd (PPh 3) 4.
Further, the reaction is preferably carried out at a temperature of 0 ° C between the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing the compound represented by the formula (1) according to the present invention, the step (2) is a step for producing the compound represented by the formula (5) by performing the reduction reaction of the compound represented by the formula (4) Specifically, a step of adding a Pd / C catalyst to a compound represented by the formula (4), stirring the mixture under 1 atm of hydrogen, and filtering the mixture to prepare a compound represented by the formula (5).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. (THF): ethanol (1: 2) may be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing a compound represented by the general formula (1) according to the present invention, the above step 3 is a step of reacting the compound represented by the general formula (5) obtained in the above step 2 with the compound represented by the general formula (6) More specifically, the compound represented by the formula (5) is dissolved in an organic solvent, and the di-tertiary-butyric carbonate represented by the formula (6) is added dropwise to the ice bath and stirred to obtain the compound .
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing a compound represented by the general formula (1) according to the present invention, the step (4) is a step for preparing a compound represented by the general formula (9) by reacting the compound represented by the general formula More specifically, the compound represented by the general formula (7) is dissolved in an organic solvent, and then the compound represented by the general formula (8) is added and stirred to prepare the compound represented by the general formula (9).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing a compound represented by the general formula (1) according to the present invention, the step (5) is a step for obtaining a compound represented by the general formula (1) by removing the peptide protecting group of the compound represented by the general formula (9) Is a step for slowly removing a protecting group-removed sample from an ice bath and slowly stirring the compound represented by the formula (9) to obtain a compound represented by the formula (1).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
In addition, trifluoroacetic acid (TFA) may be used as the sample for removing the protecting group.
Further, the reaction is preferably carried out at a temperature of 0 ° C between the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
The present invention also relates to a process for producing a compound represented by the formula
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
Reacting the compound represented by the formula (4) and the compound represented by the formula (10) obtained in the above step 1 to prepare a compound represented by the formula (11) (step 2);
A step of performing a reduction reaction of the compound represented by the formula (11) obtained in the step 2 to prepare a compound represented by the formula (12) (step 3);
Reacting a compound represented by the formula (6) with the compound represented by the formula (12) obtained in the step 3 to prepare a compound represented by the formula (13) in which a peptide protecting group is formed (step 4);
Reacting a compound represented by the formula (8) with a compound represented by the formula (13) to obtain a compound represented by the formula (14) (step 5); And
And removing the peptide protecting group of the compound represented by the formula (14) obtained in the step 5 to obtain a compound represented by the formula (1) (step 6).
[Reaction Scheme 2]
(In the above Reaction Scheme 2,
L, X, Y, and Z are as defined in Formula 1;
R 1 is
Hereinafter, the method for preparing the compound represented by the formula (1) according to the present invention will be described in detail.
In the method for preparing the compound represented by the formula (1) according to the present invention, the above step 1 is a step for preparing the compound represented by the formula (4) by reacting the compound represented by the formula (2) with the compound represented by the formula , The compound represented by the general formula (2) is dissolved in an organic solvent, and the compound represented by the general formula ( 3 ) and an aqueous solution of calcium carbonate (K 2 CO 3 ) are added and reacted. After degassing for 30 minutes, And performing a coupling reaction to prepare a compound represented by the formula (4).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. , A solution prepared by mixing dimethoxyethane (DME): methanol (3: 1) may be used.
Further, the catalyst may be a Pd (PPh 3) 4.
Further, the reaction is preferably carried out at a temperature of 0 ° C between the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing the compound represented by the formula (1) according to the present invention, the above step 2 is a step of reacting the compound represented by the formula (4) obtained in the above step 1 with the compound represented by the formula (10) More specifically, the compound represented by formula (4) is dissolved in an organic solvent, and the compound represented by formula (10) and potassium carbonate are added and refluxed to prepare a compound represented by formula (11).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Acetone can be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the process for preparing the compound represented by the formula (1) according to the present invention, the step (3) is a step for producing the compound represented by the formula (12) by performing the reduction reaction of the compound represented by the formula (11) Specifically, a step of adding a Pd / C catalyst to a compound represented by the formula (11), stirring the mixture under 1 atm of hydrogen, and then filtering the mixture to prepare a compound represented by the formula (12).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. (THF): ethanol (1: 2) may be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In step (4), the compound represented by formula (12) is reacted with the compound represented by formula (6) to obtain a compound represented by formula (13) More specifically, the compound represented by the formula (12) is dissolved in an organic solvent, and the di-tertiary-butyric carbonate represented by the formula (6) is added dropwise to the ice bath and stirred to obtain the compound .
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the method for preparing the compound represented by the formula (1) according to the present invention, the above step 5 is a step for preparing a compound represented by the formula (14) by reacting the compound represented by the formula More specifically, the compound represented by the formula (13) is dissolved in an organic solvent, and the compound represented by the formula (8) is added and stirred to prepare the compound represented by the formula (14).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
The reaction temperature is preferably between 0 ° C and the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
In the method for preparing the compound represented by the formula (1) according to the present invention, the step 6 is a step for removing the peptide protecting group of the compound represented by the formula (14) obtained in the step 5 to obtain the compound represented by the formula (1) The compound represented by the general formula (14) is slowly dropped from the ice bath to remove the protecting group and stirred to obtain the compound represented by the general formula (1).
The organic solvent may include acetone, dimethoxyethane (DME), methanol, ethanol, ethyl acetate, tetrahydrofuran (THF), diethyl ether, diphenyl ether, diisopropyl ether (DIPE) (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), dichloromethane (DCM), chlorobenzene, toluene, benzene, or a mixture of two or more thereof. Dichloromethane (DCM) can be used.
In addition, trifluoroacetic acid (TFA) may be used as the sample for removing the protecting group.
Further, the reaction is preferably carried out at a temperature of 0 ° C between the boiling point of the solvent, and the reaction time is not particularly limited, but preferably 0.5-24 hours.
The present invention also provides a liquid crystal aligning agent comprising a polymer compound comprising at least one repeating unit selected from the group consisting of the following formulas (15) and (16).
[Chemical Formula 15]
[Chemical Formula 16]
In the above formulas (15) and (16)
X 1 and X 2 are independently a tetravalent organic group derived from a single species or a combination of two or more species selected from the group consisting of alicyclic dianhydrides and aromatic acid dianhydrides;
Y 1 And Y 2 independently represent a divalent organic group derived from a single diamine monomer compound or a combination of two or more thereof, and the diamine monomer compound necessarily contains the photoreactive diamine monomer compound represented by Formula 1 and; And
The repeating units represented by formulas (15) and (16) independently have a weight average molecular weight (Mw) of 1,000 to 200,000 g / mol.
The alicyclic dianhydride may be 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2- Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene- Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- Dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ c] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro- Yl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- hexahydro-7-methyl-5- (tetrahydro- Furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro- 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl- 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b-hexahydro (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] , 9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3- 1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene- Tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dicarboxylic anhydride, bicyclo [2.2.2] Dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione)
Wherein the aromatic acid dianhydride is selected from the group consisting of pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4 ' -Biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4, 4'-biphenylether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, Bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bisphenol-bis (triphenylphthalic acid) dianhydride, bis (Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol- Hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) Propane-bis (anhydrotrimellitate), and the like.
Further, Y 1 And Y < 2 > are independently a divalent organic group derived from a combination of two or more diamine monomer compounds, the diamine monomer compound may further include compounds represented by the following general formulas (19) to (21).
[Chemical Formula 19]
H 2 NA-NH 2
The compound represented by the above-mentioned formula (19) forms a main chain and plays a role of exhibiting the required characteristics. The compound represented by the formula (19) is a compound represented by the general formula Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- 4'-diaminobiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1 - (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl Ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- Aminophenoxy) phenyl] sulfone, 1,4-bis Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5- Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy- , 4'-diaminobiphenyl, 1,4,4 '- (p-phenyleneisopropylidene) bisaniline, 4,4' - (m-phenyleneisopropylidene) bisaniline, 2,2'- Bis (trifluoromethyl) biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, Di (4-aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-thiadiazol- Trimethyl-1H-inden-5-amine, 1,1-methoxysilylenediamine, 1,3-propanediamine, tetramethylene But are not limited to, diamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylene di Aliphatic or alicyclic diamines such as tricyclo [6.2.1.02,7] undecylenediimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) ; Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, Aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide or 1- (3,5-diaminophenyl) -3-octadecylsuccinimide is preferable.
[Chemical Formula 20]
In the above formula (20)
R 21 is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or - (CH 2 ) m -, wherein m is an integer of 1 to 12;
R 22 is unsubstituted or one or more fluorine groups (-F) a substituted C 3 -20 straight or branched chain alkyl, unsubstituted or substituted C 6 -10 aryl, or a steroid group, and
Any of -CH 2 - included in the above unsubstituted or straight-chain or branched alkyl of C 3 -20 substituted with at least one fluorine group (-F) is -O-, -CH = CH- or -C≡C- , ≪ / RTI >
The aryl-substituted C 6 -10 is -F, -CH 3, -OCH 3, -OCH 2 F, -OCHF 2 or -OCF 3 a C 6 -10 are one or more substituents selected from the group consisting of a substituted Lt; / RTI >
The steroid group
The compound represented by Formula 20 plays a role in inducing the vertical implementation.
[Chemical Formula 21]
In Formula 21,
R 2 is C 3 -6 2 is an organic aliphatic or aromatic hydrocarbon group of;
m is an integer of 1 to 100;
The diaminosiloxane represented by the formula (21) serves to increase the adhesion to the surface of the substrate and preferably contains 0.1 to 20% by weight of the liquid crystal aligning agent.
The repeating units represented by the above-mentioned formulas (15) and (16) are preferably 5 to 70 mol%, more preferably 5 to 50 mol%, and most preferably 5 to 30 mol% based on the total amount of the liquid crystal aligning agent desirable. When the repeating units represented by the above formulas (15) and (16) are contained in the above range of the preferable mole%, excellent heat resistance, durability, solvent resistance and permeability are obtained and a stable pretilt angle can be realized, ratio, VHR), residual direct current (RDC), liquid crystal orientation, and the like can be improved.
The liquid crystal aligning agent may include a solvent for dissolving the polymer compound.
Examples of the solvent include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- Ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N- D Butyl and the like can be used propanamide, 3-hexyloxy -N, N- dimethylpropanamide.
In the liquid crystal aligning agent, the content of the solvent is not particularly limited, but may be such that the solid content of the polymer in the liquid crystal aligning agent is 0.1 to 30% by weight, 25% by weight. When the content of the solid content is within the above desirable solid content range, the uniformity of the film can be appropriately maintained and the proper viscosity can be maintained by being less influenced by the stain on the substrate surface at the time of printing, The lowering of the uniformity can be prevented, and the appropriate transmittance can be exhibited.
Further, the present invention provides a liquid crystal alignment layer comprising the liquid crystal aligning agent. Specifically, the liquid crystal alignment layer can be produced by applying the liquid crystal aligning agent onto the substrate and heating the liquid crystal alignment layer.
The liquid crystal aligning agent can be applied by a roll coater method, a spinner method, a printing method, an ink jet method, or the like, and then the coated surface can be heated to produce a liquid crystal alignment film.
After the application of the liquid crystal aligning agent is completed, preliminary heating (preliminary baking) may be performed to prevent the liquid flow of the applied liquid crystal alignment layer. At this time, the prebaking temperature may be 30 to 300 ° C, preferably 40 to 200 ° C, and more preferably 50 to 150 ° C.
Subsequently, the solvent is completely removed and a firing (post bake) process may be performed to thermally imide the polyamic acid represented by the formula (15). At this time, the firing (post bake) temperature may be 80 to 300 ° C, preferably 120 to 250 ° C. The imidization ratio of the polyamic acid contained in the liquid crystal aligning agent is preferably 20-100%, more preferably 40-100%, and most preferably 40-80%. If the imidization ratio is not within the range of 20-100%, there is a problem that the coating stability of the liquid crystal aligning agent is lowered and the orientation stability and reliability are poor.
A coating film to be a liquid crystal alignment film is formed by applying a liquid crystal aligning agent containing a polyamic acid represented by the following formula (15), removing the organic solvent after coating, and heating to proceed dehydration ring closure to form a more imaged liquid crystal alignment film have. At this time, the film thickness of the liquid crystal alignment film to be formed may be 0.001 to 1 mu m, preferably 0.005 to 0.5 mu m.
The dried film surface may be subjected to an alignment treatment by irradiating ultraviolet rays in the range of 150 to 450 nm. At this time, the intensity of the exposure can be irradiated with an energy of 50 mJ / cm 2 to 10 J / cm 2, preferably 500 mJ / cm 2 to 5 J / cm 2. If the exposure dose is too large, there is a disadvantage that the organic material is decomposed, leading to lower reliability. Therefore, an optimal alignment film production process is required to improve the reliability and characteristics of the alignment film.
After a series of processes according to the above-described photo-alignment, a liquid crystal alignment layer having excellent thermal stability and high alignability can be obtained.
The present invention also provides a liquid crystal display element comprising the liquid crystal alignment layer.
The liquid crystal display element may be manufactured according to a conventional method known in the art. Specifically, one of the two substrates on which the liquid crystal alignment layer is formed is coated with an adhesive containing a ball spacer on the end portion of the substrate, and the remaining one substrate is adhered to bond the cells. Thereafter, the liquid crystal cell is completed by injecting liquid crystal into the completed cell and heat-treating it.
The liquid crystal display element having the liquid crystal alignment film exhibits excellent alignment state and excellent thermal stability in the liquid crystal alignment state.
Therefore, when a liquid crystal aligning agent is prepared by using the photoreactive diamine monomer compound according to the present invention, unreacted mesogens can be minimized to improve the reliability of the panel and to improve the response speed and the voltage holding ratio. The desired line inclination angle can be formed in accordance with the application, and the stability of line inclination angle after the photo-crosslinking can be improved and maintained, so that it can be usefully used for an alignment film of a liquid crystal display element.
First, experiments were conducted to calculate the weight average molecular weights of the polymers contained in the liquid crystal aligning agents prepared in Examples 19-21 and Comparative Example 4 to be described later. As a result, it was confirmed that the liquid crystal aligning agents prepared in Examples 19-21 and Comparative Example 4 The weight average molecular weight of the polymer contained in the liquid crystal aligning agent was confirmed to be about 2,000 to 1,500,000 g / mol (see Experimental Example 1).
Further, experiments were carried out to measure the imidization ratios of the polyamic acid contained in the liquid crystal aligning agents prepared in Examples 19-21 and Comparative Example 4. As a result, it was found that the liquid crystal aligning agents prepared in Examples 19-21 and Comparative Example 4, It was confirmed that the imidization ratio of the polyamic acid contained in the alignment agent was about 20-100% (see Experimental Example 2).
Further, experiments were conducted to evaluate the characteristics of the liquid crystal alignment layers (Examples 22-24) and the liquid crystal display devices (Examples 25-27) according to the present invention. As a result, the liquid crystal alignment layer and the liquid crystal display according to the present invention exhibited vertical It was confirmed that the liquid crystal aligning agent for electric field driving has characteristics equivalent to or superior to those of the comparative example, such as surface tension, orientation, squareness, linear stability, and voltage retention. In particular, the liquid crystal display devices of Examples 25-27 were easy to fix liquid crystal director, unlike the liquid crystal display device of Comparative Example 6. It was thus confirmed that the liquid crystal display element of the present invention has a remarkable effect that it is possible to form a pretilt angle without rubbing process by irradiating UV and further to determine the direction of the pretilt angle (Tables 2 and 3 of Experimental Example 3 And Fig. 2).
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.
< Example 1> 3,5- Diamino -4'- Acryloyloxybiphenyl synthesis
Step 1: 3,5- Di Nitro -4'- Hydroxybiphenyl synthesis
1-Iodo-3,5-dinitrobenzene (25 g, 85.3 mmol) was added to the reaction vessel and dissolved in DME / methanol (310 mL, 3/1), and 4-hydroxyphenylboronic acid g, 128.0 mmol), and 2M aqueous potassium carbonate solution (50 mL) was added. After degassing for 30 minutes, palladium tetrakis (triphenylphosphine) (10 g, 8.53 mmol) was added and the mixture was stirred at 80 ° C for 24 hours. Water was added to the reaction vessel to terminate the reaction, and the reaction mixture was extracted with dichloromethane. The solvent was evaporated and the residue was purified by column chromatography (silica, hexane / ethyl acetate = 5/1) to obtain a pale yellow compound (17.7 g, 80 %).
1H NMR (300 MHz, CDCl 3 ) δ 9.90 (s, 1H), 8.67 (s, 2H), 8.64 (s, 1H), 7.72 (d, 2H), 6.87 (d, 2H);
MS m / z 260 (M < + >).
Step 2: 3,5- Diamino -4'- Hydroxybiphenyl synthesis
To the reaction vessel was added 3,5-dinitro-4'-hydroxybiphenyl (8.0 g, 30.7 mmol) and palladium / activated carbon (5 wt.%, 4.0 g), and THF (100 mL) Respectively. The mixture was stirred under 1 atm of hydrogen for 24 hours and then filtered. The filtrate was concentrated and used in the next reaction without further purification (6.1 g, ~ 100%).
1H NMR (300 MHz, CDCl 3 ) δ 7.36 (d, 2H), 6.84 (d, 2H), 6.19 (s, 2H), 5.96 (s, 1H), 4.33 (dr s, 4H);
MS m / z 200 (M < + >).
Step 3: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4'- Hydroxybiphenyl synthesis
3,5-Diamino-4'-hydroxybiphenyl (6.0 g, 3.0 mmol) was added to the reaction vessel, and dichloromethane (200 mL) was added to dissolve it. Di-tertiary-butyl carbonate (16.5 mL, 7.2 mmol) was added dropwise to the reaction vessel in an ice bath, followed by stirring at room temperature for 12 hours. Water was added to the reaction vessel to terminate the reaction, followed by extraction with dichloromethane, and all the organic solvent was evaporated. The resulting mixture was separated by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a white solid (7.2 g, 61%).
1H NMR (300 MHz, CDCl3)? 7.37 (d, 2H), 7.24 (m, 2H), 6.83 (d, 2H), 6.60 (s, 1H), 1.52
MS m / z 400 (M < + >).
Step 4: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4'- Acryloyloxybiphenyl synthesis
To the reaction vessel, 3,5-bis [(tert-butoxycarbonyl) amino] -4'-hydroxybiphenyl (6.5 g, 16.2 mmol) was added and dissolved in dichloromethane (200 mL). Triethylamine (22 mL, 162.0 mmol) was added to the reaction vessel, acryloyl chloride (2 mL, 24.3 mmol) was added to the ice bath, and the mixture was stirred at 40 ° C for 12 hours. The reaction vessel was poured into water, extracted with dichloromethane, and all of the organic solvent was evaporated. The obtained mixture was separated by column chromatography (silica, hexane / ethyl acetate = 5/1) to obtain a white solid (4.0 g, 55%).
1H NMR (300 MHz, CDCl 3 ) δ 8.49 (br s, 2H), 7.79 (s, 1H), 7.67 (d, 2H), 7.56 (s, 2H), 7.29 (d, 2H), 6.58 (d, 1H), 6.39-6.45 (m, 1H), 6.12 (d, 1H), 1.52 (s, 18H);
MS m / z 454 (M < + >).
Step 5: 3,5- Diamino -4'- Acryloyloxybiphenyl synthesis
To the reaction vessel was added 3,5-bis [(tert-butoxycarbonyl) amino] -4'-acryloyloxybiphenyl (2.0 g, 4.4 mmole), and trifluroacetic acid (13 mL, 176.0 mmole) was slowly added dropwise. After stirring at room temperature for 3 hours, water was added to stop the reaction. After extraction with ethyl acetate, all of the organic solvent was evaporated to obtain a white solid compound (1.1 g, 99%).
1H NMR (300 MHz, CDCl 3 ) δ 7.57 (d, 2H), 7.20 (d, 2H), 6.57 (d, 1H), 6.38 - 6.43 (m, 1H), 6.27 (s, 2H), 6.10 (d , 1 H), 6.04 (s, 1 H), 4.45 (br s, 4 H);
MS m / z 254 (M < + >).
< Example 2> 3,5- Diamino -4'- Methacryloyloxybiphenyl synthesis
The procedure of Example 1 was repeated except that methacryloyl chloride was used instead of acryloyl chloride in the step 4 of Example 1 to obtain the desired compound.
< Example 3> 3,5- Diamino -4'- Cinnamoyloxybiphenyl synthesis
The target compound was obtained in the same manner as in <Example 1> except that cinnamoyl chloride was used instead of acryloyl chloride in Step 4 of Example 1 above.
< Example 4> 3,5- Diamino -4 ' - (3- Acryloyloxypropyloxy ) Biphenyl synthesis
Step 1: 3,5- Di Nitro -4 ' - (3- Hydroxypropyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-dinitro-4'-hydroxybiphenyl (9.0 g, 34.6 mmol) and dissolved in acetone (250 mL). To the mixture was added 1- Potassium furoate (9.5 g, 69.2 mmol) was added, and the mixture was refluxed for 12 hours. Water was added to the reaction vessel, followed by extraction with dichloromethane, followed by evaporation of the organic solvent. The resulting mixture was separated by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a yellow solid (9.0 g, 83%).
1H NMR (300 MHz, CDCl 3 ) δ 8.86 (s, 1H), 8.83 (s, 2H), 7.88 (d, 2H), 7.16 (d, 2H), 4.23 (t, 2H), 3.78 (t, 2H ), 2.00 (t, 2H);
MS m / z 318 (M < + >).
Step 2: 3,5- Diamino -4 ' - (3- Hydroxypropyloxy ) Biphenyl synthesis
To the reaction vessel, 3,5-dinitro-4 '- (3-hydroxypropyloxy) biphenyl (9.0 g, 28.3 mmol) and palladium / activated carbon (5 wt. And ethanol (200 mL). The mixture was stirred under 1 atm of hydrogen for 24 hours and then filtered. The filtrate was concentrated and used in the next reaction without further purification (7.3 g, 99%).
Step 3: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4 ' - (3- Hydroxypropylox Hour) biphenyl synthesis
To the reaction vessel, 3,5-diamino-4 '- (3-hydroxypropyloxy) biphenyl (6.8 g, 26.3 mmol) was added and dissolved in THF (100 mL) and ethanol (50 mL). Di-tertiary-butyl carbonate (14.5 mL, 63.2 mmol) was added dropwise to the reaction vessel in an ice bath, triethylamine (22 mL, 158.0 mmol) was added thereto, and the mixture was stirred at room temperature for 12 hours. Water was added to the reaction vessel to terminate the reaction, followed by extraction with dichloromethane, and all the organic solvent was evaporated. The resulting mixture was separated by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a white solid (7.0 g, 58%).
1H NMR (300 MHz, CDCl 3 ) δ 8.45 (br s, 2H), 7.74 (s, 1H), 7.52-7.57 (m, 4H), 7.03 (d, 2H), 4.17 (t, 2H), 3.78 ( t, 2 H), 2.00 (t, 2 H), 1.51 (s, 18 H);
MS m / z 458 (M < + >).
Step 4: 3,5- Diamino -4 ' - (3- Acryloyloxypropyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-bis [(tert-butoxycarbonyl) amino] -4'- (3-hydroxypropyloxy) biphenyl (7.0 g, 15.2 mmol) and dissolved in dichloromethane . Triethylamine (15 mL, 152.0 mmol) was added to the reaction vessel, acryloyl chloride (1.8 mL, 22.9 mmol) was added to the ice bath, and the mixture was stirred at 40 ° C for 12 hours. The reaction vessel was poured into water, extracted with dichloromethane, and all of the organic solvent was evaporated. The resulting mixture was vacuum dried, and then, in an ice bath, trifluoroacetic acid (12 mL, 156.0 mmole) was slowly added dropwise. After stirring at room temperature for 3 hours, water was added to stop the reaction. After extraction with ethyl acetate, all of the organic solvent was evaporated to obtain a white solid compound (2.5 g, 25%).
1H NMR (300 MHz, CDCl 3 ) δ 7.45-7.52 (m, 2H), 6.96-7.01 (m, 2H), 6.36-6.40 (m, 2H), 6.14-6.23 (m, 2H), 5.89-6.00 ( (m, 2H), 4.37 (t, 2H), 4.17 (t, 2H), 2.84 (brs, 4H), 2.19
MS m / z 312 (M < + >).
< Example 5> 3,5- Diamino -4 ' - (3- Methacryloyloxypropyloxy ) Biphenyl synthesis
The target compound was obtained in the same manner as in <Example 4>, except that methacryloyl chloride was used instead of acryloyl chloride in the step 4 of Example 4.
< Example 6> 3,5- Diamino -4 ' - (3- Cinnamoyloxypropyloxy ) Biphenyl synthesis
The procedure of Example 4 was repeated except that cinnamoyl chloride was used instead of acryloyl chloride in step 4 of Example 4 to obtain the desired compound.
< Example 7> 3,5- Diamino -4 ' - (6- Acryloyloxyhexyloxy ) Biphenyl synthesis
Step 1: 3,5- Di Nitro -4 ' - (6- Hydroxyhexyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-dinitro-4'-hydroxybiphenyl (9.0 g, 34.6 mmol), and the resulting mixture was dissolved in acetone (250 mL). 1-Bromo-3-hexanol (6.8 mL, 23.0 mmol) , Potassium carbonate (9.5 g, 69.2 mmol) was added thereto, and the mixture was refluxed for 12 hours. Water was added to the reaction vessel, followed by extraction with dichloromethane, followed by evaporation of the organic solvent. The resulting mixture was separated by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a yellow solid (10.0 g, 80%).
1H NMR (300 MHz, CDCl 3 ) δ 8.86 (s, 1H), 8.83 (s, 2H), 7.89 (d, 2H), 7.15 (d, 2H), 4.12 (t, 2H), 3.58 (t, 2H ), 1.85 (t, 2H), 1.48-1. 60 (m, 6H);
MS m / z 360 (M < + >).
Step 2: 3,5- Diamino -4 ' - (6- Hydroxyhexyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-dinitro-4 '- (6-hydroxyhexyloxy) biphenyl (10.0 g, 27.7 mmol) and palladium / activated carbon (5 wt.%, 5.0 g) ) And ethanol (200 mL). The mixture was stirred under 1 atm of hydrogen for 24 hours and then filtered. The filtrate was concentrated and used in the next reaction without further purification (8.3 g, 99%).
1H NMR (300 MHz, CDCl 3 ) δ 7.45 (d, 2H), 6.95 (d, 2H), 6.23 (s, 2H), 5.99 (s, 1H), 4.03 (t, 2H), 3.57 (t, 2H ), 1.82 (t, 2H), 1.44 - 1.58 (m, 6H);
MS m / z 300 (M < + >).
Step 3: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4 ' - (6- Hydroxyhexyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-diamino-4 '- (6-hydroxyhexyloxy) biphenyl (8.3 g, 27.6 mmol) and dissolved in THF (100 mL) and ethanol (50 mL). Di-tertiary-butyl carbonate (15 mL, 66.4 mmol) was added dropwise to the reaction vessel in an ice bath, triethylamine (23 mL, 166.0 mmol) was added thereto, and the mixture was stirred at room temperature for 12 hours. Water was added to the reaction vessel to terminate the reaction, followed by extraction with dichloromethane, and all the organic solvent was evaporated. The obtained mixture was separated by column chromatography (silica, hexane / ethyl acetate = 1/1) to obtain a white solid (8.5 g, 62%).
1H NMR (300 MHz, CDCl 3 ) δ 7.49 (d, 2H), 7.42 (s, 1H), 7.28 (s, 2H), 6.91 (d, 2H), 6.78 (s, 2H), 3.97 (t, 2H ), 3.67 (t, 2H), 1.81 (t, 2H), 1.45-1.58 (m, 24H);
MS m / z 500 (M < + >).
Step 4: 3,5- Diamino -4 ' - (6- Acryloyloxyhexyloxy ) Biphenyl synthesis
The reaction vessel was charged with 3,5-bis [(tert-butoxycarbonyl) amino] -4'- (6-hydroxyhexyloxy) biphenyl (8.5 g, 17.0 mmol) and dichloromethane Melted. Triethylamine (25 mL, 170.0 mmol) was added to the reaction vessel, acryloyl chloride (2.1 mL, 25.5 mmol) was added to the ice bath, and the mixture was stirred at room temperature for 12 hours. The reaction vessel was poured into water, extracted with dichloromethane, and all of the organic solvent was evaporated. The resulting mixture was vacuum dried, and then trifluoroacetic acid (11 mL, 144.0 mmole) was slowly added dropwise from the ice bath. After stirring at room temperature for 3 hours, water was added to stop the reaction. After extraction with ethyl acetate, all of the organic solvent was evaporated to obtain a white solid compound (1.2 g, 20%).
2H), 6.21 (d, 2H), 6.55 (d, 1H), 6.38-6.40 (m, 1H), 6.05 (s, IH), 4.02 (t, 2H), 3.98 (t, 2H), 1.90 (t, 2H), 1.45 - 1.53 (m, 6H);
MS m / z 354 (M < + >).
< Example 8> 3,5- Diamino -4 ' - (6- Methacryloyloxyhexyloxy ) Biphenyl synthesis
The procedure of Example 7 was repeated except that methacryloyl chloride was used instead of acryloyl chloride in the step 4 of Example 7 to obtain the desired compound.
< Example 9> 3,5- Diamino -4 ' - (6- Cinnamoyloxyhexyloxy ) Biphenyl synthesis
The procedure of Example 7 was repeated except that cinnamoyl chloride was used instead of acryloyl chloride in Step 4 of Example 7 to obtain the desired compound.
< Example 10> 3,5- Diamino -4''- Acryloyloxy -1,1 ': 4', 1 " - Terphenyl synthesis
Step 1: 3,5- Di Nitro -4''- Methoxy -1,1 ': 4', 1 " - Terphenyl synthesis
Except that 4'-methoxybiphenyl-4-ylboronic acid was used instead of 4-hydroxyphenylboronic acid in the above Step 1 of Example 1, The procedure of Step 1 of Example 1 was repeated to obtain the desired compound.
Step 2: 3,5- Di Nitro -4 "-hydroxy-1,1 ': 4', 1" - Terphenyl synthesis
3,5-dinitro-4 'obtained in Step 1' - methoxy -1,1 ': 4', 1 '' - terphenyl-a was dissolved in CH 2 Cl 2 solvent, and maintained at 0 ℃ and BBr 3 And the mixture was stirred for 1 hour to obtain the target compound.
Step 3: 3,5- Diamino -4 "-hydroxy-1,1 ': 4', 1" - Terphenyl synthesis
Instead of using 3,5-dinitro-4'-hydroxybiphenyl in step 2 of Example 1 above, 3,5-dinitro-4 "-hydroxy-1,1 ': 4 ', 1''- terphenyl was used in place of the compound obtained in Example 1, to give the title compound.
Step 4: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4'-hydroxy-1,1 ': 4', 1 "-terphenyl Synthesis
Instead of using 3,5-diamino-4'-hydroxybiphenyl in the above Step 3 of Example 1, 3,5-diamino-4 "-hydroxy-1,1 ': 4 ', 1''- terphenyl was used in place of the compound obtained in Step 1 of Example 1 to obtain the desired compound.
Step 5: 3,5- Diamino - 4''- Acryloyloxy -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-bis [(tert-butoxycarbonyl) amino] -4'-hydroxybiphenyl in Step 4 of Example 1 above, 3,5-bis [(tert- Step 4 and Step 5 of Example 1] were repeated except that 4'-tert-butoxycarbonylamino) -4 '' - hydroxy-1,1 ' To give the desired compound.
< Example 11> 3,5- Diamino -4''- Methacryloyloxy -1,1 ': 4', 1 " - Terphenyl synthesis
The procedure of Step 5 of Example 10 was followed except that methacryloyl chloride was used instead of acryloyl chloride in Step 5 of Example 10 to obtain the desired compound .
< Example 12> 3,5- Diamino -4''- Cinnamoyloxy -1,1 ': 4', 1 " - Terphenyl synthesis
The target compound was obtained in the same manner as in <Step 5> of Example 10, except that cinnamoyl chloride was used instead of acryloyl chloride in Step 5 of Example 10 above.
< Example 13> 3,5- Diamino -4 "-( 3- Acryloyloxypropyloxy ) -1,1 ': 4', 1 "-terphenyl synthesis
Step 1: 3,5- Di Nitro -4 "-( 3- Hydroxypropyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-dinitro-4'-hydroxybiphenyl in step 1 of Example 4 above, 3,5-dinitro-4 "-hydroxy-1,1 ': 4 ', 1''- terphenyl was used in place of 1-tert-butoxycarbonylamino-4-methylphenylboronic acid to obtain the desired compound.
Step 2: 3,5- Diamino -4 "-( 3- Hydroxypropyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-dinitro-4 '- (3-hydroxypropyloxy) biphenyl in step 2 of Example 4 above, 3,5-dinitro-4 " Hydroxypropyloxy) -1,1 ': 4', 1 '' - terphenyl was used in place of the compound obtained in Step 2 of Example 4, the target compound was obtained.
Step 3: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4 "-( 3- Hydroxypropylox Hour) -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-diamino-4 '- (3-hydroxypropyloxy) biphenyl in step 3 of Example 4 above, 3,5-diamino-4 " Hydroxypropyloxy) -1,1 ': 4', 1 "-terphenyl was used in place of the compound obtained in Step 3 of Example 4 to obtain the desired compound.
Step 4: 3,5- Diamino -4 "-( 3- Acryloyloxypropyloxy ) - 1,1 ': 4', 1 " - foundation Phenyl synthesis
Instead of using 3,5-bis [(tert-butoxycarbonyl) amino] -4 '- (3-hydroxypropyloxy) biphenyl in step 4 of Example 4 above, 3,5- Except that the bis [(tert-butoxycarbonyl) amino] -4 '' - (3-hydroxypropyloxy) -1,1 ': 4', 1 " Step 4 of Example 4] to obtain the target compound.
< Example 14> 3,5- Diamino -4 "-( 3- Methacryloyloxypropyloxy ) -1,1 ': 4', 1 "-terphenyl synthesis
The procedure of Step 4 of Example 13 was repeated except that methacryloyl chloride was used instead of acryloyl chloride in Step 4 of Example 13 to obtain the desired compound .
< Example 15> 3,5- Diamino -4 "-( 3- Cinnamoyloxypropyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
The target compound was obtained in the same manner as in <Step 4> of Example 13, except that cinnamoyl chloride was used instead of acryloyl chloride in Step 4 of Example 13 above.
< Example 16> 3,5- Diamino -4 "-( 6- Acryloyloxyhexyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
Step 1: 3,5- Di Nitro -4 "-( 6- Hydroxyhexyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
In the same manner as in Example 1, except that 6-bromohexan-1-ol was used instead of 1-bromo-3-propanol in the step 1 of Example 13, The target compound was obtained.
Step 2: 3,5- Diamino -4 "-( 6- Hydroxyhexyloxy ) -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-dinitro-4 "- (3-hydroxypropyloxy) -1,1 ': 4', 1" -terphenyl in Step 2 of Example 13 above, Step 2 of Example 13 was repeated except that 3,5-dinitro-4 "- (6-hydroxyhexyloxy) -1,1 ': 4', 1"≫ to obtain the desired compound.
Step 3: 3,5-Bis [( tert - Butoxycarbonyl ) Amino] -4 " - (6- Hydroxyhexylox Hour) -1,1 ': 4', 1 " - Terphenyl synthesis
Instead of using 3,5-diamino-4 "- (3-hydroxypropyloxy) -1,1 ': 4', 1" -terphenyl in step 3 of Example 13 above, Step 3 of Example 13 was repeated except that 3,5-diamino-4 '' - (6-hydroxyhexyloxy) -1,1 ': 4', 1 "≫ to obtain the desired compound.
Step 4: 3,5- Diamino -4 "-( 6- Acryloyloxyhexyloxy ) - 1,1 ': 4', 1 " - The Neil synthesis
(Tert-butoxycarbonyl) amino] -4 "- (3-hydroxypropyloxy) -1,1 ': 4', 1 ' (Tert-butoxycarbonyl) amino] -4 " - (6-hydroxyhexyloxy) -1,1 ': 4', 1 '' - terphenyl was used in the same manner as in <Step 4> of Example 13 to obtain the desired compound.
< Example 17> 3,5- Diamino -4 "-( 6- Methacryloyloxyhexyloxy ) -1,1 ': 4', 1 "-terphenyl synthesis
The procedure of Step 4 of Example 16 was repeated except that methacryloyl chloride was used instead of acryloyl chloride in Step 4 of Example 16 to obtain the desired compound .
< Example 18> 3,5- Diamino -4 "-( 6- Cinnamoyloxyhexyloxy ) -1,1 ': 4', 1 " - The Neil synthesis
The target compound was obtained in the same manner as in <Step 4> of Example 16, except that cinnamoyl chloride was used instead of acryloyl chloride in Step 4 of Example 16 above.
< Comparative Example 1> 3,5- Diaminobenzyl Acrylate Produce
3,5-diaminobenzyl acrylate was prepared by referring to Korean Patent Publication No. 10-0837788.
< Comparative Example 2 > 2- (3,5- Diaminophenoxy )ethyl Methacrylate Produce
2- (3,5-diaminophenoxy) ethyl methacrylate was produced by referring to Japanese Patent Publication No. 2013-145389.
< Comparative Example 3> (E) -3,5- Diaminobenzyl 3- ( Biphenyl Yl) Acrylate Produce
(E) -3,5-diaminobenzyl 3- (biphenyl-4-yl) acrylate was prepared by referring to Korean Patent Publication No. 10-0837788.
Table 1 summarizes the chemical structures of the compounds prepared in Examples 1-18.
< Example 19> Preparation of liquid crystal aligning agent 1
(9.8 mmol) of 4,4'-methylene dianiline, 1.06 g (9.8 mmol) of p-phenylenediamine, 2.92 g (5.6 mmol) of cholestan-3-ol 3,5-diaminobenzoate and The reaction solution in which 0.71 g (2.8 mmol) of 3,5-diamino-4'-acryloyloxybiphenyl prepared in Example 1 was dissolved in 45.08 g of N-methyl-2-pyrrolidone was stirred at room temperature, 2.74 g (13.9 mmol) of 2,3,4-cyclobutane tetracarboxylic dianhydride and 3.04 g (13.9 mmol) of pyromellitic dianhydride were slowly added dropwise to the reaction solution in 26.82 g of? -Butyrolactone for 2 hours And reacted for 6 hours to obtain a polyamic acid solution.
The obtained polyamic acid solution was dissolved in a mixed solvent of gamma -butyrolactone and butyl cellosolve in an amount of 8: 2 to prepare a solution having a concentration of 5% by weight. The solution was filtered with a filter having a size of 0.1 mu m to obtain a polyimide precursor (liquid crystal aligning agent) Respectively.
< Example 20> Preparation of liquid crystal aligning agent 2
(8.4 mmol) of 4,4'-methylene dianiline, 0.91 g (8.4 mmol) of p-phenylenediamine, 2.51 g (4.8 mmol) of cholestan-3-ol 3,5-diaminobenzoate, (2.4 mmol) of 3,5-diamino-4 '- (3-acryloyloxypropyloxy) biphenyl prepared in Example 4 was dissolved in 39.29 g of N-methyl-2-pyrrolidone While maintaining the solution at room temperature, 2.34 g (12.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2.62 g (12.0 mmol) of pyromellitic dianhydride were dissolved in 23.37 g of? -Butyrolactone The reaction solution was slowly added dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
The obtained polyamic acid solution was dissolved in a mixed solvent of gamma -butyrolactone and butyl cellosolve in an amount of 8: 2 to prepare a solution having a concentration of 5% by weight, and the solution was filtered through a 0.1-μm filter to obtain a polyimide precursor (liquid crystal aligning agent) Respectively.
< Example 21> Preparation of liquid crystal aligning agent 3
The polyamic acid solution prepared in Example 19 and the polyamic acid solution prepared in Comparative Example 4 were mixed at an 8: 2 ratio and stirred for 4 hours to obtain a polyamic acid mixed solution. And filtered through a filter of 0.1 mu m to prepare a polyimide precursor (liquid crystal aligning agent).
< Comparative Example 4> Production of liquid crystal aligning agent 4
(11.5 mmol) of 4,4'-methylenedianiline, 1.24 g (11.5 mmol) of p-phenylenediamine and 3.00 g (5.7 mmol) of cholestan-3-ol 3,5-diaminobenzoate were dissolved in N -Methyl-2-pyrrolidone was kept at room temperature, and 3.22 g (14.3 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 3.12 g of pyromellitic dianhydride (14.3 mmol) was slowly added dropwise to the reaction solution in which 31.34 g of? -Butyrolactone was dissolved for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
The obtained polyamic acid solution was dissolved in a solvent mixed with? -Butyrolactone and butyl cellosolve to prepare a solution having a concentration of 5% by weight, and the solution was filtered with a filter of 0.1 占 퐉 to prepare a polyimide precursor (liquid crystal aligning agent).
< Example 22> Production of Liquid Crystal Orientation Film Forming Substrate 1
The polyimide precursor (liquid crystal aligning agent) prepared in Example 19 was coated on a glass substrate having a transparent conductive film patterned by a spinner method. After the application, pre-baking was performed at 100 占 폚 for 30 minutes and baking was performed at 250 占 폚 for 1 hour to obtain a substrate on which a polyimide alignment film having a thickness of 700 占 was formed.
< Example 23> Production of Liquid Crystal Orientation Film Forming Substrate 2
The procedure of Example 22 was repeated except that the polyimide precursor (liquid crystal aligning agent) prepared in Example 20 was used instead of the polyimide precursor (liquid crystal aligning agent) prepared in Example 19 Thereby obtaining a substrate having a polyimide alignment film having a thickness of 700 Å.
< Example 24> Production of Liquid Crystal Orientation Film Forming Substrate 3
The procedure of Example 22 was repeated except that the polyimide precursor (liquid crystal aligning agent) prepared in Example 21 was used instead of the polyimide precursor (liquid crystal aligning agent) prepared in Example 19 Thereby obtaining a substrate having a polyimide alignment film having a thickness of 700 Å.
< Comparative Example 5 > Production of Substrate Forming Liquid Crystal Orientation Film 4
The procedure of Example 22 was repeated except that the polyimide precursor (liquid crystal aligning agent) prepared in Comparative Example 4 was used instead of the polyimide precursor (liquid crystal aligning agent) prepared in Example 19 Thereby obtaining a substrate having a polyimide alignment film having a thickness of 700 Å.
< Example 25> Production of liquid crystal display element 1
Two substrates were placed opposite to each other with a certain gap (cell gap) therebetween without rubbing the orientation film surface of the two liquid crystal alignment film formation substrates prepared in Example 22, and the peripheral portions of the two substrates were covered with an epoxy resin- , Liquid crystal was injected and filled in the cell gap defined by the surface of the substrate and the sealant, and the injection hole was sealed to fabricate the liquid crystal cell. Thereafter, a polarizing plate was bonded to the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell so that the direction of the polarization axis thereof was orthogonal to each other, thereby manufacturing a liquid crystal display device.
< Example 26> Production of liquid crystal display device 2
A liquid crystal display device was manufactured in the same manner as in Example 25 except that the liquid crystal alignment film formation substrate prepared in Example 22 was used instead of the liquid crystal alignment film formation substrate prepared in Example 22. [
< Example 27> Fabrication of Liquid Crystal Display Device 3
A liquid crystal display device was manufactured in the same manner as in Example 25 except that the liquid crystal alignment film formation substrate prepared in Example 24 was used instead of the liquid crystal alignment film formation substrate prepared in Example 22. [
< Comparative Example 6> Fabrication of Liquid Crystal Display Device 4
A liquid crystal display device was manufactured in the same manner as in Example 25 except that the liquid crystal alignment film formation substrate prepared in Example 22 was used instead of the liquid crystal alignment film formation substrate prepared in Comparative Example 5.
< Experimental Example 1> Evaluation of weight average molecular weight
Gel permeation chromatography (GPC) was performed to calculate the weight average molecular weights of the polymers contained in the liquid crystal aligning agents prepared in Examples 19-21 and Comparative Example 4. The retention time of the column packed with the polymer substance was measured at 60 ° C. using dimethylacetamide (DMAc) as a mobile phase. The average molecular weight and the retention time of the styrene polymer were corrected. The average of the polyamic acid solids The molecular weight was calculated.
As a result, the weight average molecular weight of the polymer contained in the liquid crystal aligning agent prepared in Example 19-21 and Comparative Example 4 was found to be about 2,000 to 1,500,000 g / mol.
< Experimental Example 2> Imidated Rate evaluation
Imide in the FT-IR (Fourier transform infrared spectroscopy ) For the measurement, on the benzene ring C = C stretching (stretching) the absorption intensity (A 1500) at 1500 ㎝ -1 as a function of temperature, 1380 ㎝ -1 ( imide) ring CN stretching Absorption intensity (A 1380 ) of the polyamic acid contained in the liquid crystal aligning agent prepared in Example 19-21 and Comparative Example 4 by the following equation (1) Respectively.
[Equation 1]
In the above equation (1)
T (%) is the imidization rate; And
* Is multiplication.
As a result, the imidization ratio of the polyamic acid contained in the liquid crystal aligning agent prepared in Examples 19-21 and Comparative Example 4 was found to be about 20-100%.
< Experimental Example 3> Evaluation of Characteristics of Liquid Crystal Orientation Film and Liquid Crystal Display Device
<3-1> Evaluation of surface tension
The liquid crystal alignment layers of the liquid crystal display devices prepared in Examples 25-27 and Comparative Example 6 were prepared according to the method described in literature (DK Owens. J. Appl., Pol., Vol. 13, 1741-1747 (1969) (Surface tension) of the liquid crystal alignment film was evaluated from the contact angle of pure water and the contact angle of methylene iodide measured on the surface of the liquid crystal alignment film.
Specifically, the relationship between the surface free energy (surface tension) of the liquid, the surface free energy of the solid, and the contact angle in the system in which the liquid is in contact with the surface of the solid (thin film) Lt; / RTI >
&Quot; (2) "
In Equation (2)
As described above, for pure water at < RTI ID = 0.0 > 20 C,
&Quot; (3) "
In Equation (3)
The contact angle was measured by using KRUSS DSA100 (manufacturer: KRUSS, model name: DSA100), and water and methylene iodide were dropped on the membrane and the average contact angle was measured for 10 seconds.
<3-2> Liquid crystal Orientation evaluation
The presence or absence of an abnormal domain in the liquid crystal cell when the liquid crystal display device manufactured in Examples 25-27 and Comparative Example 6 was applied with or cut off voltage was observed under a microscope.
≪ 3-3 > Pretilt angle evaluation
Ne laser light (632.8 nm) according to the method described in the literature (TJ Schffer, et.al., J., Appl., Phys., Vol. 19, 2013 Respectively.
<3-4> Evaluation of voltage holding ratio of liquid crystal display element
A voltage of 5 V was applied to the liquid crystal display device manufactured in Examples 25-27 and Comparative Example 6 for 60 micrometers second, and the voltage maintenance ratio after 16.67 milliseconds from the application of the voltage was measured.
<3-5> Director Fixed or not evaluation
The following experiments were carried out in order to more specifically evaluate whether the liquid crystal display device manufactured in Examples 25-27 and Comparative Example 6 had liquid crystal director fixation.
Specifically, the liquid crystal display devices manufactured in Examples 25-27 and Comparative Example 6 were subjected to a polarizing microscope, to which an image in which liquid crystal molecules were finally oriented by applying a driving voltage, And the image of the finally aligned state was obtained when the driving voltage was re - examined. As a result, the presence or absence of liquid crystal alignment was evaluated as O and X. The results of all the experiments including the Experimental Examples <3-1> to <3-4> are shown in Table 2 below.
[dyne / cm]
Fixed or not
As shown in Table 2, in the case of Examples 25-27 and Comparative Example 6 according to the present invention, as the liquid crystal aligning agent for vertical field driving, the surface tension, the orientation, the pretilt angle, the pretilt angle stability, Respectively.
In particular, the liquid crystal display devices of Examples 25-27 were easy to fix liquid crystal director, unlike the liquid crystal display device of Comparative Example 6. As a result, it can be seen that the liquid crystal display of the present invention can form a pre-scan square without irradiating UV and can determine the direction of the pre-scan rectangle without rubbing.
More specifically, FIGS. 1 and 2 show images of Example 25 and Comparative Example 6 of the images of the liquid crystal display device manufactured in Examples 25-27 and Comparative Example 6 obtained through the polarizing microscope.
FIG. 1 shows a photograph of a liquid crystal display device manufactured in Comparative Example 6 in which a liquid crystal molecule is finally aligned by applying a driving voltage using a polarizing microscope, a photograph in which the applied driving voltage is removed, It is an image representing a photo in an oriented state.
Fig. 2 is a photograph showing the state in which the liquid crystal molecules are finally aligned by applying a driving voltage to the liquid crystal display device manufactured in Example 25 using a polarization microscope, and a photograph in which the applied driving voltage is removed, It is an image representing a photo in an oriented state.
As shown in FIGS. 1 and 2, the shape of the region divided by the arrangement of the liquid crystals in a state in which the liquid crystal molecules are finally oriented by application of the driving voltage is irregular. This is because the liquid crystals are inclined in an arbitrary direction because the liquid crystal is arranged by applying a driving voltage to these electrodes in a state where no means for controlling the tilting direction of the liquid crystal is formed in any of the electrodes of the upper and lower glass substrates.
On the other hand, in the case of the liquid crystal display device manufactured in Example 25, when the driving voltage is initially applied and the liquid crystal molecules are finally aligned and the driving voltage is removed, the final alignment state of the liquid crystal molecules is the same.
That is, the shape of the region divided by the arrangement of the liquid crystal when the driving voltage is applied is always the same. This is because the driving voltage is applied between the electrodes of the upper and lower glass substrates to arrange the liquid crystal molecules in an arbitrary direction, and the diamine having the photoreactive group is photocured to semi-permanently fix the director of the liquid crystal molecules adjacent to the orientation film, . When the linearly polarized square is formed, the direction in which the liquid crystal molecules are tilted when the driving voltage is applied is fixed and the final alignment state is fixed. Therefore, when the voltage is applied, the liquid crystal molecules are easily returned to the final final alignment state. The response speed is improved. Therefore, the problem of afterimage of a moving image can be solved.
Claims (12)
[Chemical Formula 1]
(In the formula 1,
L is
X is a single bond, -CH 2 -, -S-, -NH- , or -O-, and;
Y is a single bond, - (CH 2 ) n -, - (CF 2 ) n -, - (CH 2 ) n - (CF 2 ) m - or - (CH 2 CH 2 O) n -
Wherein n and m are integers between 1 and 20;
Z is
L is
X is a single bond, -CH 2 -, -NH-, or -O-;
Y is a single bond, - (CH 2 ) n -, - (CF 2 ) n -, - (CH 2 ) n - (CF 2 ) m - or - (CH 2 CH 2 O) n -
Wherein n and m are integers between 1 and 10;
Z is
L is
X is a single bond, or -O-;
Y is a single bond, or - (CH 2 ) n -
Wherein n is an integer between 3 and 6;
Z is
Wherein the compound represented by Formula 1 is any one selected from the group consisting of the following compounds:
(1) 3,5-diamino-4'-acryloyloxybiphenyl;
(2) 3,5-diamino-4'-methacryloyloxybiphenyl;
(3) 3,5-Diamino-4'-cinnamoyloxybiphenyl;
(4) 3,5-Diamino-4 '- (3-acryloyloxypropyloxy) biphenyl;
(5) 3,5-Diamino-4 '- (3-methacryloyloxypropyloxy) biphenyl;
(6) 3,5-Diamino-4 '- (3-cinnamoyloxypropyloxy) biphenyl;
(7) 3,5-Diamino-4 '- (6-acryloyloxyhexyloxy) biphenyl;
(8) 3,5-Diamino-4 '- (6-methacryloyloxyhexyloxy) biphenyl;
(9) 3,5-Diamino-4 '- (6-cinnamoyloxyhexyloxy) biphenyl;
(10) 3,5-Diamino-4 "-acryloyloxy-1,1 ': 4', 1"-terphenyl;
(11) 3,5-Diamino-4 "-methacryloyloxy-1,1 ': 4', 1"-terphenyl;
(12) 3,5-Diamino-4 "-cinnamoyloxy-1,1 ': 4', 1"-terphenyl;
(13) 3,5-Diamino-4 '' - (3-acryloyloxypropyloxy) -1,1 ': 4', 1 "-terphenyl;
(14) 3,5-Diamino-4 "- (3-methacryloyloxypropyloxy) -1,1 ': 4', 1"-terphenyl;
(15) 3,5-Diamino-4 '' - (3-cinnamoyloxypropyloxy) -1,1 ': 4', 1 "-terphenyl;
(16) 3,5-Diamino-4 "- (6-acryloyloxyhexyloxy) -1,1 ': 4', 1"-terphenyl;
(17) 3,5-Diamino-4 '' - (6-methacryloyloxyhexyloxy) -1,1 ': 4', 1 "-terphenyl; And
(18) 3,5-Diamino-4 '' - (6-cinnamoyloxyhexyloxy) -1,1 ': 4', 1 "-terphenyl.
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
A step of reducing the compound represented by the formula (4) obtained in the step (1) to produce a compound represented by the formula (5) (step 2);
Reacting a compound represented by Chemical Formula 6 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 7 having a peptide protecting group (Step 3);
Reacting a compound represented by the formula (8) with a compound represented by the formula (7) to obtain a compound represented by the formula (9) (step 4); And
(Step 5) of removing the peptide protecting group of the compound represented by the formula (9) obtained in the step 4 to obtain a compound represented by the formula (1): < EMI ID =
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
L, X, Y, and Z are as defined in Chemical Formula 1 of claim 1;
R 1 is
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (4) (step 1);
Reacting the compound represented by the formula (4) and the compound represented by the formula (10) obtained in the above step 1 to prepare a compound represented by the formula (11) (step 2);
A step of performing a reduction reaction of the compound represented by the formula (11) obtained in the step 2 to prepare a compound represented by the formula (12) (step 3);
Reacting a compound represented by the formula (6) with the compound represented by the formula (12) obtained in the step 3 to prepare a compound represented by the formula (13) in which a peptide protecting group is formed (step 4);
Reacting a compound represented by the formula (8) with a compound represented by the formula (13) to obtain a compound represented by the formula (14) (step 5); And
(Step 6) of removing the peptide protecting group of the compound represented by the formula (14) obtained in the step 5 to obtain a compound represented by the formula (1).
[Reaction Scheme 2]
(In the above Reaction Scheme 2,
L, X, Y, and Z are as defined in Chemical Formula 1 of claim 1;
R 1 is
[Chemical Formula 15]
[Chemical Formula 16]
(In the above formulas 15 and 16,
X 1 and X 2 are independently a tetravalent organic group derived from a single species or a combination of two or more species selected from the group consisting of alicyclic dianhydrides and aromatic acid dianhydrides;
Y 1 And Y < 2 > independently represent a divalent organic group derived from a single diamine monomer compound or a combination of two or more thereof, and the diamine monomer compound is necessarily a photoreactive diamine monomer compound represented by the general formula (1) / RTI > And
The repeating units represented by formulas (15) and (16) independently have a weight average molecular weight (Mw) of 1,000 to 200,000 g / mol.
The alicyclic dianhydride may be 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracar 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6- Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- Dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4,5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] - furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3- ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro- 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro- , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] 9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) - 1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and 3-oxabicyclo [3.2.1] octane- - spiro-3 '- (tetrahydrofuran-2', 5'-dione);
Wherein the aromatic acid dianhydride is selected from the group consisting of pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4 ' -Biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4, 4'-biphenylether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, Bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bisphenol-bis (triphenylphthalic acid) dianhydride, bis (Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol- Hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate) and 2,2-bis (4-hydroxyphenyl) Wherein the liquid crystal aligning agent is at least one selected from the group consisting of propane-bis (anhydrotrimellitate).
Y 1 And Y 2 are independently a divalent organic group derived from a combination of two or more diamine monomer compounds, the diamine monomer compound may further include at least one member selected from the group consisting of compounds represented by the following general formulas A liquid crystal aligning agent characterized by:
[Chemical Formula 19]
H 2 NA-NH 2
(Wherein the compound represented by Formula 19 is at least one compound selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4 ' Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'- 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3 (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- , 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'- diaminobiphenyl, 2,2'- Diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '- (p-phenyleneisopropylidene) , 4,4'- (m-phenylene isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, di (4-aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 1,1-methoxysilylene diamine, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptane, Methylene diamine, octamethylene diamine, nonamethylene diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 2,7] -undecylene Aliphatic or alicyclic diamines such as dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane; Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, (3,5-diaminophenyl) -3-decylsuccinimide and 1- (3,5-diaminophenyl) - 3- Octadecylsuccinimide, and octadecylsuccinimide).
[Chemical Formula 20]
(In the above formula (20)
R 21 is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or - (CH 2 ) m -, wherein m is an integer of 1 to 12;
R 22 is unsubstituted or one or more fluorine groups (-F) a substituted C 3 -20 straight or branched chain alkyl, unsubstituted or substituted C 6 -10 aryl, or a steroid group, and
Any of -CH 2 - included in the above unsubstituted or straight-chain or branched alkyl of C 3 -20 substituted with at least one fluorine group (-F) is -O-, -CH = CH- or -C≡C- , ≪ / RTI >
The aryl-substituted C 6 -10 is -F, -CH 3, -OCH 3, -OCH 2 F, -OCHF 2 or -OCF 3 a C 6 -10 are one or more substituents selected from the group consisting of a substituted Lt; / RTI >
The steroid group
[Chemical Formula 21]
(In the formula (21)
R 2 is C 3 -6 2 is an organic aliphatic or aromatic hydrocarbon group of;
and m is an integer of 1 to 100).
The liquid crystal aligning agent according to claim 7, wherein the repeating unit represented by the general formula (15) and the general formula (16) is 5 to 70 mol% based on the total amount of the liquid crystal aligning agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104117221A TW201544489A (en) | 2014-05-30 | 2015-05-28 | Preparation of photoreactive diamine monomer and alignment layer for LCD using the same |
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| KR1020140066300 | 2014-05-30 | ||
| KR20140066300 | 2014-05-30 |
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| KR1020150063895A KR20150139426A (en) | 2014-05-30 | 2015-05-07 | Synthesis of photo-reactive diamine monomer for LCD alignment layer |
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| KR (1) | KR20150139426A (en) |
| TW (1) | TW201544489A (en) |
| WO (1) | WO2015182894A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538031A (en) * | 2020-12-02 | 2021-03-23 | 吉林奥来德光电材料股份有限公司 | Antioxidant for thin film packaging, composition and application thereof |
| US11073728B2 (en) | 2016-11-28 | 2021-07-27 | Lg Chem, Ltd. | Liquid crystal alignment film, method for preparing the same and liquid crystal display device using the same |
| US11370971B2 (en) | 2017-10-17 | 2022-06-28 | Lg Chem, Ltd. | Liquid crystal alignment film and liquid crystal display device using the same |
| US11667843B2 (en) | 2019-01-17 | 2023-06-06 | Lg Chem, Ltd. | Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200026376A (en) * | 2018-08-30 | 2020-03-11 | 삼성디스플레이 주식회사 | Photo alignment agent and liquid crystal display |
| CN112266457B (en) * | 2020-11-06 | 2022-04-05 | 广州市嵩达新材料科技有限公司 | Photocuring hydrophilic polyurea nano particle and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5359029B2 (en) * | 2007-06-06 | 2013-12-04 | Ｊｎｃ株式会社 | Acid dianhydride, liquid crystal alignment film, and liquid crystal display element |
| TWI393732B (en) * | 2009-03-31 | 2013-04-21 | Daxin Materials Corp | Liquid crystal alignment solution |
| JP5975227B2 (en) * | 2011-03-31 | 2016-08-23 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element |
-
2015
- 2015-05-07 WO PCT/KR2015/004548 patent/WO2015182894A1/en active Application Filing
- 2015-05-07 KR KR1020150063895A patent/KR20150139426A/en unknown
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11073728B2 (en) | 2016-11-28 | 2021-07-27 | Lg Chem, Ltd. | Liquid crystal alignment film, method for preparing the same and liquid crystal display device using the same |
| US11370971B2 (en) | 2017-10-17 | 2022-06-28 | Lg Chem, Ltd. | Liquid crystal alignment film and liquid crystal display device using the same |
| US11667843B2 (en) | 2019-01-17 | 2023-06-06 | Lg Chem, Ltd. | Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same |
| CN112538031A (en) * | 2020-12-02 | 2021-03-23 | 吉林奥来德光电材料股份有限公司 | Antioxidant for thin film packaging, composition and application thereof |
| CN112538031B (en) * | 2020-12-02 | 2022-05-06 | 吉林奥来德光电材料股份有限公司 | Antioxidant for thin film packaging, composition and application thereof |
Also Published As
| Publication number | Publication date |
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| TW201544489A (en) | 2015-12-01 |
| WO2015182894A1 (en) | 2015-12-03 |
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