CN111320567A

CN111320567A - Reactive light stabilizer compound and liquid crystal composition containing same

Info

Publication number: CN111320567A
Application number: CN201911300831.XA
Authority: CN
Inventors: 尹星壹; 崔珍郁; 白宇铉; 李宰荣; 宋贞寅; 李炫知; 申圭淳
Original assignee: Dongjin Semichem Co Ltd
Current assignee: Dongjin Semichem Co Ltd
Priority date: 2018-12-17
Filing date: 2019-12-17
Publication date: 2020-06-23
Also published as: KR20200074814A

Abstract

The present invention relates to a reactive light stabilizer compound, a liquid crystal composition comprising the same, and a liquid crystal display device comprising the same. The reactive light stabilizer compound according to an embodiment of the present invention can improve the residual image by increasing the Voltage Holding Ratio (VHR) and decreasing the RDC in a mode requiring an exposure process while achieving the low temperature stability and the residual image improving effect without adversely affecting various physical properties of the liquid crystal composition, such as the clear point, the elastic modulus, the dielectric anisotropy, or the refractive index anisotropy of the liquid crystal composition.

Description

Reactive light stabilizer compound and liquid crystal composition containing same

Technical Field

The present invention relates to a reactive light stabilizer compound, a liquid crystal composition comprising the same, and a liquid crystal display device comprising the same.

Background

A Liquid Crystal Display (LCD) is one of the most widely used flat panel displays (flat panel displays) at present. The liquid crystal display device generates an electric field in the liquid crystal layer by applying a voltage to the electric field generating electrodes to orient a plurality of liquid crystal molecules of the liquid crystal layer and adjusts light transmittance through the liquid crystal layer, so that a switch (ON/OFF) can be displayed. They are applicable to transmissive or reflective type liquid crystal display devices, and thus, various modes such as Twisted Nematic (TN), in-Plane Switching (IPS), Optically compensated bend (O CB), Vertical Alignment (VA), Electrically Controlled Birefringence (ECB), Super Twisted Nematic (STN), and the like have been developed.

Liquid crystal display devices used in various industrial applications are required to satisfy various requirements, for example, to operate in a wide temperature range with low voltage driving and high-speed response, i.e., to have a large absolute value of Δ ∈, a low rotational viscosity (η), and a high nematic phase-isotropic liquid phase transition temperature (tni), and to have appropriate dielectric anisotropy, refractive index anisotropy, and elastic modulus.

In addition to these various physical properties, the liquid crystal composition used in the liquid crystal display device is required to have chemical resistance against external stimuli such as moisture, air, heat, light (infrared ray, visible light, ultraviolet ray) and the like. In particular, the liquid crystal display device receives light from a backlight, and thus stability of liquid crystal becomes a problem, and a display defect known as an image sticking (image sticking) may be caused by a light-induced reaction of a liquid crystal substance. This becomes a factor of greatly reducing the life of the liquid crystal display device.

To prevent such a problem, the liquid crystal composition may contain a light stabilizer. Examples of the conventional photostabilizer include an ultraviolet screening agent (UV screener), an ultraviolet absorber (UV absorber), a delustering agent (Quencher), and a Radical scavenger (radial scavenger), and in the field of liquid crystal display devices, a Hindered Amine photostabilizer (hals, Hindered Amine Light Stabilzer) is generally used as a Radical scavenger.

For example, international patent publication No. WO 2009/129911 proposes a nematic liquid crystal mixture having negative dielectric anisotropy, which contains a small amount of a compound of the following formula (TINUVIN, registered trademark) 770 as a light stabilizer. However, the corresponding liquid crystal mixtures have properties which are unsuitable for many practical applications. These are not sufficiently stable to illumination using typical Cold Cathode Fluorescent Lamp (CCFL) backlights, among other things.

In addition, some of the conventionally known hindered amine light stabilizers have excellent low-temperature stability but no afterimage improving effect, and on the contrary, some of the other hindered amine light stabilizers have a problem that the afterimage improving effect is excellent but the low-temperature stability is poor.

Therefore, there is an urgent need to develop a novel light stabilizer compound which can improve the residual image by increasing the Voltage Holding Ratio (VHR) and reducing the RDC in a mode requiring an exposure process while achieving the low temperature stability and the residual image improving effect without affecting various physical properties of the liquid crystal composition such as the transparent point, the elastic modulus, the dielectric anisotropy, or the refractive index anisotropy of the liquid crystal composition.

Documents of the prior art

Patent document

International patent publication No. WO 2009/129911

Disclosure of Invention

The present invention has been made to solve the above problems, and it is an object of the present invention to provide a light stabilizer compound capable of improving residual images by increasing a Voltage Holding Ratio (VHR) and reducing RDC in a mode requiring an exposure process, without adversely affecting various physical properties of a liquid crystal composition such as a transparent point, an elastic modulus, dielectric anisotropy, or refractive index anisotropy of the liquid crystal composition, and to provide a liquid crystal composition containing the same.

However, the problems to be solved by the present invention are not limited to the above-described problems, and other problems not described should be clearly understood by those skilled in the art from the following description.

A first embodiment of the present invention provides a reactive light stabilizer compound represented by the following chemical formula I.

Chemical formula I

In the chemical formula I above, the compound of formula I,

T₁to T₃Each independently hydrogen (H), one of the following chemical formulas 1 to 4, or a polymerizable functional group (in this case, T)₁To T₃At least one of the following chemical formulas 1 to 3, and the remaining at least one is the polymerizable functional group),

sp is a single bond, -CH ═ CH-, -C ≡ C-, -CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-CO-、-O-、-OCH₂-、-CH₂O-、-OCF₂-or-CF₂O-，

R¹Is H or C_1～10Straight or branched alkyl (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

R²to R⁵Each independently is C_1～10Straight or branched alkyl (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

y is H, C_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10Straight chain or branched alkenyl (in this case, C)_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10One or more nonadjacent methylene groups (-CH) of a linear or branched alkenyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

n2 is an integer from 1 to 4,

A₁to A₃Each independently represented by the following chemical formula 5,

chemical formula 5

L is a single bond, -CH ═ CH-, -C ≡ C-, -CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-CO-、-O-、-OCH₂-、-CH₂O-、-OCF₂-or-CF₂O-，

Z is C_1～10Straight or branched alkylene or C_5～20Cyclic alkylene (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkylene group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkylene group may be replaced by F, Cl or CF₃Alternative, C_5～20More than one carbon (C) atom of the cyclic radical being able to be substituted by O, N or S, C_5～20More than one hydrogen of a cyclic group can be represented by F, Cl or CF₃Instead) of the above-described embodiment,

n3 is an integer of 1 or 2, when n3 is 2, L, Z can be the same or different.

A second embodiment of the present invention provides a liquid crystal composition comprising the light stabilizer compound represented by the above chemical formula I.

A third embodiment of the present invention provides a liquid crystal display device including the liquid crystal composition.

The light stabilizer compound according to an embodiment of the present invention can improve the low temperature stability and the residual image while not adversely affecting various physical properties of the liquid crystal composition, such as a transparent point, an elastic modulus, dielectric anisotropy, or refractive index anisotropy of the liquid crystal composition, and can improve the residual image by increasing a Voltage Holding Ratio (VHR) and reducing RDC in a mode requiring an exposure process.

Drawings

FIG. 1 shows a Nuclear Magnetic Resonance (NMR) spectrum of a reactive light stabilizer compound of an example of the invention.

FIG. 2 shows the nuclear magnetic resonance spectrum of a reactive light stabilizer compound according to an embodiment of the present invention.

Detailed Description

Examples and embodiments of the present invention are described in detail below with reference to the accompanying drawings so that those skilled in the art can easily implement the invention.

However, the present invention can be realized in various forms and is not limited to the examples and embodiments described herein. In the drawings, for the purpose of clearly explaining the present invention, portions not related to the explanation are omitted, and like reference numerals are given to like portions throughout the specification.

Throughout the present specification, when an element is "on" another element, it includes not only the case where the element is in contact with the other element, but also the case where the other element is present between the two elements.

Throughout the present specification, when a portion "includes" a structural element, it is meant that other structural elements may be included, but not excluded, unless otherwise stated. The terms "about," "substantially," and the like, as used throughout the specification are used in the sense of their numbers or close to their numbers to indicate inherent preparation and material tolerances, so as to prevent an assiduous intruder from inadvertently making use of the disclosure in which exact or absolute numbers are mentioned to assist in understanding the invention. The term "step(s)" or "step(s)" used throughout the present specification does not mean "step(s) used for.

Throughout the present specification, the term "combination thereof" contained in an expression of Markush (Markush) means a mixture or combination of one or more kinds selected from the group consisting of a plurality of structural elements described in an expression of Markush, and means including one or more kinds selected from the group consisting of the plurality of structural elements.

Throughout the present specification, the expression "A and/or B" means "A or B, or A and B".

Throughout the present specification, the term "aryl" or "arylene" may be meant to encompass C_6-50The aromatic hydrocarbon ring group of (2), for example, phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthryl, triphenylalkenyl, phenylalkenyl,

A base,Fluoranthenyl, benzofluorenyl, benzotriaenyl, benzo

An aromatic ring such as a phenyl group, an anthracenyl group, a stilbene group, or a pyrenyl group, the term "heteroaryl group" or "heteroarylene group" as the C group containing at least one hetero element_2-50The aromatic ring of (a) is meant to include, for example, a heterocyclic group formed of pyrrolinyl, pyrazinyl, pyridyl, indolyl, isoindolyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthryl cry yl, acridinyl, phenanthrolinyl, thienyl, and a heterocyclic group formed of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an indole ring, a quinoline ring, an acridine ring, a pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, a piperazine ring, a carbazole ring, a furan ring, a thiophene ring, an oxazole ring, an oxadiazole ring, a benzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring, and a dibenzofuran ring.

Throughout the present specification, the term "substituted" or "substitutable" may mean substituted with one or more groups selected from the group consisting of deuterium, oxygen, halogen, amino, nitrile, nitro, silane or C_1～30Alkyl of (C)_2～30Alkenyl of, C_1～30Alkoxy group of (C)_3～20Cycloalkyl of, C_3～20Heterocycloalkyl of (A), C_6～30Aryl and C_2～30Substituted with one or more groups of the group consisting of heteroaryl groups of (a). In addition, throughout the present specification, the same reference numerals may have the same meaning unless otherwise specified.

Reactive light stabilizer compounds

Chemical formula I

In the chemical formula I above, the compound of formula I,

T₁to T₃Each independently hydrogen (H), one of the following chemical formulas 1 to 4, or a polymerizable functional group (in this case, T)₁To T₃At least one of the above chemical formulas 1 to 3, and the remaining at least one is the above polymerizable functional group),

R¹Is hydrogen (H) or C_1～10Straight or branched alkyl (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

R²to R⁵Each independently is C_1～10Straight or branched alkyl (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

y is H, C_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10Straight chain or branched alkenyl (in this case, C)_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10One or more linear or branched alkenyl groupsAdjacent methylene (-CH)₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10More than one hydrogen of the linear or branched alkyl group can be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

n2 is an integer from 1 to 4,

A₁to A₃Each independently represented by the following chemical formula 5,

chemical formula 5

Z is C_1～10Straight or branched alkylene or C_5～20Cyclic alkylene (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkylene group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkylene group may be replaced by F, Cl or CF₃Alternative, C_5～20More than one carbon (C) atom of the cyclic group being substituted by O, N or S, C_5～20More than one hydrogen of the cyclic group may be replaced by F, Cl or CF₃Instead) of the above-described embodiment,

n3 is an integer of 1 or 2, when n3 is 2, L, Z can be the same or different.

That is, the light stabilizer compound of the present invention is characterized by including a polyfunctional group such as amine as a core (core). This has a linker such as an alkyl group, and thus improves solubility, thereby obtaining excellent low-temperature stability. Further, by introducing one or more hindered amine light stabilizer functional groups to the terminal of the amine, the afterimage of the liquid crystal display device can be improved. Furthermore, since one or more polymerizable groups are introduced into the other end of the amine, the reactive liquid crystal monomer (RM) is directly bonded to the amine in the exposure step, and thus a high Voltage Holding Ratio (VHR) can be maintained.

According to an embodiment of the present invention, the polymerizable functional group may be one of the following formulas, specifically may be acrylate or methacrylate:

according to an embodiment of the present invention, the above T₁To T₃One or more of them may be the following chemical formula 1 or chemical formula 2, and the remaining at least one may be the polymerizable functional group. Thus, the Voltage Holding Ratio (VHR), Residual DC (RDC), resistivity and other characteristics of the liquid crystal display device can be improved, and the residual image can be improved.

Also, according to an embodiment of the invention, Sp may be-CH ═ CH-, -C ≡ C-, -CH ≡ C ═ CH-, -C ≡ C-, -C ═ CH-, -C ≡ C-, -C ═ C-, -C₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-CO-、-O-、-OCH₂-、-CH₂O-、-OCF₂-or-CF₂O-may be specifically-COO-.

And, according to an embodiment of the present invention, the above R¹May be hydrogen (H).

Also, according to an example of the present invention, n2 may be an integer of 1 or 2, and specifically, n2 may be 2. When n2 is 2, the structure can be more stable.

And, according to an example of the present invention,

l is a single bond,

z may be C_1～10Straight or branched alkylene (in this case, C)_1～10One or more methylene groups (-CH) of a linear or branched alkylene group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10Linear or branched vinylenesMore than one hydrogen (H) of the alkyl group may be replaced by F, Cl or CF₃Instead). This has a linker such as an alkyl group, and thus improves solubility, thereby obtaining excellent low-temperature stability.

The reactive light stabilizer compound of the above chemical formula I according to an embodiment of the present invention has a multi-functional structure by introducing into the amine core group, thereby improving solubility and having excellent low temperature stability. In addition, the reactive light stabilizer compound of the chemical formula I has a Hindered Amine Light Stabilizer (HALS) functional group introduced into a terminal thereof, and thus performs a scavenger (scuvenger) action capable of effectively trapping ions, radicals, and the like remaining in the liquid crystal composition or the alignment film, thereby exhibiting an excellent residual image improving effect of the liquid crystal display device. Further, the reactive light stabilizer compound of the chemical formula I is directly bonded to the reactive liquid crystal monomer (RM) in the exposure process, thereby increasing the intermolecular bonding force and effectively removing the unreacted residual substance, thereby maintaining a high Voltage Holding Ratio (VHR).

In one embodiment of the present invention, the reactive light stabilizer compound represented by the above chemical formula I can be synthesized by the following reaction formula 1, but is not limited thereto, and can be synthesized by various methods.

Reaction scheme 1

At this time, when there is one polymerizable functional group, the synthesis is performed by the same method as in the reaction formula 1, and specifically, the synthesis may be performed through an intermediate step process as in the following reaction formula 2.

And, in reaction formula 1, use

Etc. instead of

Alternatively, various forms of the reactive light stabilizer compound represented by the following chemical formula I can be synthesized by substituting methacrylic acid for acrylic acid or the like.

In one embodiment of the present invention, the reactive compound represented by the above chemical formula I may be a compound set forth below. But is not limited thereto.

Polymerizable composition

In general, in a PSA-mode or PS-VA mode liquid crystal display device, a proper line tilt angle is maintained by a liquid crystal medium mixed with a polymerizable compound. In general, in the VA mode, a line tilt angle of 87 to 89 DEG is preferably maintained.

In one embodiment of the present invention, the polymerizable compound may be a compound represented by the following compound 11 and compound 12. But is not limited thereto.

Compound 11

Compound 12

Liquid crystal composition

The second embodiment of the present invention provides a liquid crystal composition in which the reactive light stabilizer compound represented by the above chemical formula I includes one or more species. In the liquid crystal composition of the present embodiment, the contents described in the first embodiment of the present invention can be applied to any one of them, and the present invention is not limited to this.

The liquid crystal composition includes the reactive light stabilizer compound represented by the chemical formula I, so that the low temperature stability and the afterimage improvement effect can be achieved without adversely affecting various physical properties of the liquid crystal composition, such as a transparent point, an elastic coefficient, dielectric anisotropy, or refractive index anisotropy of the liquid crystal composition, and the Voltage Holding Ratio (VHR) is increased and the RDC is reduced in a mode requiring an exposure process, thereby improving the afterimage.

Also, according to an example of the present invention, the light stabilizer compound represented by the above chemical formula I may include 0.001 to 5 parts by weight, 0.001 to 4 parts by weight, 0.001 to 3 parts by weight, 0.001 to 2 parts by weight, 0.001 to 1 part by weight, specifically, 0.001 to 0.5 parts by weight, 0.001 to 0.3 parts by weight, 0.003 to 1 part by weight, 0.003 to 0.5 parts by weight, or 0.003 to 0.3 parts by weight in 100 parts by weight of the liquid crystal composition, which may not be limited thereto. The liquid crystal composition may not contain a light stabilizer compound in an amount of 100 parts by weight. When the content is more than the above range, the physical properties of the liquid crystal composition may be changed, and when the content is less than the above range, the improvement effect may be reduced.

On the other hand, in the liquid crystal composition, the reactive light stabilizer compound represented by the above chemical formula I may be combined with a plurality of kinds of liquid crystal compounds according to the characteristics of a liquid crystal panel to which the composition is applied.

According to an embodiment of the present invention, the liquid crystal composition may further include a compound represented by the following chemical formula II.

Chemical formula II

In the chemical formula II described above,

ring A and ring B are each independently a 1, 4-cyclohexylene group in which the ring carbon (C) is substituted or unsubstituted with one or more oxygen (O), or a 1, 4-phenylene group in which one or more hydrogen (H) is substituted or unsubstituted with halogen,

R⁶and R⁷Each independently is C_1～7Alkyl radical, C_1～7Alkoxy or C_2～7An alkenyl group, which is a radical of an alkenyl group,

n4 is an integer from 1 to 3, and when n4 is 2 or 3, rings B can be the same or different.

According to an embodiment of the present invention, the halogen may be fluorine (F).

According to an embodiment of the present invention, the compound represented by the above chemical formula II may include, but is not limited to, compounds represented by the following chemical formulas II-1 to II-6.

Chemical formula II-1

Chemical formula II-2

Chemical formula II-3

Chemical formula II-4

Chemical formula II-5

Chemical formula II-6

In the above chemical formulas II-1 to II-6,

R⁶and R⁷The same as defined in formula II above.

The compound represented by the above chemical formula II-1 may function to maintain the viscosity of the liquid crystal composition low.

In one embodiment of the present invention, the compound represented by the above chemical formula II-1 may include compounds represented by the following chemical formulae II-1-1 to II-1-7. These compounds can be particularly effective in maintaining a low viscosity of the liquid crystal composition.

Chemical formula II-1

Chemical formula II-1-2

Chemical formula II-1-3

Chemical formula II-1-4

Chemical formula II-1-5

Chemical formula II-1-6

Chemical formula II-1-7

The compound represented by the above chemical formula II has a dielectric anisotropy of about-1 to 3, and is a compound that can provide a liquid crystal composition having a low rotational viscosity and maintaining a wide liquid crystal upper range.

In one embodiment of the present invention, the compound represented by the above chemical formula II may be included in an amount of 10 to 50 parts by weight in 100 parts by weight of the liquid crystal composition, but is not limited thereto. When less than 10 parts by weight, the liquid crystal composition exceeds the range on the liquid crystal under normal temperature conditions or it may be difficult to achieve low rotational viscosity, and when more than 50 parts by weight, the dielectric anisotropy of the liquid crystal composition decreases, so that it may be difficult to adjust the driving voltage of the display.

In particular, the substance having a double bond at the terminal is a substance weaker than an afterimage due to Ultraviolet (UV) rays, like the compound represented by the above chemical formula II-1-2. When the compound represented by chemical formula I is added to the liquid crystal composition comprising 10 to 50 parts by weight of the compound represented by chemical formula II-1-2, the afterimage of the composition can be improved.

In the present invention, 100 parts by weight of the total liquid crystal composition can be calculated as the content of all the components contained in the liquid crystal composition, but is not limited thereto, and for example, may be calculated by including a liquid crystal compound, a light stabilizer compound, and other additives.

However, the present invention can be embodied in combination with a plurality of compounds having different forms, and is not limited to the chemical formula II described herein.

Liquid crystal display device having a plurality of pixel electrodes

A third embodiment of the present invention provides a liquid crystal display device including the liquid crystal composition. The contents described in the first embodiment or the second embodiment of the present invention can be applied to the liquid crystal display device of this embodiment, and the present invention is not limited to this.

Therefore, the liquid crystal composition can be applied to a liquid crystal display device by various methods known In the art to which the present invention pertains, and can be prepared as a liquid crystal display device of various modes such as Vertical Alignment (VA), multi-domain Vertical Alignment (MVA), Patterned Vertical Alignment (PVA), Polymer Stabilized Alignment (PSA), Polymer Stabilized Vertical Alignment (PS-VA), Polymer Stabilized Vertical Alignment (IPS, In-Plane Switching), Fringe Field Switching (FFS, front Field Switching), Plane line Switching (PLS, Plane to line Switching), Twisted nematic (TN, Twisted nematic), and the like.

However, the present invention is not limited to the liquid crystal display device described herein as long as it can be applied to liquid crystal display devices of various forms.

Examples

Hereinafter, the present invention will be described more specifically by examples, and the scope of the present invention is not limited to the examples.

The liquid crystal compounds used in examples and comparative examples are represented by codes. The code is prepared by sequentially recording marks of rings forming a central group of the liquid crystal compound from the left side, recording linking groups for linking the rings of the central group in order, and then recording terminal groups on the right side. In this case, although no distinction is made between the ring connecting the center group and the connecting group connecting the ring of the center group, distinction is made between the center group and the terminal groups by the "-" and distinction is made between the terminal groups by the "-" or the like. The individual notations (codes) of the substances are collated in the following Table 1.

TABLE 1

Referring to table 1 above, the following codes refer to liquid crystal compounds having the structures shown below.

Examples of the invention

BAF-3.O2

Preparation examples 1 to 3: preparation of Mixed liquid crystals having a negative (-) dielectric constant

The liquid crystal compositions of the following examples were prepared by mixing the components described in the following table 2 in the amounts described, and the physical properties of the finish were shown.

TABLE 2

Code	Preparation example 1	Preparation example 2	Preparation example 3
				BB-2.3	18.8	19.7
BB-3.4	6.0	3.8
				BB-3.V			20.0
BB-3.U1			11.0
				AA-1.3	4.8	4.6
AA-1.5	14.0	6.8
				BAA-3.1		6.8
BAA-3.2	5.0	5.3	5.7
				BF-3.O2		8.7	11.5
BF-5.O2			6.8
				AF-3.O2		11.0	12.0
BBF-3.O1	6.6
				BBF-3.O2		9.2	11.0
BBF-5.O2			4.0
				BAF-2.O2	9.0		9.0
BAF-3.O2	9.0	4.7	9.0
				BYF-3.O2	8.4
BBYF-2.O2	9.2	9.7
				BBYF-3.O2	9.2	9.7

(unit: weight ratio)

The liquid crystal composition prepared above showed physical properties as finished in the following table 3.

TABLE 3

Preparation example 4: preparation of Mixed liquid crystals having a Positive (-) dielectric constant

The liquid crystal compositions of the following examples were prepared by mixing the components described in the following table 4 in the amounts described, and the physical properties of the finish were shown.

TABLE 4

(unit: weight ratio)

Example 1: synthesis of Compound 5

[ Synthesis example 1] Synthesis of Compound 1

As shown in the following reaction scheme 1, 5-bromo-1-pentanol (5-bromo-1-pentanol) (50.00g, 299.31mmol) and 3,4-dihydro-2H-pyran (3,4-dihydro-2H-pyran) (30.21g, 359.17mmol) were mixed in 500mL of tetrahydrofuran (tetrahydrofuran), to which p-toluenesulfonic acid (0.57g, 2.99mmol) was added and stirred for 1 hour. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and water, the reaction product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain compound 1(64.50g, 86% yield (yield)) as a colorless transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝4.55-4.56(1H，m)，3.82-3.87(1H，m)，3.71-3.77(1H，m)，3.48-3.50(1H，m)，3.35-3.43(3H，m)，1.49-1.92(12H，m)

Reaction scheme 1

[ Synthesis example 2] Synthesis of Compound 2

As shown in the following reaction scheme 2, Compound 1(30.30g, 120.64mmol) and glycine methyl ester hydrochloride (7.57g, 60.32mmol) were mixed in 200mL of acetonitrile (acetonitrile), to which potassium carbonate (potassium carbonate) (33.35g, 241.28mmol) and potassium iodide (potassium iodide) (40.05g, 241.28mmol) were added to carry out a back-and-forth flow reaction for 48 hours. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and water, the reaction product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain compound 2(18.74g, 72% yield) as a colorless transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝4.55-4.56(2H，m)，3.83-3.88(2H，m)，3.71-3.75(2H，m)，3.69(3H，s)，3.48-3.50(2H，m)，3.34-3.40(2H，m)，3.32(2H，s)，2.56(4H，t，J＝7.2Hz)，1.32-1.85(24H，m)

Reaction formula 2

[ Synthesis example 3] Synthesis of Compound 3

As shown in the following reaction scheme 3, compound 2(15.44g, 35.94mmol) and 4-hydroxy-2,2,6,6-tetramethylpiperidine (4-hydroxy-2,2,6,6-tetramethylpiperidine) (11.00g, 71.88mmol) were mixed in 200mL of toluene (tolumene), to which titanium isopropoxide (2.13mL, 7.19mmol) was added and subjected to reflux reaction for 24 hours. The reaction solution was concentrated, and the concentrated reaction product was purified by silica gel column chromatography to obtain compound 3(13.50g, 68% yield) as a yellow liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝5.22(1H，tt，J＝11.2，4.0Hz)，4.55-4.57(2H，m)，3.83-3.89(2H，m)，3.70-3.76(2H，m)，3.47-3.50(2H，m)，3.35-3.39(2H，m)，3.30(2H，s)，2.58(4H，t，J＝7.2Hz)，1.91(2H，dd，J＝12.0，4.0Hz)，1.31-1.85(24H，m)，1.23(6H，s)，1.11-1.17(8H，m)

Reaction formula 3

[ Synthesis example 4] Synthesis of Compound 4

As shown in the following reaction formula 4, compound 3(13.50g, 23.33mmol) was mixed with 90mL of methanol (methanol), and then 1N aqueous hydrogen chloride (1N hydrochloric acid) (90mL) was added thereto and stirred for 30 minutes. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and 2M aqueous sodium hydroxide solution (2M NaOH solution), the reaction product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain compound 4(5.60g, 60% yield) as a colorless and transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝5.22(1H，tt，J＝11.2，4.0Hz)，3.63(4H，t，J＝6.4Hz)，3.28(2H，s)，2.58(4H，t，J＝7.2Hz)，1.92(2H，dd，J＝12.4，4.4Hz)，1.34-1.61(12H，m)，1.23(6H，s)，1.12-1.18(8H，m)

Reaction formula 4

[ Synthesis example 5] Synthesis of Compound 5

As shown in the following reaction scheme 5, Compound 4(3.10g, 8.02mmol) and methacrylic acid (1.70mL, 20.05mmol) were mixed in 120mL of dichloromethane (dichromethane), to which N, N '-dicyclohexylcarbodiimide (N, N' -dicyclohexylcarbodiimide) (4.14g, 20.05mmol) and 4-dimethylaminopyridine (4-dimethylaminopyridine) (0.98g, 8.02mmol) were added and stirred for 24 hours. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and water, the reaction product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain compound 5(1.10g, 26% yield) as a colorless transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝6.08(2H，s)，5.54(2H，s)，5.22(1H，tt，J＝11.2，4.0Hz)，4.13(4H，t，J＝6.4Hz)，3.29(2H，s)，2.58(4H，t，J＝6.4Hz)，1.89-1.93(8H，m)，1.68(4H，quintet，J＝6.8Hz)，1.48(4H，quintet，J＝7.2Hz)，1.38(4H，quintet，J＝7.2Hz)，1.23(6H，s)，1.11-1.17(8H，m)

Reaction formula 5

¹H NMR(CDCl₃Varian 400 MHz): as shown in fig. 1.

Example 2: synthesis of Compound 9

[ Synthesis example 6] Synthesis of Compound 6

As shown in the following reaction formula 6, compound 1(20.00g, 79.63mmol) and dimethyl iminodiacetate hydrochloride (15.74g, 79.63mmol) were mixed in 400mL of acetonitrile (acetonitrile), to which potassium carbonate (44.00g, 318.52mmol) and potassium iodide (52.87g, 318.52mmol) were added to carry out a reflux reaction for 48 hours. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and water, the reaction product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain compound 6(19.12g, 72% yield) as a colorless transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝4.55-4.57(1H，m)，3.82-3.88(1H，m)，3.71-3.75(1H，m)，3.70(6H，s)，3.54(4H，s)，3.46-3.53(1H，m)，3.34-3.40(1H，m)，2.69(2H，t，J＝7.2Hz)，1.32-1.85(12H，m)

Reaction formula 6

[ Synthesis example 7] Synthesis of Compound 7

As shown in the following reaction scheme 7, compound 6(19.12g, 57.70mmol) and 4-hydroxy-2,2,6,6-tetramethylpiperidine (4-hydroxy-2,2,6,6-tetramethylpiperidine) (45.36g, 288.47mmol) were mixed in 250mL of toluene (tolumene), to which titanium isopropoxide (3.42mL, 11.54mmol) was added to carry out a reflux reaction for 24 hours. The reaction solution was concentrated, and the concentrated reaction product was purified by silica gel column chromatography to obtain compound 7(19.00g, 57% yield) as a yellow liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝5.22(2H，quintet，J＝11.2，4.4Hz)，4.55-4.57(1H，m)，3.83-3.88(1H，m)，3.70-3.76(1H，m)，3.52(4H，s)，3.46-3.50(1H，m)，3.35-3.40(1H，m)，2.71(2H，t，J＝7.6Hz)，1.93(4H，dd，J＝12.4，4.0Hz)，1.33-1.83(12H，m)，1.23(12H，s)，1.12-1.18(16H，m)

Reaction formula 7

[ Synthesis example 8] Synthesis of Compound 8

As shown in the following reaction formula 8, compound 7(19.00g, 32.66mmol) was mixed with 125mL of methanol (methanol), and 1N aqueous hydrogen chloride solution (1N hydrochloric acid) (125mL) was added thereto and stirred for 30 minutes. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and 2M aqueous sodium hydroxide (2M NaOH solution), the reaction product obtained by concentrating the organic layer was recrystallized using hexane (hexane) to obtain compound 8(11.18g, 69% yield) as a white solid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝5.22(2H，quintet，J＝11.2，4.4Hz)，3.64(2H，t，J＝6.8Hz)，3.51(4H，s)，2.72(2H，t，J＝7.2Hz)，1.93(4H，dd，J＝12.0，4.0Hz)，1.38-1.60(6H，m)，1.23(12H，s)，1.12-1.18(16H，m)

Reaction formula 8

[ Synthesis example 9] Synthesis of Compound 9

As shown in the following reaction scheme 9, compound 8(2.00g, 4.02mmol) and methacrylic acid (0.36mL, 4.22mmol) were mixed in 40mL of dichloromethane (dichromethane), to which N, N '-dicyclohexylcarbodiimide (N, N' -dicyclohexylcarbodiimide) (1.00g, 4.82mmol) and 4-dimethylaminopyridine (4-dimethylaminopyridine) (0.25g, 2.01mmol) were added and stirred for 24 hours. After the reaction solution was extracted with ethyl acetate (ethyl acetate) and water, the reaction product obtained by concentrating the organic matter was purified by silica gel column chromatography to obtain compound 9(1.00g, 44% yield) as a colorless transparent liquid.

¹H-NMR(CDCl₃，Varian 400MHz)：δ＝6.08(1H，s)，5.54(1H，s)，5.22(2H，tt，J＝11.2，4.0Hz)，4.13(2H，t，J＝6.8Hz)，3.51(4H，s)，2.71(2H，t，J＝7.2Hz)，1.90-1.93(7H，m)，1.69(2H，quintet，J＝7.2Hz)，1.52(2H，quintet，J＝6.8Hz)，1.41(2H，quintet，J＝6.8Hz)，1.24(12H，s)，1.13-1.19(16H，m)

Reaction formula 9

¹H NMR(CDCl₃Varian 400 MHz): as shown in fig. 2.

In order to confirm the physical properties of the synthesized reactive light stabilizer compound, evaluation was performed according to the following method in comparison with known ones. The following compound 10 was used as a comparative example.

Chemical formula 10

Polymerizable compound

Before confirming the physical properties of the synthesized reactive light stabilizer compound, known polymerizable compounds, compound 11 and compound 12, were used as examples and comparative examples in order to form an appropriate line tilt angle.

Preparation of liquid Crystal composition

Liquid crystal compositions of examples 3 to 13 and comparative examples 1 to 7 were prepared according to the composition of table 5 below.

TABLE 5

Liquid crystal compound and method for evaluating liquid crystal composition

The low temperature stability and physical properties of the liquid crystal compound and the liquid crystal composition were evaluated by the methods described below.

(1) Stability at Low temperature

In a 10mL vial, 2g of a liquid crystal mixture (mixed liquid crystal; and a liquid crystal composition obtained by mixing 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight of the compound represented by formula I with 100 parts by weight of the mixed liquid crystal; and mixing 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight of the mixed liquid crystal with 100 parts by weight of the mixed liquid crystal for a period of time of 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight

The resulting liquid crystal composition) was stored in a freezer at-25 ℃. Whether recrystallization was carried out was confirmed every other day. "precipitation" is indicated when recrystallization occurs from the first day of storage in the freezer to 20 days before, and "excellence" is indicated when the liquid crystal phase is maintained without change even after 20 days.

(2) Transparent dot (Tc)

A sample for measuring a transparent spot was prepared by dropping a drop of the liquid crystal composition to be measured on a glass slide with a dropper, and then covering with a cover glass.

The sample was placed in a facility equipped with a mertlettodol FP90 (mettletoledo FP90) temperature regulator, and the change in the sample was observed while raising the temperature at a rate of 3 ℃/min using an FP82HT Hot stage (Hot stage). The temperature of the site where the hole was made in the sample was recorded and this was repeated 3 times to derive an average value. This value is defined as the clear point of the liquid crystal composition.

(3) Refractive index anisotropy (n)

The refractive index anisotropy (n) of a liquid crystal composition was measured at a temperature of 20 ℃ using light having a wavelength of 589nm using an amfold refractometer having a polarizing plate attached to an eyepiece.A liquid crystal composition to be measured was dropped on a main prism after rubbing the surface of the main prism in one direction, and then the refractive index (n /) when the direction of polarization was parallel to the direction of rubbing and the refractive index (n ⊥) when the direction of polarization was perpendicular to the direction of rubbing were measured and the refractive index anisotropy (n) was measured by substituting the above refractive index values into formula 1.

Equation 1

n＝n∥-n⊥

(4) Anisotropy of dielectric constant (. epsilon)

The dielectric anisotropy (. epsilon.). The dielectric anisotropy (. epsilon./. epsilon. ⊥) of the liquid crystal composition was calculated by substituting the values of ε/. epsilon. and ε ⊥, which were measured as follows, into equation 2.

Equation 2

ε＝ε∥-ε⊥

① measurement of dielectric constant ε/A dielectric constant (. epsilon. /) of a device at 1kHz, 0.3V and 20 ℃ was measured using 4294A equipment manufactured by Agilent (Agilent).

② measurement of dielectric constant ε ⊥ the dielectric constant (. epsilon. ⊥) of a device at 1kHz, 0.3V and 20 ℃ was measured using 4294A equipment manufactured by Agilent, after applying a horizontal alignment agent to the surface of 2 glass substrates on which an indium tin oxide pattern was formed, applying a spacer to one of the 2 glass substrates so that the horizontal alignment films were opposed and the gap (cell gap) between the 2 glass substrates was 4 μm, and then bonding the 2 glass substrates together.

(5) Rotational viscosity (gamma 1)

A horizontal alignment agent was applied to the surface of 2 glass substrates on which the indium tin oxide pattern was formed to form a horizontal alignment film. Next, a spacer was applied to one of the 2 glass substrates so that the horizontal alignment films were opposed to each other and the gap (cell gap) between the 2 glass substrates was 20 μm, and then the 2 glass substrates were bonded to each other. Then, a liquid crystal composition is injected into the device to perform sealing. Thereafter, the rotational viscosity of the device was measured at a temperature of 20 ℃ using a Model 6254 apparatus of Toyo Corp, equipped with a temperature controller (controller) (Model SU-241) manufactured by Espeek Corp.

(6) Voltage Holding Ratio (VHR)

Initial Voltage Holding Ratio (VHR)₀) Measurement of (2)

A horizontal alignment agent was applied to the surface of 2 glass substrates on which the indium tin oxide pattern was formed to form a horizontal alignment film. Next, a spacer was applied to one of the 2 glass substrates so that the horizontal alignment films were opposed to each other and the gap (cell gap) between the 2 glass substrates was 4 μm, and then the 2 glass substrates were bonded to each other and dried in a vacuum oven at 120 ℃ for about 4 hours. Then, the liquid crystal compositions of examples and comparative examples were injected into the device to seal the device.

Next, the initial Voltage Holding Ratios (VHR) of the liquid crystal cells of the reference examples, examples and comparative examples were measured under the conditions of 60Hz, 3Hz or 0.6Hz by applying a voltage of 1V for 60us at 100 ℃ using a TOYO Corporation Model 6254C device₀)。

Voltage Holding Ratio (VHR) after UV irradiation_t) Measurement of (2)

A cell similar to the cell for measuring the initial voltage holding ratio is prepared, AC 120Hz and 10V are applied, UV of 3 to 5J based on 365nm is irradiated, and an appropriate line inclination angle of 87 to 89 degrees is formed. At this time, a band-pass filter is used to shield visible light of 300nm or less.

According to circumstances, in order to minimize the residual reactive liquid crystal monomer, additional UV is further irradiated in a state where no voltage is applied.

The voltage holding ratio after UV irradiation was measured under the same conditions as those for measuring the initial voltage holding ratio.

(7) Residual Direct Current (RDC)

Cells were prepared using the liquid crystal compositions of examples 3 to 13 and comparative examples 1 to 7 in the same method as the cell for measuring the above-described initial voltage holding ratio, and a residual direct current was measured using a model 6254C device of TOYO Corporation (TOYO Corporation) under the following conditions.

V was derived by setting the measurement temperature to 60 ℃, the measurement voltage DC to 5V, the relaxation time (relaxation time) within 600 seconds to 2900 seconds, and the warm-up time (warming up time) to 5hrs_max、V₂₁₀₀The value is obtained.

(8) Ion Density (Ion Density, pC)

The ion density was measured by setting a measurement voltage of 10V at 0.1Hz at a measurement temperature of 60 ℃ or 100 ℃ using the same unit and equipment as those used for measuring the above-mentioned RDC.

The ion density can be determined based on the following formula 3.

Equation 3

The physical properties of examples 3 to 6 were confirmed to confirm the change in the basic physical properties depending on the presence or absence of the reactive light stabilizer. The results are shown in Table 6 below.

TABLE 6

When comparing the physical properties of examples 3 to 6 with those of preparation examples 1 to 4 described above, it was confirmed that the physical properties such as the transparent point, the refractive index anisotropy, the dielectric anisotropy, and the rotational viscosity were not changed even if the reactive light stabilizer was added.

In order to confirm the residual image improving effect of the reactive light stabilizer of the present invention with different contents, the Voltage Holding Ratio (VHR), RDC and ion density were measured after the exposure process, and the characteristics of examples 7 to 9 and preparation examples 1 to 3 were compared, and the results thereof are shown in table 7 below.

TABLE 7

In examples 7 to 9, the higher the content of the reactive light stabilizer of the invention, the higher the ionic density, but to a lesser extent, whereas VHR is increased and the RDC value is lowered and gradually increased. In particular, in example 7, the Voltage Holding Ratio (VHR) and the ion density were equivalent to each other, but the RDC was very excellent, as compared with comparative example 1 in which no reactive light stabilizer was added. On the contrary, in comparative examples 2 to 3, the Voltage Holding Ratio (VHR), RDC and ion density were increased together as the content of the conventional reactive light stabilizer was increased. Example 7 has a 2-fold higher content of the reactive light stabilizer than comparative example 3, but is excellent in that the ion density at 100 ℃ in the measurement environment is not more than half. Generally, the higher the VHR value, the lower the RDC and ion density, and thus the excellent afterimage improvement effect.

The Voltage Holding Ratio (VHR), RDC, and ion density were measured for each of the liquid crystal compositions and the polymerizable compounds before and after the exposure process, and the characteristics of examples 10 to 13 and comparative examples 4 to 7 were compared, and the results are shown in table 8 below.

TABLE 8

In examples 10 to 13, the Voltage Holding Ratio (VHR) was reduced before the exposure process, as compared with comparative examples 4 to 7. However, after the exposure process, the Voltage Holding Ratio (VHR) is improved at an equivalent level to more than that. Examples 10 to 13 have equivalent ion densities compared to comparative examples 4 to 7. Instead, it was confirmed that examples 10 to 13 are superior to comparative examples 4 to 7 in that the RDC measured before/after the exposure process, the liquid crystal composition, and the polymerizable compound were reduced.

The above description of the present invention is intended to be illustrative, and it will be understood by those skilled in the art that the present invention can be easily modified in other specific ways without changing the technical idea or essential features of the present invention. It is therefore to be understood that the above described embodiments are illustrative in all respects, rather than restrictive. For example, each component described as a single type may be implemented as a dispersion, and similarly, a plurality of components described as a dispersion may be implemented as a combination.

The scope of the present invention is indicated by the appended claims rather than the foregoing detailed description, and all changes and modifications that come within the meaning and range of equivalency of the claims are to be construed as being included in the scope thereof.

Claims

1. A reactive light stabilizer compound represented by the following formula I:

chemical formula I

In the chemical formula I, the compound represented by the formula I,

T₁to T₃Each independently hydrogen (H), one of the following chemical formulas 1 to 4, or a polymerizable functional group, in which case T₁To T₃At least one of the following chemical formulas 1 to 3, the remaining at least one being the polymerizable functional group,

R¹Is hydrogen (H) or C_1～10Straight or branched alkyl, in which case, C_1～10Linear or branchedMore than one methylene (-CH) group of alkyl₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead of this, the user can,

R²to R⁵Each independently is C_1～10Straight or branched alkyl, in which case, C_1～10One or more methylene groups (-CH) of a linear or branched alkyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead of this, the user can,

y is H, C_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10A linear or branched alkenyl radical, in which case C_1～10Straight or branched alkyl, C_1～10Straight or branched alkoxy or C_2～10One or more nonadjacent methylene groups (-CH) of a linear or branched alkenyl group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens of the linear or branched alkyl group may be replaced by F, Cl or CF₃Instead of this, the user can,

n2 is an integer from 1 to 4,

A₁to A₃Each independently represented by the following chemical formula 5,

chemical formula 5

L is a single bond, -CH ═ CH-, -C ≡ C-, -CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO

-、-CO-、-O-、-OCH₂-、-CH₂O-、-OCF₂-or-CF₂O-，

Z is C_1～10Straight or branched alkylene or C_5～20Cyclic alkylene, in this case, C_1～10One or more methylene groups (-CH) of a linear or branched alkylene group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkylene group may be replaced by F, Cl or CF₃Alternative, C_5～20More than one carbon (C) atom of the cyclic radical being able to be substituted by O, N or S, C_5～20More than one hydrogen of a cyclic group can be represented by F, Cl or CF₃Instead of this, the user can,

n3 is an integer of 1 or 2, when n3 is 2, L, Z can be the same or different.

2. The reactive light stabilizer compound of claim 1, wherein the polymerizable functional group is a polymerizable compound represented by one of the following formulae:

3. the reactive light stabilizer compound of claim 1, wherein T is₁To T₃At least one of the following chemical formula 1 or chemical formula 2, and the remaining at least one is the polymerizable functional group,

4. a reactive light stabilizer compound according to claim 1, wherein Sp is-CH ═ CH-, -C ≡ C-, -CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-CO-、-O-、-OCH₂-、-CH₂O-、-OCF₂-or-CF₂O-。

5. A reactive light stabilizer compound according to claim 3 wherein Sp is-COO-.

6. The reactive light stabilizer compound of claim 1, wherein R is¹Is hydrogen (H).

7. The reactive light stabilizer compound of claim 1, wherein n2 is an integer of 1 or 2.

8. The reactive light stabilizer compound according to claim 1,

the L is a single bond,

z is C_1～10Straight-chain or branched alkylene, in which case, C_1～10One or more methylene groups (-CH) of a linear or branched alkylene group₂-) can each, independently of one another, be replaced by-O-, -S-, -CO-O-, -O-CO-or-O-CO-O-in such a way that oxygen (O) atoms are not linked directly to one another, C_1～10One or more hydrogens (H) of the linear or branched alkylene group may be replaced by F, Cl or CF₃And (4) replacing.

9. The reactive light stabilizer compound of claim 1, wherein the formula I is represented by the following formula:

10. a liquid crystal composition comprising the reactive light stabilizer compound according to any one of claims 1 to 9.

11. The liquid crystal composition of claim 10, further comprising a compound represented by the following formula II:

chemical formula II

In the chemical formula II, the compound represented by the formula II,

ring A and ring B are each independently a 1, 4-cyclohexylene group in which the carbon (C) in the ring is substituted or unsubstituted with one or more oxygen (O) or a 1, 4-phenylene group in which one or more hydrogen (H) is substituted or unsubstituted with a halogen,

12. Liquid crystal composition according to claim 11, characterized in that the halogen is fluorine (F).

13. The liquid crystal composition of claim 10, wherein the reactive light stabilizer compound is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the liquid crystal composition.

14. A liquid crystal display device comprising the liquid crystal composition according to claim 10.