KR102236093B1 - Photostabilizer compound and liquid crystal composition containing the same - Google Patents

Abstract

The present invention relates to a light stabilizer compound, a liquid crystal composition comprising the same, and a liquid crystal display device comprising the same, and the light stabilizer compound according to the present invention can impart heat and light stability without deteriorating the properties of the liquid crystal composition, Low temperature stability can be secured.

Description

A light stabilizer compound and a liquid crystal composition comprising the same TECHNICAL FIELD [0002] PHOTOSTABILIZER COMPOUND AND LIQUID CRYSTAL COMPOSITION CONTAINING THE SAME}

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

Liquid crystal display devices are currently widely used in various measuring devices, automobile panels, printers, notebook computers, monitors, TVs, and advertisement display boards, and liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, and There are VA (vertical orientation) type using TFT (thin film transistor), FFS (fringe electric field) type, IPS (in-plane switching) type, and the like. Liquid crystal compositions used in these liquid crystal display devices require low-voltage and low-viscosity characteristics. In particular, liquid crystal compositions used in active matrix-driven liquid crystal display devices driven by TFT devices have high specific resistance and high voltage retention (VHR). It is necessary to have characteristics. In addition, it must have stable characteristics against external factors such as moisture, air, heat, and light in order not to cause display defects and to improve the life of the device. In order to improve the heat and light stability, antioxidants and light stabilizers are used.

Stability may be obtained by adding an antioxidant and a light stabilizer to the liquid crystal composition, but the initial voltage retention (VHR), etc. may be rather lowered. In addition, when the content is increased to prevent the occurrence of stains, there is a problem in that low-temperature stability is deteriorated.

Republic of Korea Patent Publication No. 10-2016-0127729

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

One aspect of the present invention provides a light stabilizer compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a direct bond or a carbonyl group,

n is an integer greater than or equal to 1.

One aspect of the present invention provides a liquid crystal composition comprising a compound represented by the following formula (1).

An aspect of the present invention is a first substrate and a second substrate disposed opposite to each other; An electric field generating electrode formed on at least one of the first substrate and the second substrate;

A first alignment layer formed on the first substrate and a second alignment layer formed on the second substrate; And a liquid crystal layer formed of a plurality of liquid crystal molecules interposed between the first substrate and the second substrate, wherein the liquid crystal layer includes a light stabilizer compound according to an embodiment of the present invention. do.

The light stabilizer compound according to the present invention can be applied to all liquid crystal compositions having positive or negative dielectric anisotropy.

In addition, since the light stabilizer compound according to the present invention has both light stabilizer properties and antioxidant properties, it is possible to significantly reduce the amount of light stabilizers and antioxidants used in conventional liquid crystal compositions.

In addition, the light stabilizer compound according to the present invention can impart heat and light stability without deteriorating characteristics such as initial voltage retention (VHR) of the liquid crystal composition, and can secure low temperature stability with good solubility.

In addition, the light stabilizer compound according to the present invention may be used with a liquid crystal compound having a high dielectric constant anisotropy or a liquid crystal compound having an alkenyl group, which is used to lower the driving voltage and lower the viscosity of the liquid crystal composition. It can reduce the problem of poor stability.

The compound of the present invention can increase long-term stability of a liquid crystal display device while being used in a very small amount compared to a conventional light stabilizer.

The liquid crystal composition containing the compound of the present invention maintains stability and maintains the initial voltage retention (VHR), so that various modes of liquid crystal display devices, especially VA mode, PSA mode, PS-VA mode, IPS mode, or FFS mode liquid crystal display It is possible to provide a liquid crystal composition optimized for a device.

1 is a schematic cross-sectional view of a liquid crystal display device according to an exemplary embodiment of the present disclosure.

Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present disclosure.

However, the present application may be implemented in various different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a member is said to be positioned "on" another member, this includes not only the case where a member is in contact with the other member, but also the case where another member exists between the two members.

In the entire specification of the present application, when a certain part "includes" a certain constituent element, it means that other constituent elements may be further included rather than excluding other constituent elements unless otherwise specified. The terms "about", "substantially", etc. to the extent used throughout the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and the understanding of the present application To assist, accurate or absolute numerical values are used to prevent unreasonable use of the stated disclosure by unscrupulous infringers. As used throughout the specification of the present application, the term "step (to)" or "step of" does not mean "step for".

In the entire specification of the present application, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of the Makushi format, and the constituent elements It means to include one or more selected from the group consisting of.

Throughout this specification, the description of “A and/or B” means “A or B, or A and B”.

Throughout this specification, the term "alkyl" may be one including linear or branched, saturated or unsaturated C ₁ -C ₈ alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, hepyl, It may include octyl or all possible isomers thereof, but may not be limited thereto.

Throughout the present specification, the term "alkoxy" refers to an alkyl group bonded to oxygen, and may include _{C 1} -C _{8 alkoxy.}

Throughout the present specification, the terms "which may be substituted" or "substituted" refer to hydrogen, deuterium, oxygen, halogen, amino group, nitrile group, nitro group, silane group, alkyl group, or C ₁ to C ₂₀ alkyl group, alkenyl group, or C ₂ ~ C ₂₀ alkenyl group, alkoxy group or C ₁ ~ C ₂₀ alkoxy group, cycloalkyl group or C ₃ ~ C ₂₀ cycloalkyl group, heterocycloalkyl group or C ₃ ~ C ₂₀ heterocycloalkyl group or C ₅ ~ C ₃₀ It means that can be substituted with one or more groups selected from the group consisting of an aryl group of or C ₅ ~ C _{30 heteroaryl group.}

In addition, throughout the specification of the present application, the same symbols may have the same meaning unless otherwise specified.

One aspect of the present invention provides a light stabilizer compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a direct bond or a carbonyl group,

n is an integer of 1 or more.

In one embodiment of the present invention, the compound may be represented by the following formula (2), but is not limited thereto:

[Formula 2]

In Chemical Formula 2,

n is an integer of 1 or more, and specifically may be an integer of 6 to 12, but is not limited thereto.

In one embodiment of the present invention, the compound may be a compound represented by Formula 3 below, but is not limited thereto:

[Formula 3]

In Chemical Formula 3,

n is an integer of 1 or more, specifically an integer of 4 or more, and more specifically, an integer of 12 to 20, but is not limited thereto.

One aspect of the present invention provides a liquid crystal composition including the compound represented by Formula 1.

The liquid crystal composition according to an embodiment of the present invention may include a compound represented by Formula 1 and various kinds of liquid crystal compounds. The compound represented by Formula 1 may include a compound represented by Formula 2 or Formula 3.

In one embodiment of the present invention, the light stabilizer compound represented by Formula 1 is 0.001 to 1 parts by weight, for example, 0.001 to 0.5 parts by weight, 0.001 to 0.3 parts by weight, 0.003 to 100 parts by weight of the liquid crystal composition. It may be included in an amount of 1 part by weight, 0.003 to 0.5 parts by weight, or 0.003 to 0.3 parts by weight, and may not be limited thereto.

According to an embodiment of the present invention, the liquid crystal composition is a compound represented by the following formula (1); And one or two or more compounds represented by the following formula (5).

[Formula 1]

The symbol of Chemical Formula 1 is as described above.

[Formula 5]

In Chemical Formula 5,

R ₄ is alkenyl having 2 to 8 carbon atoms, in which case, a hydrogen atom may be replaced by a halogen,

R ₅ is C 1 to C 8 alkyl, C 1 to C 8 alkoxy or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -is each independently of each other, O (oxygen) atoms are not directly connected to each other -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO-O- Can be replaced, hydrogen atom can be replaced by halogen,

Rings E, F and G are each independently trans-1,4-cyclohexylene, H (hydrogen), which can be substituted with one or two O (oxygen) carbons in the ring. Trans-1,4-cyclohexylene, which can be substituted with one or two F (fluorine), or 1 that can be substituted with one or two F (fluorine), H (hydrogen) ,4-phenylene (1,4-phenylene),

c and d are each independently an integer of 0, 1 or 2.

The compound represented by Formula 1 may include a compound represented by Formula 2 or Formula 3.

In one embodiment of the present invention, the light stabilizer compound represented by Formula 1 is 0.001 to 1 parts by weight, for example, 0.001 to 0.5 parts by weight, 0.001 to 0.3 parts by weight, 0.003 to 100 parts by weight of the liquid crystal composition. It may be included in an amount of 1 part by weight, 0.003 to 0.5 parts by weight, or 0.003 to 0.3 parts by weight, and may not be limited thereto.

According to an embodiment of the present invention, at least one of the compounds represented by Formula 5 may include a compound represented by the following Formula 5-1.

[Chemical Formula 5-1]

In Formula 5-1,

R ₄ is alkenyl having 2 to 5 carbon atoms,

c is an integer of 0 or 1,

R ₅ , rings E and F are as defined in Chemical Formula 5.

In one embodiment of the present invention, the compound represented by Formula 5 may include a compound represented by the following formula.

In the above formula,

R ₄ may be alkenyl having 2 to 5 carbon atoms, and R ₅ may be alkyl having 1 to 8 carbon atoms or alkoxy having 1 to 8 carbon atoms.

More specifically, according to one embodiment of the present invention, the compound represented by Formula 5-1 may include a compound represented by the following formula.

In the above formula,

R ₅ may be C 1 to C 8 alkyl or C 1 to C 8 alkoxy.

The compound represented by Formula 5 may allow the liquid crystal composition to have a wide range of liquid crystal phases.

In one embodiment of the present invention, the compound represented by Formula 5 may be included in an amount of 10 to 65 parts by weight based on 100 parts by weight of the liquid crystal composition, but may not be limited thereto.

In addition, in one embodiment of the present invention, the compound represented by Formula 5-1 may contain 10 parts by weight or more based on 100 parts by weight of the liquid crystal composition. If it is included in an amount of less than 10 parts by weight, the transparent point may be lowered and the driving temperature range may be reduced.

The liquid crystal composition according to an embodiment of the present invention may further include one or two or more compounds represented by the following formula (6). More specifically, an embodiment of the present invention is a compound represented by Formula 1; And it provides a liquid crystal composition comprising a compound represented by the following formula (6). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; And it provides a liquid crystal composition comprising a compound represented by the following formula (6).

[Formula 6]

In Chemical Formula 6,

R ₆ and R ₇ are each independently alkyl having 1 to 8 carbon atoms, or alkoxy having 1 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, in a manner in which the O atoms are not directly connected to each other Can be replaced by -C≡C-, -CF ₂ O-, -OCF ₂ -, -O-, -CO-O-, -O-CO- or -O-CO-O-, the hydrogen atom is halogen Can be replaced with

Rings H and I are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted, or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),

e and f are each independently an integer of 0, 1, or 2, and e+f≤2.

The compound represented by Formula 6 may allow the liquid crystal composition to have a wide liquid crystal phase range.

In one embodiment of the present invention, the compound represented by Formula 6 may be any one of the compounds represented by the following Formulas 6-1 to 6-4.

[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

In Formulas 6-1 to 6-4,

R ₆ and R ₇ are as defined in Chemical Formula 6.

In one embodiment of the present invention, the compound represented by Formula 6 may be included in an amount of 30 parts by weight or less based on 100 parts by weight of the liquid crystal composition, but may not be limited thereto.

Liquid crystal compositions according to an embodiment of the present invention may include one or two or more compounds represented by the following Formula 4-1. In this case, the liquid crystal composition may have positive dielectric anisotropy.

More specifically, an embodiment of the present invention is a compound represented by Formula 1; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-1. In addition, an embodiment of the present invention is a compound represented by Formula 1; And one or two or more compounds represented by Chemical Formula 5; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-1. An embodiment of the present invention is a compound represented by Formula 1; And one or two or more compounds represented by Formula 6; And it provides a liquid crystal composition of the compound represented by the formula 4-1. In addition, an embodiment of the present invention is a compound represented by Formula 1; And one or two or more compounds represented by Chemical Formula 5; A compound represented by Chemical Formula 6; And it is possible to provide a liquid crystal composition including the compound represented by the following formula 4-1.

[Formula 4-1]

In Formula 4-1,

R ₁ is hydrogen, branched or cyclic C 1 to C 8 alkyl, C 1 to C 8 alkoxy or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently an O atom -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O- Can be replaced by CO-O-, hydrogen atom can be replaced by halogen,

X ₂ to X ₆ are each independently H, F or OCF ₃ ,

Y ₁ is H or a methyl group,

Rings A and B are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Is substituted 1,4-phenylene (1,4-phenylene),

a is an integer of 0 or 1.

In one embodiment of the present invention, the compound represented by Formula 4-1 may include compounds represented by the following Formulas 4-1-1 to 4-1-8.

[Formula 4-1]

[Formula 4-1-1]

[Formula 4-1-2]

[Formula 4-1-3]

[Formula 4-1-4]

[Formula 4-1-5]

[Formula 4-1-6]

[Formula 4-1-7]

[Formula 4-1-8]

In Formulas 4-1-1 to 4-1-8,

R ₁ is hydrogen, branched or cyclic C 1 to C 8 alkyl, C 1 to C 8 alkoxy or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently an O atom -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O- Can be replaced by CO-O-, and hydrogen atom can be replaced by halogen. Although not limited thereto, specifically, it may be an alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms, and more specifically, it may be an alkyl having 1 to 8 carbon atoms.

In one embodiment of the present invention, the compound represented by Formula 4-1 is a high-k anisotropic compound, and may be included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the liquid crystal composition, but may not be limited thereto.

Liquid crystal compositions according to an embodiment of the present invention may include one or two or more compounds represented by the following formula (7). More specifically, an embodiment of the present invention is a compound represented by Formula 1; 1 type or 2 or more types of compounds represented by the following formula 4-1; And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (7). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (7). In addition, a liquid crystal composition according to an embodiment of the present invention may include a compound represented by Formula 1; One or two or more compounds represented by Formula 5; And a compound represented by Formula 4-1. And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (7). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; A compound represented by Chemical Formula 6; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula (7). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; A compound represented by Chemical Formula 6; And one or two or more compounds represented by Formula 4-1; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula (7).

[Formula 7]

In Chemical Formula 7,

R ₈ is C 1 to C 8 alkyl, C 1 to C 8 alkoxy, or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently of each other, in a manner in which O atoms are not directly connected to each other To be replaced by -C≡C- _{, -CF 2 O-, -OCF 2} -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO-O- Hydrogen atom can be replaced by halogen,

X ₉ to X ₁₁ are each independently H, F or OCF ₃ ,

Rings J and K are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),

g is an integer of 0, 1 or 2.

According to an embodiment of the present invention, the compound represented by Formula 7 may exclude the compound represented by Formula 5.

In one embodiment of the present invention, the compound represented by Formula 7 can make the liquid crystal composition have an appropriate dielectric anisotropy, and thus is advantageous in matching the driving voltage required by the device.

In one embodiment of the present invention, the compound represented by Formula 7 may be any one of the compounds represented by the following Formulas 7-1 to 7-9.

[Chemical Formula 7-1]

[Formula 7-2]

[Chemical Formula 7-3]

[Chemical Formula 7-4]

[Chemical Formula 7-5]

[Formula 7-6]

[Formula 7-7]

[Formula 7-8]

[Chemical Formula 7-9]

In Formulas 7-1 to 7-9,

R ₈ is as defined in Chemical Formula 7.

In addition, in one embodiment of the present invention, the compound represented by Formula 7 may be included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the liquid crystal composition, but may not be limited thereto.

According to one embodiment of the present invention, a liquid crystal composition including one or two or more compounds represented by the following Formula 4-2 may be provided. In this case, the liquid crystal composition may have negative dielectric anisotropy. More specifically, the liquid crystal composition according to an embodiment of the present invention includes a compound represented by Formula 1; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-2. In addition, an embodiment of the present invention is a compound represented by Formula 1; One or two or more compounds represented by Formula 5; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-2. In addition, an embodiment of the present invention is a compound represented by Formula 1; One or two or more compounds represented by Formula 6; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-2. In addition, an embodiment of the present invention is a compound represented by Formula 1; One or two or more compounds represented by Formula 5; A compound represented by Chemical Formula 6; And it is possible to provide a liquid crystal composition including one or two or more compounds represented by the following formula 4-2.

[Formula 4-2]

In Formula 4-2,

R ₂ and R ₃ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, and O atoms are each independently -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO- O- may be substituted, the hydrogen atom may be replaced by halogen, specifically R ₂ may be a C 1 to C 8 alkyl or C 1 to C 8 alkoxy.

X ₇ and X ₈ are each independently H, F or OCF ₃ , at least one is F or OCF ₃ ,

Rings C and D are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),

b is an integer of 0 or 1.

In one embodiment of the invention, the ring C may be R ₂ is 2 days when the cyclohexylene, wherein R ₂ may be the same or different from each other.

In one embodiment of the present invention, the compound represented by Formula 4-2 may be represented by the following Formula 4-2-1.

[Formula 4-2-1]

In Formula 4-2-1,

R _'3 is an alkyl group having 1 to 8 carbon atoms, wherein one or more -CH ₂ - groups may be replaced by -CH = CH-, a hydrogen atom is optionally replaced by halogen,

R ₂ , X ₇ , X ₈ , ring C, ring D and b are as defined in Formula 4-2.

In one embodiment of the present invention, the compound represented by Formula 4-2 may include a compound represented by the following formula.

In the above formula

R ₂ and R ₃ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms.

Furthermore, in one embodiment of the present invention, wherein the ring C can be R ₂ it is 2 days when the cyclohexylene, wherein R ₂ may be the same or different from each other.

In one embodiment of the present invention, the compound represented by Formula 4-2 is a high-k anisotropic compound, and may be included in an amount of 5 to 70 parts by weight based on 100 parts by weight of the liquid crystal composition, but may not be limited thereto.

When the compound represented by Formula 4-2-1 is included, it may be included in an amount of 5 parts by weight or more based on 100 parts by weight of the liquid crystal composition. If it is included in an amount of less than 5 parts by weight, the rotational viscosity of the high-k anisotropic liquid crystal composition for low voltage may increase.

Liquid crystal compositions according to an embodiment of the present invention may include one or two or more compounds represented by the following Formula 8. More specifically, the liquid crystal composition according to an embodiment of the present invention includes a compound represented by Formula 1; A compound represented by Formula 4-2; And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (8). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (8). In addition, a liquid crystal composition according to an embodiment of the present invention may include a compound represented by Formula 1; One or two or more compounds represented by Formula 5; And a compound represented by Formula 4-2. And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (8). In addition, an embodiment of the present invention is a compound represented by Formula 1; One or two or more compounds represented by Formula 5; A compound represented by Chemical Formula 6; It is possible to provide a liquid crystal composition including the compound represented by the following formula (8). In addition, an embodiment of the present invention is a compound represented by Formula 1; A compound represented by Chemical Formula 5; A compound represented by Chemical Formula 6; A compound represented by Formula 4-2; And it is possible to provide a liquid crystal composition comprising a compound represented by the following formula (8).

[Formula 8]

In Chemical Formula 8,

R ₉ and R ₁₀ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, O atoms are -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO Can be replaced by -O-, hydrogen atom can be replaced by halogen,

Z ₁ is -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -CF ₂ O-, or -OCF ₂ -,

Rings L and M are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted, or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),

h is an integer of 0, 1 or 2.

The compound represented by Chemical Formula 8 is a material having negative dielectric anisotropy, and it is advantageous to adjust the driving voltage required for the device since the liquid crystal composition can be adjusted to have appropriate dielectric anisotropy.

In one embodiment of the present invention, the compound represented by Formula 8 may include a compound represented by Formula 8-1 or Formula 8-2 below.

[Chemical Formula 8-1]

[Formula 8-2]

In Formula 8-1 and Formula 8-2,

R ₉ and R ₁₀ are as defined in Chemical Formula 8.

In one embodiment of the present invention, the compound represented by Formula 8 may be included in an amount of 30 parts by weight or less based on 100 parts by weight of the liquid crystal composition, and may not be limited thereto.

In one embodiment of the present invention, the liquid crystal composition having positive dielectric anisotropy or the liquid crystal composition having negative dielectric anisotropy may further include an antioxidant represented by Formula 9 below.

[Formula 9]

In Chemical Formula 9,

R ₁₁ is alkyl having 1 to 12 carbon atoms,

Ring N is trans-1,4-cyclohexylene, tetrahydropyran or dioxane,

i is an integer of 0, 1 or 2.

In one embodiment of the present invention, the antioxidant represented by Formula 9 may be included in an amount of 0.005 to 0.05 parts by weight based on 100 parts by weight of the liquid crystal composition.

An aspect of the present invention provides a liquid crystal display device including a liquid crystal composition according to an embodiment of the present invention.

More specifically, a first substrate and a second substrate disposed opposite to each other; An electric field generating electrode formed on at least one of the first substrate and the second substrate; A first alignment layer formed on the first substrate and a second alignment layer formed on the second substrate; And a liquid crystal layer formed of a plurality of liquid crystal molecules interposed between the first substrate and the second substrate, and the liquid crystal layer may include a liquid crystal composition according to an embodiment of the present invention.

1 is a cross-sectional view of a liquid crystal display according to an exemplary embodiment of the present invention. 1, a liquid crystal display according to an embodiment of the present invention includes a first substrate SUB1, a second substrate SUB2 facing the first substrate SUB1, and the first substrate SUB1. And a liquid crystal layer LC formed between the second substrate SUB2.

The first substrate SUB1 includes a wiring portion provided on a first base substrate BS1, a transistor TR connected to the wiring portion, a pixel electrode PE connected to the transistor TR, and the pixel electrode ( PE) and the insulated common electrode CE.

The first base substrate BS1 has a substantially rectangular shape and is made of a transparent insulating material. The wiring part includes a gate line GL and a data line GL.

A gate insulating layer GI is provided on the first base substrate BS1 on which the gate line GL is formed. The gate insulating layer GI may be made of an insulating material, and may include, for example, silicon nitride or silicon oxide.

The data line GL is provided to extend in a second direction D2 crossing the first direction D1 with the gate line GL and the gate insulating layer GI interposed therebetween.

The transistor TR is connected to the gate line GL and the data line GL. The transistor TR includes a gate electrode GE, a semiconductor pattern SM, a source electrode SE, and a drain electrode DE.

The transistor TR includes a gate electrode GE, a semiconductor pattern SM, a source electrode SE, and a drain electrode DE.

The gate electrode GE protrudes from the gate line GL or is provided on a partial area of the gate line GL.

An interlayer film IL is provided on the source electrode SE and the drain electrode DE. A passivation layer PSV is provided on the interlayer layer IL, and a contact hole CH exposing a portion of an upper surface of the drain electrode DE is provided in the interlayer layer IL and the passivation layer PSV.

The second substrate SUB2 is provided to face the first substrate SUB1. The second substrate SUB2 may include a second base substrate BS2, a color filter CF, and a black matrix BM.

The liquid crystal layer LC includes the liquid crystal composition according to the exemplary embodiment of the present invention described above.

The liquid crystal display may be in a VA mode, a PSA mode, a PS-VA mode, an IPS mode, or an FFS mode, but is not limited thereto.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and the scope of the invention is not limited to any meaning by this. In Examples and Comparative Examples, the structures of the compounds included in the liquid crystal composition were divided into a center group, a linking group, and an end group, respectively, and represented by symbols as shown in Table 1 below.

[Example]

Evaluation of the properties and parent liquid crystal of the compound represented by Formula 1 according to the present invention

(1) Transparent point measurement

It was put in a 1mm diameter capillary tube, and after mounting the capillary tube on the METTLER TOLEDO MP50, the change in transmittance was observed while raising the temperature at 3°C/min intervals. The point at which the transmittance rapidly increases by using optical change was defined as the transparent point.

(2) low temperature stability

2 g of a liquid crystal obtained by mixing 0.1 parts by weight of each of the parent liquid crystal or the compound represented by Chemical Formula 1 into 100 parts by weight of the parent liquid crystal was put in a 10 mL vial and stored in a -30°C freezer. Recrystallization was checked at 1 day intervals.

(3) refractive index anisotropy

It was measured using an Abbe refractometer at 589 nm, and after aligning the liquid crystal with lecithin, the ideal refractive index and the phase refractive index were checked at 20 degrees to obtain refractive index anisotropy.

(4) permittivity anisotropy

The dielectric anisotropy (ε) of the liquid crystal composition was calculated by substituting ε∥ and ε⊥ measured as follows into Equation 1 below.

[Equation 1]

ε = ε∥-ε⊥

① Measurement of dielectric constant ε The dielectric constant (ε ∥) of the device at 1 kHz, 0.3 V, and 20° C. was measured.

② Measurement of dielectric constant ε⊥: A test cell with a cell gap of 4 μm coated with a horizontal aligning agent on the surface of the two glass substrates on which the ITO pattern was formed was used, and the liquid crystal composition to be measured was injected and used in the 4294A equipment manufactured by Agilent with ultraviolet rays. Then, the dielectric constant (ε⊥) of the device at 1 kHz, 0.3V and 20°C was measured.

(5) Rotation viscosity

The liquid crystal composition to be measured was injected into a test cell having a cell gap of 20 μm, and ESPEC Corp. After mounting on the temperature controller (Model SU-241), the peak time and peak current of the transient current are measured at 20℃ using Toyo Corp.'s Model 6254 equipment. The rotational viscosity of the device was measured.

(6) modulus of elasticity

After injecting the liquid crystal composition to be measured into a test cell having a cell gap of 20 μm, a voltage was applied from 0V to 20V, and the modulus of elasticity was calculated by changing the capacitance. Here, K11 is the splay modulus and K33 is the band modulus. The measurement temperature is 20 degrees.

(7) Voltage retention rate (VHR)

After injecting the liquid crystal composition to be measured into a test cell having a cell gap of 4 μm, the injected inlet is sealed with a UV curing agent. After that, using Toyo Corp.'s LCM2 equipment, a voltage of 1V, 60Hz or 1V, 3Hz was applied at 60 degrees to check the VHR value.

In the case of heat stress, the VHR value was checked on the 1st, 3rd, and 10th days while storing the cell in an oven at 60 degrees. The VHR value was checked.

(8) Preparation of matrix liquid crystal

In order to evaluate the properties of the compound represented by Formula 1 according to the present invention, a parent liquid crystal having the composition of Table 2 and Table 3 was used, and the coded notation was indicated by the method of Table 1 above.

Code A liquid crystal B liquid crystal C liquid crystal D liquid crystal BB-3.V 38 45 30 44 BB-3.U1 6 5 12 8 BBA-W.1 7 6 5 6 ACEXE-3.F 5 ACEXE-4.F 5 10 ACEXE1-5.F 5 ACEXE1-2.F 7 7 9 ACEXE1-3.F 6 6 11 IaAEXE1-2.F 7 6 2 PACEXE1-H.F 2 BAA-3.2 3 3 ACA-2.F 5 5 ACA-3.F 4 3 3 BAE-3.F 3 5 BBA-3.OCF3 8 7 6 BBE-2.F 7 BBE-3.F 8 BBAE-3.F 3 BBCE-3.F 2 3 5 AEXE-3.F 8 AEXE1-3.F 4 5 Evaluation item A liquid crystal B liquid crystal C liquid crystal D liquid crystal Transparent point 83.3 82.7 84.0 75.9 Refractive index anisotropy 0.1062 0.1052 0.1076 0.1111 Ideal refractive index 1.5912 1.5894 1.5906 1.5952 Phase refractive index 1.4850 1.4842 1.4830 1.4841 Permittivity anisotropy 9.0 8.8 10.1 11.9 Horizontal permittivity 12.2 11.9 13.2 14.9 Vertical 3.2 3.2 3.2 3.0 Rotational viscosity 89 82 108 69 Modulus of elasticity K11 13.6 13.6 14.6 13.1 Modulus of elasticity K33 16.5 16.7 16.8 14.0

Code E liquid crystal F liquid crystal G liquid crystal BB-3.V 16 18 14 BB-5.V 7 BB-3.4 6 10 BB-3.5 3 ACA-2.3 4 BAA-3.1 5 6 BAA-3.2 5 6 BAA-5.2 4 BBA-V.1 8 BBA-U1.1 6 AF-3.O2 13 12 13 BF-3.O2 12 12 7 BF-3.O4 2 BF-5.O2 5 BBF-3.O1 8 6 BBF-3.O2 9 5 BBF-5.O2 3 BBF-2.1 8 BBF-3.1 9 BAF-3.O2 9 9 BBF-V.O2 10 BBF-U1.O2 10 BYF-3.O2 3 7 BYF-5.O2 5 BBYF-3.O2 5 Evaluation item E liquid crystal F liquid crystal G liquid crystal Transparent point 80.4 78.3 79.5 Refractive index anisotropy 0.1074 0.1050 0.1093 Ideal refractive index 1.5925 1.5898 1.5952 Phase refractive index 1.4851 1.4848 1.4859 Permittivity anisotropy -3.7 -3.4 -4.1 Horizontal permittivity 3.3 3.2 3.3 Vertical 7.0 6.6 7.4 Rotational viscosity 140 106 135 Modulus of elasticity K11 14.3 14.3 13.7 Modulus of elasticity K33 15.4 16.2 14.5

The compound represented by Chemical Formula 1 evaluated in this example was the material Y and the material Z in Table 4 below, and the commercially available stabilizer Tinuvin 770 (T-770) was evaluated as a comparative material.

Synthesis Example 1: Synthesis of Substance Y

Substance Y may be synthesized by Scheme 1 as follows, but is not limited thereto.

[Scheme 1]

1) Synthesis of Intermediate 1

[Intermediate 1] [Reactant 1]

As shown in Table 5, Intermediate 1 was prepared by adding 15 g of reactant 1, 2.2 g of paraformaldehyde, 5.5 g of carbon disulfide, and 70 ml of isopropanol to a 250 ml three-necked flask. A solution composed of ethylamine + 10 ml of isopropanol was added dropwise, followed by reflux reaction for 5 h after the dropwise addition was completed, and the reaction product was extracted (workup).

matter Reactant 1 Isopropanol Molecular Weight 206 （30）n 76 73 / Number of moles 0.072 0.072 0.072 0.072 / Quantity 15g 2.2g 5.5g 5.3g 80ml

Post-treatment (purification): The reaction solution was spin-dried to obtain 27 g of pale yellow viscous liquid, 3 times of n-heptane was added, passed through 1 times of silica gel column, and then rotated to dry to obtain 23 g of pale yellow liquid. It was obtained, dissolved by adding 1 times of n-heptane, frozen in a refrigerator, filtered, and eluted with a small amount of frozen n-heptane to obtain 19 g of a white solid. Table 6 below shows the results of gas chromatography (GC) after the reaction product workup and gas chromatography (GC) after the first purification.

RT/min




A% 16.279
Reactant 1

16.800

20.531 28.459
Main peak

28.910

GC after reaction product extraction
Y1017042631 3.220 22.634 2.013 67.301 2.563 1st purification GC
Y1017042632 / 2.648 / 93.550 1.963

As shown in Table 6, it was confirmed that Intermediate 1 was produced as a main peak after the first purification. The theoretical production amount is 26.7g, the actual production amount is 19g, the yield is 71.1%, and the mp of the white solid is 69.50～71.97℃.

2) Synthesis of substance Y

[Reactive substance 2]

As shown in Table 7 below, 7.7 g of reactant 2, 20 ml of tetrahydrofuran, and 1.96 g (60%) of sodium hydrogen were added to a 250 ml three-necked flask, and stirred at room temperature (25° C.) for 30 minutes, and then 18 g of A solution composed of intermediate 1+50ml of tetrahydrofuran was added dropwise, and after the dropwise addition was completed, the mixture was reacted at room temperature (25°C) for 3h and the reaction product was extracted (workup).

Post-treatment (purification): 30 ml of water was slowly added to destroy the hydrolysis, stirred for 5 min to separate the solution, and the aqueous phase was extracted once with 30 ml of ethyl acetate, the organic phases were merged, and the organic phase was 50 ml× After washing twice with water of 2, 5 g of anhydrous sodium sulfate was added, dried for 30 min, and then rotated to dry to obtain 18 g of a pale yellow liquid.

matter Intermediate 1 Reactant 2 Sodium hydrogen 60%) Tetrahydrofuran Molecular Weight 367 157 24 / Number of moles 0.049 0.049 0.049 / Quantity 18g 7.7g Actual: 1.96g (60%)
Theory: 1.17g 70ml

In order to perform column chromatography, 18 g of silica gel was added to prepare a material layer. The column body was 7 times (130 g) of silica gel, and the developing agent was n-heptane: ethyl acetate = 20:1.

The solution passed through the column was spin-dried to obtain 9 g of a pale yellow liquid (the product has a large polarity and a lot of loss), dissolved by adding twice as much n-heptane, frozen at -15°C or less in a refrigerator, and filtered , Eluting with a small amount of frozen n-heptane, and repeating the purification to finally give 2.5 g of a white solid. Specific data and product quantities are shown in Table 8 below.

RT/min

A% 11.991
Reactant 2 16.782 25.585
Main peak 27.102
Polymethyl 27.888 28.270
Intermediate 1 Quantity GC after reaction product extraction
Y1017050211 0.320 7.888 73.722 3.006 4.070 1.889 / After column chromatography
1st purification GC
Y1017050212 / 0.223 98.542 0.620 0.229 0.003 7g
Wet weight Secondary purification GC
Y1017050213 / / 99.601 0.087 / / 5.2g
Wet weight Tertiary purification GC
Y1017050214 / 0.011 99.782 0.017 / / 3.7g
Wet weight 4th refined GC
Y1017050215 / / 99.898 0.011 / / 2.5g
Dry weight

The theoretical production amount is 18.3g, the actual production amount is 2.5g, the yield is 13.6%, and the mp of white solid is 109.45~110.25℃. The reason for the low yield seems to be that n-heptane has excellent solubility, causes a certain degree of loss due to a large number of purification times, and a large loss in column chromatography.

Synthesis Example 2: Synthesis of Substance Z

Substance Z may be synthesized according to Scheme 2 below, but is not limited thereto.

[Scheme 2]

1) Synthesis of Intermediate 2

[Intermediate 2]

[Reactive substance 3] [Reactive substance 4]

As shown in Table 9 below, 20 g of reactant 3, 49.2 g of reactant 4, and 300 ml of tetrahydrofuran were added to a 1 L three-necked flask, and the temperature was lowered to -15°C to -10°C under nitrogen gas protection, _{213ml (SiMe 3} ) ₂ NNa was added dropwise while controlling the temperature to -15℃～-10℃, and after the dropwise addition was completed, the temperature was naturally restored to room temperature, and then reacted with stirring for 3h, and the reaction product was extracted (workup). ).

matter Reactant 3 Reactant 4 （SiMe ₃ ） ₂ NNa
2M Tetrahydrofuran Molecular Weight 234 443 / / Number of moles 0.085 0.111 0.427 / Quantity 20g 49.2g 213ml 300ml

Post-treatment: An acid solution composed of 20 ml of concentrated hydrochloric acid and 100 ml of water is slowly added to oxidatively hydrolyze, adjusted to PH<3, and stirred for 5 minutes to separate the liquid. The aqueous phase was extracted once with 60 ml of ethyl acetate and the organic phases were combined, the organic phase was washed twice with 100 ml X 2 of water, dried for 30 min with 10 g of anhydrous sodium sulfate, and then dried by rotation to obtain 40 g of brown-red gel-like liquid, After extracting 4 times with 90mlX4 n-heptane, 20g silica gel chromatography, and finally after flushing twice with a 20:1=n-heptane:ethyl acetate mixture (2 times the height of the column), the solution passed through the column was Combined and spin-dried to obtain 17 g of a brownish yellow viscous liquid. Among them, the content of triphenyl phosphine oxide was large.

To perform column chromatography, 15 g of silica gel was added to prepare a material layer, the column body was 7 times (120 g) of silica gel, and the developing agent was n-heptane: ethyl acetate = 20:1.

The solution passed through the column was spin-dried to obtain 9.8 g of a pale yellow liquid (the product had a large polarity and a large loss), and hydrogen was added. Specific data and product quantities are shown in Table 10 below.

RT/min


A% 20.061
Reactant 3 23.950
Triphenyl phosphine 27.052
Triphenyl phosphine oxide 24.870
Main peak (cis type) 25.896
Main peak (trans type) 26.670
Polymethyl 27.378
Polymethyl Quantity After 3h reaction, extract the reactant and GC
Y1017051011 0.222 0.210 66.435 1.311 15.121 / / / GC after extraction of reactants after overnight
Y1017051012 0.655 0.172 62.745 1.998 17.570 / / / Column Pass Solution GC
Y1017051013 2.222 / 53.121 5.318 32.745 / 1.319 17g Attempt to extract back with alkali
Y1017051014 4.264 0.018 2.773 8.809 61.994 2.888 6.812 / Column chromatography GC
Y1017051015 0.200 0.003 0.032 12.942 77.537 2.771 1.675 9.8g

The theoretical production amount was 27.1 g, the actual production amount was 9.8 g, and the yield was 36.2% to obtain a pale yellow liquid. The reason for the low yield is that the reaction degree is relatively poor, the product and triphenyl phosphine oxide are packaged together, and because the polarity is large, separation is difficult, the loss of column chromatography is large, and the subsequent re-flushed column passing solution It seems to be because triphenyl phosphine oxide is contained and not incorporated.

2) Synthesis of Intermediate 3

[Intermediate 3]

As shown in Table 11 below, 8 g of intermediate 2, 0.8 g of Pd/C, 30 ml of ethanol, and 30 ml of toluene were added to a 250 ml three-necked flask, and hydrogen gas was injected and discharged three times, and then 3 h at room temperature (25 °C), hydrogen is added and the reactants are worked up. At this time, the temperature should not be too high, the time should not be too long, and hydrogen should be sufficiently added within 3 h at 30° C. or less, otherwise dehydrogenation products may occur.

matter Intermediate 2 Pd/C ethanol toluene Molecular Weight 318 / / / Number of moles 0.025 / / / Quantity 8g 0.8g 30ml 30ml

Post-treatment (purification): After filtering the hydrogenated solution and eluting the filter cake with a small amount of ethanol (Pd/C), the filtrate was spin-dried to obtain 8 g of a pale yellow liquid. The crystals are dissolved, frozen at -15°C or less in a refrigerator, filtered, and eluted with a small amount of frozen n-heptane to obtain 6.7 g of a pale yellow solid. Table 12 below shows the results of GC after extraction of the reactants and GC after purification.

RT/min


A% 19.757 24.984
Main peak 25.945
Intermediate 2 26.091
Isomers and specific structures of raw alkenes are unclear. Quantity After 3h reaction, extract the reactant and GC
Y1017052711 1.001 92.360 0.049 1.668 8g Tablet GC
Y1017052712 0.275 97.343 0.085 1.352 6.7g

The theoretical production amount is 8.05g, the actual production amount is 6.7g, the yield is 83.2%, and the mp of the pale yellow solid is 107.51℃～108.84℃. It is possible to consider how to carry out the reaction of the next step of the job without crystallization, and to finally purify the product.

3) Synthesis of Intermediate 4

[Intermediate 4]

As shown in Table 13 below, 5 g of intermediate 3 and 20 ml of methanol were added to a 100 ml three-necked flask, and 1 ml of concentrated sulfuric acid (98%) was slowly added while stirring, followed by heating and refluxing (80° C.) to react for 3 h. Workup.

matter Intermediate 3 Methanol Concentrated sulfuric acid
（98%） Molecular Weight 320 / / Number of moles 0.015 / / Quantity 5g 20ml 1ml

Post-treatment: The reaction solution was spin-dried, 30 ml of toluene and 20 ml of water were added and stirred for 3 min. The solution was separated, the aqueous phase was extracted once with 10 ml of toluene, the organic phase was merged, and the organic phase was mixed with 20 ml X 2 of water. Washed twice until neutral, dried, and rotary dried to obtain 5 g of a pale yellow liquid and prepared. Table 14 below shows the GC results after extracting the reactants.

RT/min

A% 23.774 24.786
Main peak 25.011
Intermediate 3 25.675
Dehydrogenation 25.806
Dehydrogenation Quantity After 3h reaction, extract the reactant and GC
Y1017060111 0.198 93.883 0.128 0.646 0.380 5g

The theoretical production amount was 5.2 g, the actual production amount was 5.0 g, and the yield was 96% to obtain a pale yellow liquid.

Dehydrogenation impurities are introduced into the raw material, and the specific ethylene bonding position has not been determined.

4) Synthesis of substance Z

As shown in Table 15 below, 0.22 g of sodium and 10 ml of methanol were added to a 100 ml three-necked flask, stirred until all sodium was dissolved, and then 2.93 g of reactant 2 and 30 ml of toluene were added, followed by water separation. After constructing an apparatus and removing methanol by evaporation to 105℃, a solution composed of 5g of intermediate 3 and 10ml of toluene was added dropwise, the methanol produced in the dropping process was separated, and after the dropwise addition was completed, methanol was evaporated to 108℃. To remove, and reflux reaction for 3 h to extract (workup) the reaction product.

matter Intermediate 3 Reactant 2 salt Methanol toluene Molecular Weight 334 157 23 / / Number of moles 0.0149 0.0187 0.0097 / / Quantity 5g 2.93g 0.22g 10ml 30ml

Post-treatment (purification): 30ml of water was slowly added to destroy the hydrolysis, stirred for 5min to separate the solution, and the aqueous phase was extracted once with 30ml of toluene, the organic phase was merged, and the organic phase was mixed with 30mlX2 of water. Washed twice, dried with 5 g of anhydrous sodium sulfate for 30 min, and then rotated to dry to obtain 5.2 g of a pale yellow liquid.

To perform column chromatography, 5 g of silica gel was added to prepare a material layer. The column body was 7 times (30 g) of silica gel, and the developing agent was n-heptane: ethyl acetate = 20:1.

The solution passed through the column was spin-dried to obtain 3.5 g of brownish-yellow liquid (the product has a large polarity and a lot of loss), dissolved by adding twice as much n-heptane, and frozen at -15℃ or less in a refrigerator It was filtered, eluted with a small amount of frozen n-heptane, and purification was repeated to finally give 1.5 g of a pseudo-white solid. Specific data and product quantities are shown in Table 16 below.

RT/min

A% 12.294
Reactant 2 24.421
Intermediate 3 30.841
Main peak 32.057
Polymethyl Quantity After column chromatography
1st purification GC
Y1017060511 / 0.001 99.834 0.064 2.2g After column chromatography
Secondary purification
Y1017060512 / 0.001 99.893 0.033 1.5g

The theoretical production amount is 6.8g, the actual production amount is 1.5g, the yield is 22%, and a white solid was obtained, 46.20~48.12℃, mp 53.73~55.42℃.

As a result of confirming the reactants, the main peak is about 86%. Impurities of about 32 min were analyzed by GCMS as polymethyl, and the specific structure was not determined. The structure that can be considered is the following material Z.

[Substance Z]

The reason for the low yield is that the solubility of n-heptane is excellent, the number of purifications is large, resulting in a certain degree of loss, the loss of column chromatography is large, the polarity is subsequently adjusted to increase, and the column is flushed, so there are relatively many impurities. , It seems to be because it cannot be refined into a product.

Example 1

After mixing 0.1 parts by weight of materials Y and Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal A, the liquid crystal phase was observed at a low temperature of -30°C, and the results are shown in Table 17 below. In the case of the liquid crystal composition (AY or AZ) in which the substance Y or Z was mixed, the nematic liquid crystal phase was maintained for more than 20 days, whereas the liquid crystal composition (A-T770) mixed with Tinuvin 770 (T770) solidified on the 9th day. .

Code A-Y A-Z A-T770 Low temperature stability (-30℃) >20 days >20 days 9 days NG

Example 2

After mixing 0.1 parts by weight of materials Y and Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal B, each of the liquid crystal phases was observed at a low temperature of -30°C, and the results are shown in Table 17 below. In the case of the liquid crystal composition (BY or BZ) in which the substance Y or Z was mixed, the nematic liquid crystal phase was maintained for more than 20 days, whereas the liquid crystal composition (B-T770) mixed with Tinuvin 770 (T770) solidified on the 6th day. .

Code B-Y B-Z B-T770 Low temperature stability (-30℃) >20 days >20 days 6 days NG

Example 3

After mixing 0.1 parts by weight of each material Y, Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal C, the liquid crystal phase was observed at a low temperature of -30°C, and the results are shown in Table 7 below. In the case of a liquid crystal composition (CY or CZ) in which substances Y or Z are mixed, the nematic liquid crystal phase is maintained for more than 20 days, whereas the liquid crystal composition (C-T770) mixed with Tinuvin 770 (T770) solidified on the 11th day. .

Code C-Y C-Z C-T770 Low temperature stability (-30℃) >20 >20 11th NG

Example 4

After mixing 0.1 parts by weight of materials Y and Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal D, each of the liquid crystal phases was observed at a low temperature of -30°C, and the results are shown in Table 20 below. In the case of the liquid crystal composition (DY or DZ) in which the substance Y or Z was mixed, the nematic liquid crystal phase was maintained for more than 20 days, whereas the liquid crystal composition (D-T770) mixed with Tinuvin 770 (T770) solidified on the 5th day. .

Code D-Y D-Z D-T770 Low temperature stability (-30℃) >20 days >20 days 5 days NG

Example 5

After mixing 0.1 parts by weight of materials Y, Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal E, each of 0.1 parts by weight of the commercially available tinuvin 770 (T770) was mixed, and the liquid crystal phase was observed at a low temperature of -30°C, and the results are shown in Table 21 below. In the case of the liquid crystal composition (EY or EZ) in which the substance Y or Z was mixed, the nematic liquid crystal phase was maintained for more than 20 days, whereas the liquid crystal composition (E-T770) mixed with Tinuvin 770 (T770) solidified on the 13th day. .

Code E-Y E-Z E-T770 Low temperature stability (-30℃) >20 days >20 days 13 days NG

Example 6

After mixing 0.1 parts by weight of materials Y, Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal F, the liquid crystal phase was observed at a low temperature of -30°C, and the results are shown in Table 22 below. In the case of a liquid crystal composition (FY or FZ) in which substances Y or Z are mixed, the nematic liquid crystal phase is maintained for more than 20 days, whereas the liquid crystal composition (F-T770) mixed with Tinuvin 770 (T770) solidified on the 15th day. .

Code F-Y F-Z F-T770 Low temperature stability (-30℃) >20 days >20 days 15 days NG

Example 7

After mixing 0.1 parts by weight of materials Y and Z and commercially available Tinuvin 770 (T770) in 100 parts by weight of the parent liquid crystal G, the liquid crystal phase was observed at a low temperature of -30°C, and the results are shown in Table 23 below. In the case of the liquid crystal composition (GY or GZ) in which the substance Y or Z was mixed, the nematic liquid crystal phase was maintained for more than 20 days, whereas the liquid crystal composition (G-T770) mixed with Tinuvin 770 (T770) solidified on the 9th day. .

Code G-Y G-Z G-T770 Low temperature stability (-30℃) >20 days >20 days 9 days NG

[evaluation]

1) Heat and UV stability for AY, AZ, and A-T770 liquid crystal compositions obtained by mixing 0.1 parts by weight of substances Y, Z and commercially available Tinuvin 770 (T-770) in 100 parts by weight of the parent liquid crystal A. It evaluated as follows, and the results are shown in Tables 12 and 24 below.

After injecting each liquid crystal composition into a test cell with a cell gap of 4 μm, initial VHR and 60° C. heat were applied, and then the VHR values on the 1st, 3rd, and 10th days were checked, and after applying UV 3J and 6J, respectively. VHR fall was confirmed.

60Hz 3Hz A-Y A-Z A-T770 A-Y A-Z A-T770 Heat
stress Initial value 99.5 99.3 98.5 95.2 95.0 94.3 1 day later 99.6 99.1 98.5 95.5 95.0 94.4 3 days later 99.6 99.1 98.3 95.6 94.9 94.3 10 days later 99.6 99.0 98.0 95.6 94.8 94.2

60Hz 3Hz A-Y A-Z A-T770 A-Y A-Z A-T770 UV
stress Initial value 99.5 99.3 98.4 95.1 95 94.3 3J 99.0 98.9 97.5 93.7 93.5 92.9 6J 98.9 98.9 97.4 93.4 93.4 92.7

2) Heat and UV stability for EY, EZ, and A-T770 liquid crystals obtained by mixing 0.1 parts by weight of substances Y, Z and commercially available Tinuvin 770 (T-770) in 100 parts by weight of the parent liquid crystal E It evaluated as, and the results are shown in Tables 26 and 27 below.

After injecting each liquid crystal composition into a test cell with a cell gap of 4 μm, initial VHR and 60° C. heat were applied, and then the VHR values on the 1st, 3rd, and 10th days were checked, and after applying UV 3J and 6J, respectively. VHR fall was confirmed.

60Hz 3Hz E-Y E-Z E-T770 E-Y E-Z E-T770 Heat
stress Initial value 98.2 98.0 97.8 83.1 83.0 82.4 1 day later 98.1 97.9 97.9 83.2 82.9 82.0 3 days later 98.0 97.9 97.8 82.8 82.6 81.9 10 days later 97.9 97.8 97.5 82.0 81.9 81.1

60Hz 3Hz E-Y E-Z E-T770 E-Y E-Z E-T770 UV
stress Initial value 98.1 98.0 97.8 83.2 83.0 82.4 3J 98.0 97.9 97.9 82.8 82.6 81.9 6J 98.0 97.9 97.8 82.4 82.1 81.5

The materials of the present invention are commercially available through the above examples. Compared to the material T-770, it was confirmed that the low-temperature stability was very excellent and the VHR value was equal or higher.

SUB1: first substrate
SUB2: second substrate
LC: liquid crystal layer
PE: pixel electrode
CE: common electrode
BS1: first base substrate
BS2: second base substrate
GI: gate insulating film
GE: gate electrode
SM: semiconductor pattern
SE: source electrode
DE: drain electrode
IL: interlayer
PSV: Shield
CH: contact hole
CF: color filter

Claims (23)

delete delete delete A light stabilizer compound represented by the following formula (1);
One or two or more compounds represented by the following formula (5); And
Including a compound represented by the following formula 4-1 or 4-2,
A liquid crystal composition exhibiting a positive dielectric anisotropy of 8.8 or more or a negative dielectric anisotropy of -3.4 or less:
[Formula 1]

[Formula 5]

In Formula 1 or Formula 5,
X ₁ is a direct bond or a carbonyl group,
R ₄ is alkenyl having 2 to 8 carbon atoms, in which case, a hydrogen atom may be replaced by a halogen,
R ₅ is C 1 to C 8 alkyl, C 1 to C 8 alkoxy, or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently of each other, in a manner in which O atoms are not directly connected to each other To be replaced by -C≡C- _{, -CF 2 O-, -OCF 2} -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO-O- Hydrogen atom can be replaced by halogen,
Rings E, F and G are each independently trans-1,4-cyclohexylene, H (hydrogen), which can be substituted with one or two O (oxygen) carbons in the ring. 1, where trans-1,4-cyclohexylene or H (hydrogen) can be substituted with 1 or 2 F (fluorine), which can be substituted with 1 or 2 F (fluorine), 4-phenylene (1,4-phenylene),
n is an integer of 4 or more, c and d are each independently an integer of 0, 1 or 2,
[Formula 4-1]

In Formula 4-1,
R ₁ is hydrogen, branched or cyclic C 1 to C 8 alkyl, C 1 to C 8 alkoxy or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently an O atom -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O- Can be replaced by CO-O-, hydrogen atom can be replaced by halogen,
X ₂ to X ₆ are each independently H, F or OCF ₃ ,
Y ₁ is H or a methyl group,
Rings A and B are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted, or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),
a is an integer of 0 or 1,
[Formula 4-2]

In Formula 4-2,
R ₂ and R ₃ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, and O atoms are each independently _{-C≡C-, -CF 2} O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO- in a manner that is not directly linked Can be replaced by O-, hydrogen atom can be replaced by halogen,
X ₇ and X ₈ are each independently H, F or OCF ₃ , at least one is F or OCF ₃ ,
Rings C and D are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene), when the ring C is cyclohexylene, R _{2 may be two} , wherein R 2 may be the same or different from each other,
b is an integer of 0 or 1. The method of claim 4,
The compound represented by Formula 5 is a liquid crystal composition comprising a compound represented by Formula 5-1 below.
[Chemical Formula 5-1]

In Formula 5-1,
R ₄ is alkenyl having 2 to 5 carbon atoms,
c is an integer of 0 or 1,
R ₅ , rings E and F are as defined in Chemical Formula 5. The method of claim 4,
The liquid crystal composition is a liquid crystal composition including at least one of the following formulas as a compound represented by Chemical Formula 5.

In the above formula,
R ₄ is alkenyl having 2 to 5 carbon atoms,
R ₅ is C 1 to C 8 alkyl or C 1 to C 8 alkoxy. The method of claim 5,
The compound represented by Formula 5-1 is a liquid crystal composition comprising a compound represented by the following formula.

In the above formula,
R ₅ is C 1 to C 8 alkyl or C 1 to C 8 alkoxy. delete The method of claim 4,
The compound represented by Formula 4-1 is a liquid crystal composition comprising a compound represented by Formulas 4-1-1 to 4-1-8 below.
[Formula 4-1-1]

[Formula 4-1-2]

[Formula 4-1-3]

[Formula 4-1-4]

[Formula 4-1-5]

[Formula 4-1-6]

[Formula 4-1-7]

[Formula 4-1-8]

In Formulas 4-1-1 to 4-1-8,
R ₁ is C 1 to C 8 alkyl, C 1 to C 8 alkoxy or C 2 to C 8 alkenyl. The method of claim 4,
The liquid crystal composition further comprises one or two or more compounds represented by the following formula (6):
[Formula 6]

In Chemical Formula 6,
R ₆ and R ₇ are each independently alkyl having 1 to 8 carbon atoms, or alkoxy having 1 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, in a manner in which the O atoms are not directly connected to each other Can be replaced by -C≡C-, -CF ₂ O-, -OCF ₂ -, -O-, -CO-O-, -O-CO- or -O-CO-O-, the hydrogen atom is halogen Can be replaced with
Rings H and I are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),
e and f are each independently an integer of 0, 1, or 2, and e+f≤2. The method of claim 10,
The compound represented by Formula 6 is any one of the compounds represented by Formulas 6-1 to 6-4 below.
[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

In Formulas 6-1 to 6-4,
R ₆ and R ₇ are as defined in Chemical Formula 6. The method of claim 10,
The liquid crystal composition further comprises one or two or more compounds represented by the following formula (7):
[Formula 7]

In Chemical Formula 7,
R ₈ is C 1 to C 8 alkyl, C 1 to C 8 alkoxy, or C 2 to C 8 alkenyl, wherein at least one -CH ₂ -group is each independently of each other, in a manner in which O atoms are not directly connected to each other To be replaced by -C≡C- _{, -CF 2 O-, -OCF 2} -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO-O- Hydrogen atom can be replaced by halogen,
X ₉ to X ₁₁ are each independently H, F or OCF ₃ ,
Rings J and K are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),
g is an integer of 0, 1 or 2. However, the compound represented by Chemical Formula 5 is excluded. The method of claim 12,
The compound represented by Formula 7 is any one of the compounds represented by Formulas 7-1 to 7-9 below.
[Chemical Formula 7-1]

[Formula 7-2]

[Chemical Formula 7-3]

[Chemical Formula 7-4]

[Chemical Formula 7-5]

[Formula 7-6]

[Formula 7-7]

[Formula 7-8]

[Chemical Formula 7-9]

In Formulas 7-1 to 7-9,
R ₈ is as defined in Chemical Formula 7. The method of claim 12,
The liquid crystal composition further comprises an antioxidant represented by the following formula (9):
[Formula 9]

In Chemical Formula 9,
R ₁₁ is an alkyl group having 1 to 12 carbon atoms,
Ring N is trans-1,4-cyclohexylene, tetrahydropyran or dioxane,
i is an integer of 0, 1 or 2. delete The method of claim 4,
The compound represented by Formula 4-2 is a liquid crystal composition comprising a compound represented by Formula 4-2-1:
[Formula 4-2-1]

In Formula 4-2-1,
R _'3 is an alkyl group having 1 to 8 carbon atoms, wherein one or more -CH ₂ - groups may be replaced by -CH = CH-, a hydrogen atom is optionally replaced by halogen,
R ₂ , X ₇ , X ₈ , ring C, ring D and b are as defined in Formula 4-2. The method of claim 4,
The compound represented by Formula 4-2 is a liquid crystal composition comprising a compound represented by the following formula:

In the above formula
R ₂ and R ₃ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms. delete delete The method of claim 4,
The liquid crystal composition further comprises one or two or more compounds represented by the following formula (8):
[Formula 8]

In Chemical Formula 8,
R ₉ and R ₁₀ are each independently alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, or alkenyl having 2 to 8 carbon atoms, wherein at least one -CH ₂ -group is each independently of each other, O atoms are -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -O-, -CO-O-, -O-CO- or -O-CO Can be replaced by -O-, hydrogen atom can be replaced by halogen,
Z ₁ is -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -CF ₂ O- or -OCF ₂ -,
Rings L and M are each independently trans-1,4-cyclohexylene where 1 or 2 carbon atoms in the ring can be substituted or 1 or 2 F for H Possible 1,4-phenylene (1,4-phenylene),
h is an integer of 0, 1 or 2. The method of claim 20,
The compound represented by Formula 8 is a liquid crystal composition represented by Formula 8-1 or 8-2 below.
[Chemical Formula 8-1]

[Formula 8-2]

In Formula 8-1 and Formula 8-2,
R ₉ and R ₁₀ are as defined in Chemical Formula 8. The method of claim 20,
The liquid crystal composition further comprises an antioxidant represented by the following formula (9):
[Formula 9]

In Chemical Formula 9,
R ₁₁ is an alkyl group having 1 to 12 carbon atoms,
Ring N is trans-1,4-cyclohexylene, tetrahydropyran or dioxane,
i is an integer of 0, 1 or 2. A first substrate and a second substrate disposed opposite to each other;
An electric field generating electrode formed on at least one of the first substrate and the second substrate;
A first alignment layer formed on the first substrate and a second alignment layer formed on the second substrate; And
A liquid crystal layer formed of a plurality of liquid crystal molecules interposed between the first substrate and the second substrate, wherein the liquid crystal layer includes claims 4 to 7, 9 to 14, and 16 , A liquid crystal display device comprising the liquid crystal composition according to any one of claims 17, 20, 21, and 22.

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