WO2018097630A1 - Polymerizable compound and liquid crystal composition comprising same - Google Patents

Abstract

The present invention relates to a polymerizable compound and a liquid crystal composition comprising the polymerizable compound and, more specifically, to a polymerizable compound, which is used in the manufacture of a polymer stabilized alignment (PSA) or polymer stabilized-vertical aligned (PS-VA) mode liquid crystal display, and to a liquid crystal composition comprising the polymerizable compound. The compound according to the present invention exhibits low-temperature stability, and acquires an effect of improving the pre-tilt angle of liquid crystals in the photo-polymerization by UV.

Description

Polymerizable Compound and Liquid Crystal Composition Comprising the Same

The present invention relates to a polymerizable compound and a liquid crystal composition comprising the same.

Liquid crystal displays (LCDs) are one of the most widely used flat panel displays. The liquid crystal display may generate an electric field in the liquid crystal layer by applying a voltage to the field generating electrode to determine the direction of the liquid crystal molecules of the liquid crystal layer and adjust the transmittance of light passing through the liquid crystal layer, thereby enabling ON / OFF display. It can be applied to both transmissive and reflective types, such as twisted nematic (TN), in-plane switching (IPS), optically Compensatory Bend (OCB), vertically aligned (VA), electrically controlled Birefringence (VAB), and super twisted nematic (STN) Various types of liquid crystal display devices such as) have been developed.

Among them, a vertical alignment (VA) mode liquid crystal display includes a liquid crystal having negative dielectric anisotropy between two transparent electrodes, and in an off state where no voltage is applied, the liquid crystal molecules are aligned perpendicular to the electrode surface and In the on state where a voltage is applied to the liquid crystal molecules, the liquid crystal molecules are aligned parallel to the electrode surface. The opening and closing of the light from the backlight passing through the polarizer can be controlled according to the vertical and horizontal alignment of the liquid crystal according to the presence or absence of voltage, but the response speed becomes very high if the direction of parallel alignment when the voltage is applied to the electrode is not determined in advance. There are disadvantages.

As a method for overcoming the disadvantages of the VA mode liquid crystal display device, the polymerizable compound is mixed with the mother liquid crystal and then polymerized in the on state where a voltage is applied, so that the direction of the mother liquid crystal can be determined in advance, thereby improving the response speed. Attention has been paid to a liquid crystal display device having a polymer stabilized alignment (PSA) or a polymer stabilized vertical alignment (PS-VA) mode. In this case, the polymerizable compound to be used must move together in the direction in which the host liquid crystal lies when voltage is applied to the electrode through interaction with the vertically aligned liquid crystal. In this way, the induction of the inclination and curing through light irradiation maintains a constant inclination even when no voltage is applied, and when the voltage is applied again, the mother liquid crystal is rapidly oriented in the inclination direction, thereby realizing a high-speed response.

The liquid crystal used to implement the PSA mode liquid crystal display contains 0.1 to 2.0% of a polymerizable compound and must maintain a stable liquid crystal state at low temperature. If the liquid crystal composition containing the polymerizable compound precipitates the polymerizable compound at low temperature, the PSA mode may not be realized. Accordingly, there is a considerable need for a polymerizable compound having a high solubility with liquid crystals and a low melting point and maintaining stability at low temperatures when mixed with liquid crystals.

In addition, in the PSA mode, after the injection of the liquid crystal composition containing the polymerizable compound is irradiated with ultraviolet light, the polymerizable compound in the liquid crystal is reacted by the ultraviolet light, which is generally irradiated with 40 ~ 100J. After UV irradiation, the pretilt angle of the liquid crystal is changed from 90 degrees to a lower angle, and the lower the pretilt angle than 90 degrees, the faster the response time can be realized. In this regard, Korean Patent No. 10-0219707 has suggested a composition of the vertically aligned liquid crystal.

The present invention has been made to solve the technical necessity as described above, an object of the present invention is to provide a polymerizable compound exhibiting improved low-temperature stability, polymerizable to lower the pretilt angle of the liquid crystal during photopolymerization in PSA mode It is to provide a compound and a liquid crystal composition comprising the same.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

Accordingly, the present invention provides a polymerizable compound represented by the following [Formula 1].

[Formula 1]

In [Formula 1],

P ₁ and P ₂ are each independently a radical of any of a polymerizable functional group, hydrogen, alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or one or more of -CH ₂ -is one of the radicals directly Unsubstituted or substituted with —C≡C—, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —O—, —CO—O—, or —O—CO— Any of the radicals in which hydrogen is replaced by halogen, at least one of P ₁ and P ₂ is a polymerizable functional group,

Sp ₁ And Sp ₂ are each independently a single bond, a radical of any one of alkyl having 1 to 15 carbon atoms, at least one hydrogen in the radical is substituted with halogen, or one or more -CH ₂ -is not directly connected to oxygen atoms. Radicals replaced by -C≡C-, -CH = CH-, -O-, -CO-O-, -O-CO- or -O-CO-O-,

L ₁ each independently represents an alkyl group having 1 to 5 carbon atoms, and one or two or more -CH ₂ -groups in the alkyl group are each selected from -O-, -S-, and -NH- so that oxygen atoms do not directly adjoin. , -N (CH ₃ )-, -CO-, -CO-O-, -O-CO-, -OCOO-, -SCO-, -COS-, -CH = CH- or -C≡C- Substituted or unsubstituted,

Z ₁ to Z ₄ are each independently _{-CH 2 CH 2 -, -CH =} CH-, -CH 2 O-, -OCH 2 -, -C≡C-, -CH 2 CF 2 -, -CHFCHF-, -CF ₂ CH _2- , -CH ₂ CHF-, -CHFCH _2- , -C ₂ F _4- , -O-, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -Or a single bond,

A ₁ to A ₄ are each independently 1,4-cyclohexylene; 1,4-phenylene; Or at least one hydrogen is 1,4-phenylene substituted with halogen or an alkyl group having 1 to 5 carbon atoms,

a, b, c and d are each independently an integer of 0 to 2, and a + b + c + d is 1 to 4.

In one embodiment of the present invention, P ₁ and P ₂ are each independently

,

또는

일 수 있다.

,

or

Can be.

일 수 있다.In another embodiment of the present invention, P ₁ or P ₂ is

Can be.

In another embodiment of the present invention, the polymerizable compound of [Formula 1] may be one selected from the group consisting of the following [Formula 1-1] to [Formula 1-30].

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Formula 1-25]

[Formula 1-26]

[Formula 1-27]

[Formula 1-28]

[Formula 1-29]

[Formula 1-30]

X ₁ in [Formula 1-1] to [Formula 1-30] is each independently hydrogen (H), methyl (CH ₃ ) or methoxy (OCH ₃ ), R ₁₁ and R ₁₂ are each independently hydrogen , Or a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms, or one or more of -CH ₂ -of the radicals are -C 원자 C-, -CH = CH- Is a radical substituted with —CF ₂ O—, —OCF ₂ —, —O—, —CO—O— or —O—CO—, or one or more hydrogens of the radicals replaced with halogen.

In addition, the present invention provides a liquid crystal composition comprising the polymerizable compound of the above [Formula 1].

In one embodiment of the present invention, the composition may further include a liquid crystal compound represented by the following [Formula 2].

[Formula 2]

R ₁ and R ₂ are each independently a radical of any one of alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or at least one of -C ₂ -is one of -C≡ so that oxygen atoms are not directly connected. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Rings A and B are each independently 1,4-cyclohexylene or 1,4-phenylene.

In another embodiment of the present invention, the composition may further include a liquid crystal compound represented by the following [Formula 3].

[Formula 3]

R ₃ and R ₄ are each independently a radical of any one of alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or at least one of -C ₂ -of the radicals is -C 산소 so that oxygen atoms are not directly connected. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Z ₅ and Z ₆ are each independently a single bond; -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-, -CO- O- or -O-CO-,

e and f are each independently an integer of 0 or 1,

Ring C, D and E are each independently

이다.

to be.

In another embodiment of the present invention, the liquid crystal composition may further include a liquid crystal compound represented by the following [Formula 4].

[Formula 4]

R ₅ and R ₆ are each independently a radical of any one of alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or at least one of -C ₂ -is one of -C≡ so that oxygen atoms are not directly connected. C-, -CH = CH-, -CF ₂ O-,-OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Ring F, G and I are each independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which one or more hydrogens are replaced by halogen,

(F) is hydrogen or F,

g and h are each independently an integer of 0 or 1, and g + h is an integer of 1 or 2.

In another embodiment of the present invention, the liquid crystal composition may further include at least one or more of a compound represented by the following [Formula 5] or a compound represented by the following [Formula 6].

[Formula 5]

[Formula 6]

R ₇ is alkyl having 1 to 12 carbon atoms,

R ₈ and R ₉ are each independently hydrogen, oxygen or alkyl having 1 to 12 carbon atoms,

Ring J is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene with at least one hydrogen substituted by halogen,

i is an integer of 0 or 1, and k is an integer of 1-12.

The present invention exhibits improved low temperature stability, and provides a polymerizable compound which improves the pretilt angle of the liquid crystal upon photopolymerization by ultraviolet rays and a liquid crystal composition comprising the same. Such a polymerizable compound enables high-speed response to provide a liquid crystal composition optimized for liquid crystal displays of various modes, in particular, PSA and PS-VA modes.

1 is a view showing the results of measuring the inclination angle and response time while sequentially increasing the UV irradiation dose after producing a cell by mixing the existing material AA-H in the parent liquid crystal MixA.

2 is a view showing the results of measuring the inclination angle and response time while sequentially increasing the UV irradiation dose after producing a cell by mixing AAC1-H of the present invention material in the parent liquid crystal MixA.

As the inventive concept allows for various changes and numerous modifications, particular embodiments will be illustrated in tables and graphs and described in detail in the text. However, this should not be construed as limiting the present invention to a particular disclosed form, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a polymerizable compound having a novel structure and a liquid crystal composition including the same according to an embodiment of the present invention will be described in more detail.

The present invention relates to a polymerizable compound used in PSA mode and a composition comprising the same. The liquid crystal used in the PSA mode contains a polymerizable compound, and the polymerizable compound should basically maintain a stable state at low temperature when mixed with the liquid crystal, and should allow photopolymerization to occur effectively by ultraviolet rays.

The PSA mode refers to Polymer Stabilized Alignment (PSA), the polymerizable compound of the present invention and a composition including the same are used for PSA mode, and the term 'PSA mode' refers to the orientation of the mother liquid crystal. It refers to a driving mode that controls the directionality that is formed, and can also be expressed in terms such as 'polymer sustained (PS) mode' or 'polymer stabilized-vertical aligned (PS-VA) mode'. If it means a driving mode for controlling the orientation of the parent liquid crystal is not limited to the above-mentioned terms.

In general, a small amount of a polymerizable compound is used by using a liquid crystal medium mixed with a polymerizable compound of 2.0% or less in PSA mode. However, when a polar (meth) acrylate is used at both ends due to its molecular structure, the melting point is considerably high. Even if a small amount is used, the low temperature stability of the entire liquid crystal mixture is reduced. For example, in the following [Formula 7-1], which is introduced in Korean Patent Publication No. 2005-0009294, the melting point is very high at 148 ° C., and it has a fatal defect in low temperature stability. The melting point can go up to an impractical point. In addition, the melting point of the substance substituted with fluorine (F) at the terminal as shown in [Formula 7-2], which is a polymerizable compound of Korean Patent Publication No. 10-2013-0043693, is 10 占 폚 or more than [Formula 7-1]. Appears high.

[Formula 7-1]

[Formula 7-2]

In the present invention, by introducing a fluorine and an alkyl group at the same time as a substituent for lowering the melting point on the side of the phenyl group, it is possible to provide a polymerizable compound having a low melting point and improved low temperature stability of the polymerizable compound in the liquid crystal composition.

In addition, after injecting the liquid crystal containing the polymerizable compound in the panel in the PSA mode, the inclination angle of the liquid crystal is 90 degrees, it is possible to implement a fast response time to maintain a state lower than 90 degrees after ultraviolet irradiation. The present invention provides a polymerizable compound and a liquid crystal composition including the compound which can implement a fast response time by effectively controlling the pretilt angle of the liquid crystal by the polymerizable compound in the liquid crystal composition.

The polymerizable compound according to one embodiment of the present invention is represented by the following [Formula 1].

[Formula 1]

In [Formula 1],

P ₁ and P ₂ are each independently a radical of any of a polymerizable functional group, hydrogen, alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or one or more of -CH ₂ -is one of the radicals directly Unsubstituted or substituted with —C≡C—, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —O—, —CO—O—, or —O—CO— Any one of radicals in which hydrogen (H) is replaced by halogen, at least one of P ₁ and P ₂ is a polymerizable functional group,

Sp ₁ and Sp ₂ are each independently a single bond, a radical of any one of alkyl of 1 to 15 carbon atoms, at least one hydrogen in the radical is substituted with halogen, or one or more -CH _2- Radicals replaced by —C≡C—, —CH═CH—, —O—, —CO—O—, —O—CO— or —O—CO—O— so as not to be linked,

L ₁ each independently represents an alkyl group having 1 to 5 carbon atoms, and one or two or more -CH ₂ -groups in the alkyl group are each selected from -O-, -S-, and -NH- so that oxygen atoms do not directly adjoin. , -N (CH ₃ )-, -CO-, -CO-O-, -O-CO-, -OCOO-, -SCO-, -COS-, -CH = CH- or -C≡C- Substituted or unsubstituted,

Z ₁ to Z ₄ are each independently _{-CH 2 CH 2 -, -CH =} CH-, -CH 2 O-, -OCH 2 -, -C≡C-, -CH 2 CF 2 -, -CHFCHF-, -CF ₂ CH _2- , -CH ₂ CHF-, -CHFCH _2- , -C ₂ F _4- , -O-, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -Or a single bond,

A ₁ to A ₄ are each independently 1,4-cyclohexylene; 1,4-phenylene; Or at least one hydrogen is 1,4-phenylene substituted with halogen or an alkyl group having 1 to 5 carbon atoms,

a, b, c and d are each independently an integer of 0 to 2, and a + b + c + d is 1 to 4.

In the examples of the present invention, in consideration of the ease of synthesis and the like, Sp ₁ and Sp ₂ represent a single bond, and P ₁ and P ₂ represent a polymerizable group using the following structure.

,

또는

,

or

일 수 있다.In one embodiment of the present invention, P ₁ or P ₂ is

Can be.

Unlike the other polymerizable compounds, the polymerizable compound having a 2-alkyl-3-fluorinated phenylene structure, as shown in [Formula 1], has a low melting point and has low solubility at low temperatures when mixed with liquid crystal. It has the advantage of rapidly rising. The polymerizable compound of [Formula 1] more useful for the low temperature stability may be [Formula 1-1] to [Formula 1-30], X ₁ in the following [Formula 1-1] to [Formula 1-30] Are each independently hydrogen (H), methyl (CH ₃ ) or methoxy (OCH ₃ ), and R ₁₁ and R ₁₂ are each independently hydrogen, alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms. Or -CH ₂ -of at least one of the radicals is -C 않도록 C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-,- Radicals substituted with CO—O— or —O—CO— or with one or more hydrogens of the radicals replaced with halogen.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Formula 1-25]

[Formula 1-26]

[Formula 1-27]

[Formula 1-28]

[Formula 1-29]

[Formula 1-30]

According to an embodiment of the present invention, in Chemical Formula 1-1 to Chemical Formula 1-30, X ₁ is hydrogen in Chemical Formula 1-1, and Chemical Formula 7-1 or Chemical Formula 7 Surprisingly, the melting point decreases by more than 60 ° C. compared with [2].

In addition, terphenyl series such as [Formula 1-13] to [Formula 1-18] are excellent in pretilt angle and response time, and in particular, a polymerizable group in the sock end as shown in [Formula 1-7] to [Formula 1-10]. In the terphenyl polymerizable compound having a fluorine and an alkyl group at the same time the terminal phenyl group is substituted at the same time has a characteristic that reacts very quickly to ultraviolet rays and confirmed this experimentally in the examples. In view of low temperature stability, L ₁ is more preferably an ethyl group than a methyl group, and the ethyl substituent decreases the melting point by 20 ° C. or more as compared with the methyl substituent when confirming the polymerizable compound synthesized in the Examples.

In the liquid crystal composition according to the embodiment of the present invention, the polymerizable compound of [Formula 1] may be included in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total liquid crystal composition, and more specifically in the range of 0.05 to 2 parts by weight. It is included in. If it is less than 0.01 parts by weight it is difficult to expect the role as a polymerizable compound, and if it exceeds 5 parts by weight can reduce the characteristics of the display.

In the present invention, 100 parts by weight of the total liquid crystal composition may be calculated as the content of all the components included in the liquid crystal composition, but is not limited thereto. For example, the liquid crystal compound may include a liquid crystal compound, a polymerizable compound, and other additives. have.

According to an embodiment of the present invention, when using two or more types of polymerizable compounds, at least one kind may be more easily controlled using the compound of [Formula 1].

In order to implement the PSA mode using the above [Formula 1], it can generally be mixed with 8 to 15 liquid crystal compounds. In one embodiment of the present invention, for the liquid crystal composition applicable to the liquid crystal display, one or two or more compounds selected from the following [Formula 2] may be mixed.

[Formula 2]

R ₁ and R ₂ are each independently a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms; Or wherein at least one of the radicals -CH ₂ - is an oxygen atom to prevent direct connection _{-C≡C-, -CH = CH-, -CF 2} O-, -OCF 2 -, -O-, -CO-O- Or a radical substituted with -O-CO- or at least one hydrogen of said radicals is replaced with halogen,

Rings A and B are each independently 1,4-cyclohexylene or 1,4-phenylene.

When the liquid crystal composition includes the liquid crystal component represented by the above [Formula 2], it is easy to adjust the response time of the display due to the low viscosity property of the [Formula 2], and in the [Formula 2], the rings A and B are It is useful to improve the response time by lowering the rotational viscosity while keeping the transparent point constant when all are 1,4-cyclonuylene or R ₁ and R ₂ are all alkyl or one of R ₁ and R ₂ is alkenyl. [Formula 2] is 5 to 50 parts by weight based on 100 parts by weight of the liquid crystal composition, specifically may include 15 to 40 parts by weight. If it is less than 5 parts by weight or more than 50 parts by weight, it is difficult to secure the transparent point, which may greatly lower the operating temperature range of the display.

100 parts by weight of the liquid crystal composition in the present invention may be calculated by the amount of the liquid crystal compounds included in the liquid crystal composition.

[Chemical Formula 2] may include one or two or more kinds of compounds represented by the following [Formula 2-1] to [Formula 2-4], wherein R ₁ and R ₂ are represented by the following [Formula 2] Same as the definition of R ₁ , R ₂ , R ₁₁ may be hydrogen (H) including the definition of R ₁ .

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

The liquid crystal composition including the above [Formula 1] may include one or two or more compounds selected from the following [Formula 3] having an absolute dielectric constant greater than one.

[Formula 3]

R ₃ and R ₄ are each independently a radical of any one of alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or at least one of -C ₂ -of the radicals is -C 산소 so that oxygen atoms are not directly connected. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Z ₅ and Z ₆ are each independently a single bond, or -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-, -CO-O- or -O-CO-,

e and f each independently represent an integer of 0 or 1,

Rings C, D and E each independently represent one of the following structures.

[Formula 3] is a liquid crystal medium to increase the dielectric anisotropy to exhibit a substantial display characteristics. [Formula 3] may include 20 to 70 parts by weight based on 100 parts by weight of the liquid crystal composition. If less than 20 parts by weight, the dielectric anisotropy is too low, the driving voltage of the display is too high, and if it exceeds 70 parts by weight, the viscosity increases or the transparent point is not secured, thereby satisfying the characteristics of the display (operating temperature and response characteristics). Difficult to do Specifically, [Formula 3] may include one or two or more compounds represented by the following [Formula 3-1] to [Formula 3-8], and the definition of R ₃ and R ₄ is the above Formula 3 ] Is the same as the definition of R ₃ and R ₄ , and (F) means hydrogen or fluorine.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

Specifically, [Formula 3] is a compound selected from the group consisting of the following [Formula 3-2-1], [Formula 3-5-1] and [Formula 3-6], one or two or more. It is possible to do According to an embodiment of the present invention, the [Formula 3-2-1], [Formula 3-5-1] or [Formula 3-6] are a polymerization reaction of [Formula 1] which is a polymerizable compound in PSA mode. To increase the change of the inclination angle and improve the response time.

[Formula 3-2-1]

[Formula 3-5-1]

[Formula 3-6]

In [Formula 3-2-1], [Formula 3-5-1] and [Formula 3-6], each of R ₃ and R ₄ is independently an alkyl group having 2 to 5 carbon atoms or alkoxy having 2 to 5 carbon atoms. Which is one radical. If R ₃ and R ₄ are an alkyl group having 2 to 5 carbon atoms or alkoxy having 2 to 5 carbon atoms, there is an effect of increasing negative dielectric anisotropy.

The liquid crystal composition including the above [Formula 1] may include one or two or more compounds selected from the following [Formula 4].

[Formula 4]

R ₅ and R ₆ are each independently a radical of any one of alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or at least one of -C ₂ -is one of -C≡ so that oxygen atoms are not directly connected. C-, -CH = CH-, -CF ₂ O-,-OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Ring F, G and I each independently represent 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which one or more hydrogens are replaced by halogen,

(F) means hydrogen or F,

g and h each independently represent an integer of 0 or 1, and g + h means an integer of 1 or 2.

The liquid crystal compound represented by [Formula 4] is a material having a transparent point of 80 degrees or more, an important material for determining an operating temperature in a display, and may be included in an amount of 5 to 60 parts by weight based on 100 parts by weight of the entire liquid crystal composition. If less than 5 parts by weight or more than 60 parts by weight is used, the viscosity may be reduced or increased to obtain a desired display response time. Specifically, the [Formula 4] may include one or two or more compounds selected from the group consisting of the following [Formula 4-1] to [Formula 4-3].

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

R ₅ and R ₆ are the same as the definition of R ₅ and R ₆ in [Formula 4].

The liquid crystal composition including [Formula 1] may include one or two or more compounds selected from the group consisting of compounds represented by the following [Formula 5] to [Formula 6]. [Formula 5] is a substance that improves the thermal stability of the liquid crystal composition as an antioxidant, may be included 0.01 to 0.05 parts by weight based on the entire liquid crystal composition. If it is less than 0.01 parts by weight it is difficult to expect the role as an antioxidant, if exceeding 0.05 parts by weight can reduce the characteristics of the display. The following [Formula 6] may be included 0.01 to 0.1 parts by weight based on the entire liquid crystal composition as an ultraviolet stabilizer. If it is less than 0.01 parts by weight it is difficult to expect the role as a UV stabilizer, if exceeding 0.1 parts by weight can reduce the characteristics of the display.

[Formula 5]

[Formula 6]

R ₇ means alkyl having 1 to 12 carbon atoms

R ₈ and R ₉ each independently represent hydrogen, oxygen or alkyl having 1 to 12 carbon atoms,

Ring J is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene with at least one hydrogen substituted by halogen,

i means an integer of 0 or 1

k means an integer from 1 to 12.

Specifically, when R ₈ and R ₉ are hydrogen, the trapping efficiency of radicals that can be generated in the liquid crystal as the UV stabilizer is the highest.

According to an embodiment of the present invention, the compound represented by Chemical Formula 5 may be included in one or more kinds, wherein ring J may be the same or different from each other.

According to an embodiment of the present invention, the liquid crystal composition is

At least one polymerizable compound represented by the above [Formula 1]; One or two or more compounds selected from the group consisting of compounds represented by the following [Formula 2] to [Formula 4]; And one or two or more compounds selected from the group consisting of compounds represented by the following [Formula 5] to [Formula 6].

[Formula 2]

[Formula 3]

[Formula 4]

R ₁ to R ₆ are each independently a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms, or one or more of -C ₂ -so that -CH ₂ -of the radicals are not directly connected to oxygen atoms. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical,

Z ₅ and Z ₆ are each independently a single bond; -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-, -CO- O- or -O-CO-,

Rings A and B are each independently 1,4-cyclohexylene or 1,4-phenylene, and Rings C, D and E are each independently

이고,

ego,

Ring F, G and I are each independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which one or more hydrogens are replaced by halogen,

e and f are each independently an integer of 0 or 1, g and h are each independently an integer of 0 or 1, g + h is an integer of 1 or 2,

(F) is hydrogen or F.

[Formula 5]

[Formula 6]

R ₇ is alkyl having 1 to 12 carbon atoms,

R ₈ and R ₉ are each independently hydrogen, oxygen or alkyl having 1 to 12 carbon atoms,

Ring J is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene with at least one hydrogen substituted by halogen,

i is an integer of 0 or 1, and k is an integer of 1-12.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the following examples.

Synthesizable Polymeric Compound of Formula 1

The synthesis method for synthesizing [Formula 1] according to the present invention is shown through [Scheme 1] and [Scheme 2]. In Scheme 1, L ₁ represents methyl or ethyl group and removes hydrogen at position 3 using LDA (lithium diisopropylamide) in M1 material for lateral substitution of alkyl group with fluorine, and then methyl iodide or methyl iodide. After reacting with ethyl iodide, M2 material can be synthesized. Such synthetic methods can be found in the literature (Schlosser, M. (2005) Angew. Chem. Int. Ed., Vol 44, pp 376). In addition, the coupling reaction between the ring structure compounds can be easily obtained by reacting boronic acid (M4) with bromine compound (M3). In order to synthesize 2-methoxyallylic acid (M7) it can be obtained using the same method as in [Scheme 2].

Scheme 1

Scheme 2

The polymeric compound of [Formula 1] was obtained with the material obtained through [Scheme 1] and [Scheme 2]. Scheme 3 is a method of obtaining a polymerizable compound of a bicyclic substance, and Scheme 4 and Scheme 5 show a method of obtaining a polymerizable compound of a tricyclic substance. Synthesis method in [Scheme 3] to [Scheme 5] can be obtained through a number of documents, summarized as follows and in the present embodiment will be described the final polymerizable compound synthesis method.

How to synthesize boronic acid compounds from bromine compounds

Moleele, Simon S. (2006) Tetrahedron, 62 (12), 2831-2844

How to synthesize alcohol compound from boronic acid compound

Chen, Wei-Hong. (2011) Journal of the American Chemical Society, 133 (39), 15674-15685

How to synthesize alcohol compound from methoxy compound

: Ryu, Ilhyoung. (2002) Journal of the American Chemical Society, 124 (44), 12946-12947

How to synthesize acrylate compound from alcohol compound

Olsen, Richard K. (1995) Journal of Oragnic Chemistry, 60 (19), 6025-6031

Method of combining reaction of boronic acid compound with bromine compound

Julita S. Gasowska. (2010) Journal of Materials Chemistry 20, 299-307

Scheme 3

Scheme 4

Scheme 5

Synthesis Example 1 Synthesis of Polymerizable Compound AC1-H

2-methyl-3-fluoro- [1,1'-biphenyl] -4,4'-diol (7.1 g, 32.8 mmol, code name M8), acrylic acid (5.2 g, 72.2 mmol) under nitrogen stream , 4- (dimethylamino) pyridine (2.0 g, 16.4 mmol) and DCC (20.3 g, 98.4 mmol) were diluted in 150 ml of chloroform and stirred at room temperature for 24 hours. The solvent is removed after filtering the by-product produced in the reaction solution. Dichloromethane was separated by a silica gel column to obtain a white solid, 4,4'-bis (acryloyloxy) -2-methyl-3-fluoro- [1,1'-biphenyl].

MS (EI) m / z = 218, 272, 326 (M < + >). Melting point 85.5 ° C.

Synthesis Example 2 Synthesis of Polymerizable Compound AC1-O

2-Methyl-3-fluoro- [1,1'-biphenyl] -4,4'-diol (3.8 g, 17.4 mmol, code name M8), 4- (dimethylamino) pyridine (3.62) under nitrogen stream g, 29.6 mmol) and DCC (3.60 g, 29.6 mmol) are diluted in 80 ml of tetrahydrofuran and stirred. After 20 minutes, the mixture was heated to 60 ° C, diluted alphamethoxyacrylic acid (3.9 g, 38.3 mmol) in 15 ml of tetrahydrofuran and added dropwise thereto. Thereafter, the reaction temperature was raised to 100 ° C., stirred for 2 hours, cooled to room temperature, and stirred for 2 hours. The solvent is removed after filtering the by-product produced in the reaction solution. Dichloromethane was separated by a silica gel column to obtain a white solid, 4,4'-bis (2-methoxyacryloyloxy) -2-methyl-3-fluoro- [1,1'-biphenyl].

MS (EI) m / z = 57, 299, 386 (M +). Melting point 101.0 ° C

Synthesis Example 3 Synthesis of Polymerizable Compound AC2-O

2-ethyl-3-fluoro- [1,1'-biphenyl] -4,4'-diol (1.0 g, 4.3 mmol, code name M8), 4- (dimethylamino) pyridine (0.9 under nitrogen stream g, 7.3 mmol) and alphamethoxyacrylic acid (1.0 g, 9.5 mmol) are diluted in 20 ml of tetrahydrofuran and stirred. After 20 minutes, DCC (1.5 g, 7.3 mmol) is added dropwise. After the reaction temperature was raised to 80 ℃ stirred for 3 hours, cooled to room temperature and stirred for 24 hours. The solvent is removed after filtering the by-product produced in the reaction solution. Dichloromethane was separated by a silica gel column to give a white solid, 4,4'-bis (2-methoxyacryloyloxy) -2-ethyl-3-fluoro- [1,1'-biphenyl].

MS (EI) m / z = 65, 313, 400 (M < + >). Melting Point 117.1 ℃

Synthesis Example 4 Synthesis of Polymerizable Compound AC1A-H

2'-methyl-3'-fluoro- [1,1 ': 4', 1 ''-terphenyl] -4,4 ''-diol under nitrogen stream (12.8 g, 43.49 mmol, code name M9) , Acrylic acid (6.89 g, 95.68 mmol), 4- (dimethylamino) pyridine (2.66 g, 21.75 mmol) and DCC (26.92 g, 130.47 mmol) were diluted in 300 ml of chloroform and stirred at room temperature for 24 hours. The solvent is removed after filtering the by-product produced in the reaction solution. White solid, 4,4 '-(diacryloyloxy) -2'-methyl-3'-fluoro- [1,1': 4 ', 1' '-terphenyl separated by silica gel column in dichloromethane ] Was obtained.

MS (EI) m / z = 55, 294, 348, 402 (M < + >). Melting Point 134.6 ℃

Synthesis Example 5 Synthesis of Polymerizable Compound AC2A-H

2'-ethyl-3'-fluoro- [1,1 ': 4', 1 ''-terphenyl] -4,4 ''-diol under nitrogen stream (1.0 g, 3.2 mmol, code name M9) , Acrylic acid (0.5 g, 7.2 mmol), 4- (dimethylamino) pyridine (0.4 g, 3.2 mmol) and DCC (1.3 g, 6.5 mmol) were diluted in 50 ml of chloroform and stirred at room temperature for 24 hours. The solvent is removed after filtering the by-product produced in the reaction solution. Separated by dichloromethane with silica gel column, white solid, 4,4 '-(diacryloyloxy) -2'-ethyl-3'-fluoro- [1,1': 4 ', 1' '-terphenyl ] Was obtained.

MS (EI) m / z = 207, 308, 362, 416 (M < + >). Melting Point 109.9

Synthesis Example 6 Synthesis of Polymerizable Compound AAC1-H

3-fluoro-2-methyl- [1,1 ': 4', 1 ''-terphenyl] -4,4 ''-diol (3.5 g, 11.89 mmol, code name M10), acryl under nitrogen stream Acid (2.14 g, 29.73 mmol), 4- (dimethylamino) pyridine (0.73 g, 5.94 mmol) and DCC (7.36 g, 35.68 mmol) were diluted in 150 ml of chloroform and stirred at room temperature for 24 hours. The solvent is removed after filtering the by-product produced in the reaction solution. A white solid, 4,4 "-(diacryloyloxy) -3-fluoro-2-methyl- [1,1 ': 4', 1" -terphenyl] was separated by distillation with silica gel column in dichloromethane. Got it.

MS (EI) m / z = 55, 294, 348, 402 (M < + >). Melting Point 150.0 ℃

Evaluation of Physical Properties of Polymerizable Compounds Prepared in Synthesis Examples

In order to confirm the physical properties of the synthesized polymerizable compound was evaluated according to the method described below in comparison with the existing material. Among the existing materials, Chemical Formula 7-1 (domestic application 10-2004-7016527 known material) was named AA-H, and Chemical Formula 7-2 (domestic application 10-2013-7008422 known material) was named AC-H.

(1) State change according to temperature (measuring melting point and transparent point)

The synthesized material was placed in a capillary rod of 1 mm diameter, and a capillary tube was attached to the METTLER TOLEDO MP50, and the change in permeability of the polymerizable compound was observed while raising the temperature at 3 ° C / min intervals. The melting point was defined as the point where the transmittance rapidly increased using the optical change.

The transparent point of the liquid crystal composition containing a polymeric compound was also measured by the same method.

(2) low temperature stability

The polymerizable compound to be measured for solubility at room temperature was 0.4% by weight and 2.0% by weight, respectively, and mixed in the parent liquid crystal MixA of item (8). The mixture was stirred at 90 ° C for 15 minutes, and left at room temperature for 1 hour. After 2g transfer to 10mL vials and stored in -30 ℃ freezer. Check for recrystallization at daily intervals. When recrystallization occurred after 00 days from the first freezer storage date, "00 days NG" was displayed. If the liquid crystal phase was kept for 20 days or more, "20 days OK" was expressed.

(3) pretilt angle (θp)

In order to measure the pretilt angle, the liquid crystal was injected into the evaluation cell of item (6) and then measured by a modified crystal rotation method. The measurement method was measured using the refractive index anisotropy change of the cell injecting the liquid crystal, PAMS measuring instrument of Sesim Optoelectronic Technology Co., Ltd. was used.

(4) response time

The main system of measurement was a system in the order of "light source a polarizing plate a cell a polarizing plate a light receiving part a indicator", and LCMS measuring instrument of Sesim Optoelectronic Technology Co., Ltd. was used. After injecting liquid crystal into the evaluation cell of item (6) to measure the response time, the polarizing plate at the upper and lower parts of the cell is set to 90 degrees so that the initial state becomes a dark state. In this state, 60Hz AC voltage was applied from 0.0V to 7.0V and then again from 7.0V to 0.0V to measure the response time. At this time, the time until the transmittance is changed from 10% to 90% when applying voltage from 0.0V to 7.0V is Ton, and the time when transmittance is changed from 90% to 10% when voltage is reduced from 7.0V to 0.0V is called Toff. . In addition, the sum of Ton and Toff is indicated in the embodiment as T (total), and unless otherwise stated, the response time means T (total).

(5) refractive index anisotropy

It was measured using an Abbe refractometer at 589 nm, the refractive index anisotropy was obtained at 20 degrees by vertically aligning the liquid crystal using lecithin.

(6) Evaluation cell production

The top plate of the glass cell is made of ITO electrode of 10mm width / length that can be connected to the wire, and the vertical alignment agent is cured thereon. The vertical alignment agent rotates a roll coated with rayon fibers (500 rpm). Rub it weakly. (Rubbing depth 0.3mm) In addition, the bottom plate of the cell is a substrate with a vertical alignment agent cured in a stripe ITO pattern of 5um interval within 10mm horizontally / vertically. The upper and lower plates are bonded together to a thickness of 4um, and the electrodes of the upper and lower plates are connected to the wires separately to complete the evaluation cell.

(7) UV irradiation method

After the liquid crystal mixture to which the polymerizable compound was added was injected into the evaluation cell, ultraviolet rays were irradiated while applying alternating current of 10V. UV light used a light source whose 365 nm is the main wavelength band when irradiated, and 100J was irradiated in the present invention unless otherwise specified.

(8) Voltage Retention Rate (VHR)

When measuring the voltage retention, the VHR cell is made of ITO electrodes of 10 mm in width and length, which can be connected to wires on the upper and lower plates of glass cells, and the vertical alignment agent is cured to have a cell gap of 4 μm. After mounting the temperature controller (Model SU-241) manufactured by ESPEC Corp., this VHR cell with liquid crystal was injected, and using Toyo Corp. Model 6254 equipment, the voltage retention was maintained at 60 ° C, 60Hz, and 1.0V. Measured.

(9) Matrix liquid crystal (MixA) production

In order to confirm the low temperature stability and the pretilt angle of the synthesized polymerizable compound, a mother liquid crystal having the composition of Table 1 was used, and the coded notation was expressed by the method of Table 2.

compound weight% MixA Properties BB-3.4 11.3 Transparent point 74.4 Refractive anisotropy 0.112 Dielectric constant anisotropy -3.6 Low temperature stability 30 days OK BF-3.O2 14.0 BF-5.O2 12.2 AF-3.O2 15.0 BBF-3.O2 5.9 BBF-2.1 11.4 BBF-3.1 11.8 BAAB-3.3 1.9 BAA-3.2 6.8 BAA-5.1 2.7 BAA-3.1 7.0

* When the chemical structure of liquid crystal compound is indicated, follow the rules below.

  The symbol "n" in the terminal group means the number of carbons in the alkyl group

  -There is no separate mark between the center group and the link group

-Between center and end groups separated by?-"

The right end group and the left end group are separated by?. ",

  List from right end group

For example,

Polymerizable  Compound Example  Property evaluation

The polymerizable compounds synthesized through the examples are shown in Table 2 in comparison with the existing material AA-H. In case of mixing 2% of AA-H at low temperature stability, it cannot be used because it is recrystallized within 1 hour at room temperature. In addition, crystals were deposited in 13 days even with the minimum 0.4% for PSA mode implementation. On the other hand, in the case of the compound of Formula 1 according to the present invention, it can be seen that all remain stable for 20 days. This difference can be inferred from the melting point. The melting point of AA-H is 148.8 ℃ as a compound of formula 1 according to the present invention, the bicyclic ring compound is reduced to more than 60 ℃ to 85.5 ℃ and tricyclic compounds also reduced the melting point at least 15 ℃ more than AA-H Done.

In addition, in the tricyclic cyclic compound AAC1-H showed a similar melting point as the comparative example AA-H or AC-H, it can be seen that the low temperature stability is significantly improved in the same parent liquid crystal. When checking the pretilt angle and response time after irradiation with UV 100J, the bicyclic cyclic compound AC1-H has no significant difference compared to the existing material AA-H. However, the tricyclic cyclic compound decreases the pretilt angle by about 2 degrees. It can be seen that also improved.

Code Polymerizable compound structure Melting Point (℃) Low temperature stability (-30 ℃) Cell characteristics after ultraviolet irradiation (liquid crystal composition added 0.4 wt% polymerizable compound to MixA) 2.0 wt% 1.0 wt% 0.4 wt% Pretilt angle (°) Response time (ms) AA-H (Comparative Example)

148.8 Room temperature precipitation 9 daysNG 13 daysNG 85.1 25.0 AC-H (Comparative Example)

158.7 Room temperature precipitation 7 daysNG 15 daysNG 84.9 24.8 AC1-H

85.5 20 days OK 20 days OK 20 days OK 85.5 25.0 AC1A-H

134.6 20 days OK 20 days OK 20 days OK 83.2 22.8 AC2A-H

109.9 20 days OK 20 days OK 20 days OK 83.1 23.0 AAC1-H

150.0 20 days OK 20 days OK 20 days OK 83.4 23.1

Polymerizable  Of the liquid crystal composition containing the compound Example

In the following [Table 4], [Table 5] and [Table 6], the content of the compounds of Formulas 2 to 4 is parts by weight, and the polymerizable compound of Formula 1 is% by weight.

Reduction of the pretilt angle of the examples in which the polymerizable compound [Formula 1] of the present invention was added compared to Comparative Example 1 using the existing material AA-H through [Table 4], [Table 5] and [Table 6] Able to know. In particular, in the case of Examples 3 to 19 using the terphenyl series AC1A-H, AAC1-H, AC2A-H was confirmed that the reduction of the pretilt angle is significantly improved. When the first, second, and third components of the terphenyl series were compared with Example 11 and Example 14, Example 14 using AAC1-H improved response time and pretilt angle more than Example 11 using AC1A-H. You can see that.

Comparing Example 7 and Example 8, in which the second and third components are the same but the first components are different, it can be seen that the response time of Example 8 in which BB-3.V is mixed is 8 ms or more faster. Therefore, when BB-3.V is included in the polymerizable compound [Formula 1] of the present invention, it was confirmed that the response time is improved.

As a result of comparing Examples 8 to 10 in which the first and third components were the same but the second components were different, Examples 9 and 10 including AF-3.O2 and / or AFA-2.3 were compared with Example 8 which was not. It can be seen that the pretilt angle decreases. From these results, the polymerizable compound [Formula 1] of the present invention can be seen that the pretilt angle is improved when mixed with AF or AFA series. In addition, looking at Examples 18 to 19 using the ANAF-3.O2 of the second component shows the most improved pretilt angle of the embodiment of the present invention.

When using 2 or more types of polymeric compounds, it is easy to control a pretilt angle. Looking at Examples 10 and 12 and Examples 11 and 13, the liquid crystal composition was the same, and the weight percent of the polymerizable compound was the same, but it was confirmed that fine line tilt angles can be adjusted through the combination of two or more polymerizable compounds.

division Substance / characteristic Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Compound of [Formula 2] BB-3.V 35 BB-3.4 11.3 4.6 4.2 14.1 11.3 BB-3.5 4.3 6.6 BA-3.O2 10.2 4.3 6.7 Compound of [Formula 3] AF-3.O2 15 7.1 12.3 15 11.7 12.3 15 BF-3.O2 14 13.2 10.8 10 10.3 14.9 14 BF-5.O2 12.2 13.2 11.4 10.8 9.4 12.2 BBF-3.O1 8.5 8 6.7 6.2 BBF-3.O2 5.9 10.1 10 2.9 5.4 5.9 BBF-4.O2 BBF-2.1 11.4 12.2 12.9 14.1 7.3 11.4 BBF-3.1 11.8 12.2 12.9 12.3 7.3 11.8 BAF-2.O2 5 BAF-3.O2 10 AFA-2.3 2 4 BYDF-3.O2 2 Compound of [Formula 4] BAA-3.1 7 5 5.1 5 6.6 8.6 7 BAA-3.2 6.8 5.1 5.2 7.1 7.7 6.8 BAA-5.2 2.7 5.1 4.4 4.2 2.8 2.7 BAAB-3.3 1.9 2 1.7 1.9 [Formula 1] polymerizable compound AA-H 0.4 AC1-H 0.4 0.4 AC2A-H 0.4 0.4 0.4 AAC1-H 0.4 Properties Transparent point 75.4 80.9 80.2 74.6 80.1 78.9 75.4 Refractive index anisotropy 0.113 0.111 0.114 0.107 0.114 0.117 0.113 T (total) 25 22.7 20.9 16.4 19.3 17.2 23.1 Ton 18.8 16 14.1 11.2 12 10.3 16.8 Toff 6.2 6.7 6.8 5.2 7.3 6.9 6.3 Pretilt 85.1 83.7 84.3 80.2 82.2 81.5 83.4

division Substance / characteristic Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Compound of [Formula 2] BB-3.V 15 15 15 25 15 25 BB-2.3 5 5 5 5 5 5 5 BB-3.4 15 Compound of [Formula 3] AF-3.O2 10 10 10 10 10 BF-3.O2 10 10 10 10 10 10 10 BF-3.O4 10 10 BF-5.O2 15 15 15 15 10 15 10 BBF-3.O1 5 5 5 5 0 5 0 BBF-3.O2 10 10 0 0 5 0 5 BBF-5.O2 10 10 10 10 10 10 10 BBF-2.1 5 5 5 0 0 0 0 BAF-3.O2 10 10 13 10 13 AFA-2.3 0 5 5 5 5 Compound of [Formula 4] BAA-3.1 5 5 5 5 5 5 5 BAA-3.2 5 5 5 5 5 BAA-5.2 5 5 5 5 5 BAAB-3.3 2 2 [Formula 1] polymerizable compound AA-H 0.2 AC1-H 0.2 AC1A-H 0.4 0.4 0.4 0.4 0.4 0.2 0.2 Properties Transparent point 83.1 80.7 79.2 80.7 76.9 77.7 76.9 Refractive index anisotropy 0.094 0.094 0.11 0.118 0.11 0.118 0.11 T (total) 25.2 16.3 15.8 17.4 22.3 20.5 22.7 Ton 18.8 9.8 9 10.4 17 13.3 17.5 Toff 6.4 6.4 6.8 7 5.3 7.2 5.2 Pretilt 83.2 83.4 80.8 80.9 82.3 82.3 83.9

division Substance / characteristic Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Compound of [Formula 2] BB-3.V 25 35 20 BB-2.3 5 5 BB-3.4 14.1 4.6 15 BA-3.O2 10.2 Compound of [Formula 3] AF-3.O2 10 12.3 7.1 15 15 BF-3.O2 10 14.9 13.2 10 10 10 BF-3.O4 10 BF-5.O2 10 9.4 13.2 15 10 BBF-3.O1 0 6.2 5 5 10 BBF-3.O2 5 5.4 10.1 10 10 10 BBF-5.O2 10 10 BBF-2.1 0 7.3 12.2 5 BBF-3.1 7.3 12.2 BAF-3.O2 13 10 10 AFA-2.3 5 4 ANAF-3.O2 10 5 Compound of [Formula 4] BAA-3.1 5 8.6 5 5 5 BAA-3.2 7.7 5.1 5 5 BAA-5.2 2.8 5.1 5 5 BAAB-3.3 2 2 [Formula 1] polymerizable compound AAC1-H 0.4 0.4 0.4 0.4 0.4 0.4 Properties Transparent point 76.9 79 81 82.8 70.4 75.4 Refractive index anisotropy 0.11 0.117 0.111 0.094 0.112 0.118 T (total) 22 21 22.9 24.9 17.7 17 Ton 15.9 13.8 15.2 17.5 12.9 9.6 Toff 6.1 7.2 7.7 7.4 4.8 7.4 Tilt angle 81.2 82.4 82 81.2 80.1 80

Polymerizable  According to the UV intensity in the liquid crystal composition containing the compound Example

1 and 2 are respectively prepared by mixing 0.4% by weight of AA-H and AAC1-H of the present invention in the parent liquid crystal MixA to 0.4% by weight of the present invention, while increasing the amount of UV irradiation sequentially and the inclination angle and response time The measurement results are shown. As can be seen in Figure 1, AAC1-H reacts faster with less ultraviolet light than AA-H, in particular, the response time of the liquid crystal composition containing AAC1-H even if only 3J as shown in Figure 2 You can see that this is going very fast.

Due to this feature, the compound of the present invention, AAC1-H, was confirmed that the display reliability characteristics can be improved by minimizing the residues in the composition.

Polymerizable  In the liquid crystal composition containing the compound and the additive Example

Example 20 is a composition in which 0.03% by weight of [Formula 6] in which R ₈ and R ₉ are hydrogen and k is 8 is added to Example 7. After injecting the composition of Example 7 and Example 20 to the VHR cells, VHR was measured after UV irradiation and heat stress as shown in Table 7. As a result, it was confirmed that Example 20, to which the UV stabilizer such as [Formula 6] was added, was significantly superior in VHR characteristics than Example 7.

VHR Cell Stress Progress Example 7 Example 20 Before UV irradiation 99.00% 98.80% After UV 40J 66.90% 83.10% 100 ℃ 3 hours stress

The present invention exhibits improved low temperature stability, and provides a polymerizable compound which improves the pretilt angle of the liquid crystal upon photopolymerization by ultraviolet rays and a liquid crystal composition comprising the same. Such a polymerizable compound enables high-speed response to provide a liquid crystal composition optimized for liquid crystal displays of various modes, in particular, PSA and PS-VA modes.

Claims (16)

The polymeric compound represented by following [Formula 1]. [Formula 1]

In [Formula 1], P ₁ and P ₂ are each independently a radical of any of a polymerizable functional group, hydrogen, alkyl having 1 to 7 carbon atoms and alkoxy having 1 to 7 carbon atoms, or one or more of -CH ₂ -is one of the radicals directly Unsubstituted or substituted with —C≡C—, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —O—, —CO—O—, or —O—CO— Any one of radicals in which hydrogen (H) is replaced by halogen, at least one of P ₁ and P ₂ is a polymerizable functional group, Sp ₁ And Sp ₂ are each independently a single bond, a radical of any one of alkyl having 1 to 15 carbon atoms, at least one hydrogen in the radical is substituted with halogen, or one or more -CH ₂ -is not directly connected to oxygen atoms. Radicals replaced by -C≡C-, -CH = CH-, -O-, -CO-O-, -O-CO- or -O-CO-O-, L ₁ each independently represents an alkyl group having 1 to 5 carbon atoms, and one or two or more -CH ₂ -groups in the alkyl group are each selected from -O-, -S-, and -NH- so that oxygen atoms do not directly adjoin. , -N (CH ₃ )-, -CO-, -CO-O-, -O-CO-, -OCOO-, -SCO-, -COS-, -CH = CH- or -C≡C- Substituted or unsubstituted, Z ₁ to Z ₄ are each independently _{-CH 2 CH 2 -, -CH =} CH-, -CH 2 O-, -OCH 2 -, -C≡C-, -CH 2 CF 2 -, -CHFCHF-, -CF ₂ CH _2- , -CH ₂ CHF-, -CHFCH _2- , -C ₂ F _4- , -O-, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -Or a single bond, A ₁ to A ₄ are each independently 1,4-cyclohexylene; 1,4-phenylene; Or at least one hydrogen is 1,4-phenylene substituted with halogen or an alkyl group having 1 to 5 carbon atoms, a, b, c and d are each independently an integer of 0 to 2, and a + b + c + d is 1 to 4. The method of claim 1, In the polymerizable compound of [Formula 1], P ₁ and P ₂ are each independently

,

or

It is a polymeric compound. The method of claim 1, In the polymerizable compound of [Formula 1], P ₁ and P ₂ are

Phosphorus, a polymerizable compound. The method of claim 1, The polymeric compound of the said Chemical formula 1 contains 1 or more types chosen from the group which consists of the following [Formula 1-1]-[Formula 1-30]. [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Formula 1-25]

[Formula 1-26]

[Formula 1-27]

[Formula 1-28]

[Formula 1-29]

[Formula 1-30]

X ₁ in [Formula 1-1] to [Formula 1-30] is each independently hydrogen (H), methyl (CH ₃ ) or methoxy (OCH ₃ ), R ₁₁ and R ₁₂ are each independently hydrogen , Or a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms, or one or more of -CH ₂ -of the radicals are -C 원자 C-, -CH = CH- Is a radical substituted with —CF ₂ O—, —OCF ₂ —, —O—, —CO—O— or —O—CO—, or at least one hydrogen of the radicals replaced by halogen. 1 or more types of polymeric compounds represented by [Formula 1] of Claim 1; And One or two or more compounds selected from the group consisting of compounds represented by the following [Formula 2] to [Formula 4]; Comprising a liquid crystal composition. [Formula 2]

[Formula 3]

[Formula 4]

R ₁ to R ₆ are each independently a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms, or one or more of -C ₂ -so that -CH ₂ -of the radicals are not directly connected to oxygen atoms. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical, Z ₅ and Z ₆ are each independently a single bond; -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-, -CO- O- or -O-CO-, Rings A and B are each independently 1,4-cyclohexylene or 1,4-phenylene, and Rings C, D and E are each independently

Ring F, G and I are each independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which at least one hydrogen is substituted with halogen, e and f are each independently an integer of 0 or 1, g and h are each independently an integer of 0 or 1, g + h is an integer of 1 or 2, (F) is hydrogen or F. The method of claim 5, wherein [Chemical Formula 2] is a liquid crystal composition comprising one kind or two or more kinds of compounds represented by the following [Formula 2-1] to [Formula 2-4]. [Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

Where R ₁ and R ₂ are the same as the definition of R ₁ , R ₂ of the above [Formula 2], R ₁₁ may be hydrogen (H) including the definition of R ₁ . The method of claim 5, wherein [Chemical Formula 3] is a liquid crystal composition comprising one or two or more compounds represented by the following [Formula 3-1] to [Formula 3-8]. [Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

In [Formula 3-1] to [Formula 3-8], R ₃ and R ₄ are the same as the definition of R ₃ , R ₄ of the [Formula 3], (F) is hydrogen or fluorine. The method of claim 5, wherein [Formula 3] is a liquid crystal containing one or two or more compounds selected from the group consisting of the following [Formula 3-2-1], [Formula 3-5-1] and [Formula 3-6] Composition. [Formula 3-2-1]

[Formula 3-5-1]

[Formula 3-6]

R ₃ and R ₄ are each independently a radical of either an alkyl group having 2 to 5 carbon atoms or alkoxy having 2 to 5 carbon atoms. The method of claim 5, wherein [Chemical Formula 4] is a liquid crystal composition comprising one or two or more compounds selected from the group consisting of the following [Formula 4-1] to [Formula 4-3]. [Formula 4-1]

[Formula 4-2]

[Formula 4-3]

R ₅ and R ₆ are the same as the definitions of R ₅ and R ₆ in [Formula 4] (F) is hydrogen or F. 1 or more types of polymeric compounds represented by [Formula 1] of Claim 1; And One or two or more compounds selected from the group consisting of compounds represented by the following [Formula 5] to [Formula 6]; Comprising a liquid crystal composition. [Formula 5]

[Formula 6]

R ₇ is alkyl having 1 to 12 carbon atoms, R ₈ and R ₉ are each independently hydrogen, oxygen or alkyl having 1 to 12 carbon atoms, Ring J is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene with at least one hydrogen substituted by halogen, i is an integer of 0 or 1, and k is an integer of 1-12. The method of claim 10, A liquid crystal composition comprising the compound represented by the following formula (6). [Formula 6]

R ₈ and R ₉ are hydrogen, k is an integer of 1-12. 1 or more types of polymeric compounds represented by [Formula 1] of Claim 1; One or two or more compounds selected from the group consisting of compounds represented by the following [Formula 2] to [Formula 4]; And One or two or more compounds selected from the group consisting of compounds represented by the following [Formula 5] to [Formula 6]; Comprising a liquid crystal composition. [Formula 2]

[Formula 3]

[Formula 4]

R ₁ to R ₆ are each independently a radical of any one of alkyl of 1 to 7 carbon atoms and alkoxy of 1 to 7 carbon atoms, or one or more of -C ₂ -so that -CH ₂ -of the radicals are not directly connected to oxygen atoms. C-, -CH = CH-, -CF ₂ O-, -OCF _2- , -O-, -CO-O- or -O-CO- or substituted at least one hydrogen of the radicals with halogen Radical, Z ₅ and Z ₆ are each independently a single bond; -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C≡C-, -CO- O- or -O-CO-, Rings A and B are each independently 1,4-cyclohexylene or 1,4-phenylene, and Rings C, D and E are each independently

ego, Ring F, G and I are each independently 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene in which one or more hydrogens are replaced by halogen, e and f are each independently an integer of 0 or 1, g and h are each independently an integer of 0 or 1, g + h is an integer of 1 or 2, (F) is hydrogen or F. [Formula 5]

[Formula 6]

R ₇ is alkyl having 1 to 12 carbon atoms, R ₈ and R ₉ are each independently hydrogen, oxygen or alkyl having 1 to 12 carbon atoms, Ring J is 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene with at least one hydrogen substituted by halogen, i is an integer of 0 or 1, and k is an integer of 1-12. The method of claim 12, The compound represented by [Formula 2] is 5 to 50 parts by weight based on 100 parts by weight of the liquid crystal composition; The compound represented by [Formula 3] is 20 to 70 parts by weight; The compound represented by [Formula 4] is 5 to 60 parts by weight; Liquid crystal composition comprising. The method of claim 12, To 100 parts by weight of the total liquid crystal composition, the polymerizable compound represented by [Formula 1] of claim 1 is 0.01 to 5 parts by weight; The compound represented by [Formula 5] is 0.01 to 0.05 parts by weight or the compound represented by the formula [6] is 0.01 to 0.1 parts by weight; Liquid crystal composition comprising a. The liquid crystal display containing the liquid crystal composition of any one of Claims 5-14. The method of claim 15, The liquid crystal display is a liquid crystal display for polymer stabilized alignment mode.

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