JP6996818B2 - Polymerizable liquid crystal composition and its liquid crystal display device - Google Patents

Description

The present invention relates to a polymerizable liquid crystal composition, specifically, a polymerizable liquid crystal composition having good stability and high reliability, and a liquid crystal display device thereof.

The liquid crystal display element is used in various home appliances such as watches and electronic computers, measuring devices, automobile panels, word processors, computers, printers, televisions and the like. Typical display modes of the liquid crystal display element are PC (phase change, phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence). Refringence), OCB (optically compensated bend, optical compensation bend), IPS (in-plane switching, in-plane switching), VA (vertical alignment, vertical alignment), CSH (color super homeotropic), color super homeotropic, etc. .. The liquid crystal display element is classified into a PM (passive matrix) type and an AM (active matrix) type depending on the drive method of the element. PM can be divided into static and multiplex methods. AM is classified into TFTs (thin film transistors), MIMs (metal insulators metal, metals-insulators-metals) and the like. As the TFT method, there are amorphous silicon (amorphous silicon) and polycrystalline silicon (polycrystal silicon). The latter is divided into a high temperature type and a low temperature type according to the manufacturing method. Depending on the type of light source, the liquid crystal display element is classified into a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight source.

Among these display modes, the IPS mode, ECB mode, VA mode, CSH mode, etc., and the TN mode or STN mode, which are often used at present, are the points that the former uses a liquid crystal material having negative dielectric anisotropy. Is different. Further, among these display modes, the VA type display driven by AM is required to be applied to a display element having a high speed and a wide viewing angle. Above all, it is most expected to be applied to liquid crystal elements in televisions and the like.

Both VA mode and IPS mode are normally black, but in the VA mode panel, a liquid crystal material with negative dielectric anisotropy is used for the liquid crystal molecules in the liquid crystal layer, and transparent electrodes are provided on the upper and lower substrates. The difference is that an electric field perpendicular to is formed. When no electric field is applied, the longitudinal axis of the liquid crystal molecules is perpendicular to the substrate and a dark state is formed. When an electric field is applied, the longitudinal axis of the liquid crystal molecule tilts in a direction parallel to the substrate. However, since the initial orientation also requires rubbing against the substrate, problems such as contamination and static electricity occur, and it becomes difficult to control the pretilt angle. To solve the problems related to the initial orientation of VA mode, various derivative modes such as Multi-Domain Vertical Alignment (MVA), Patterned Vertical Alignment (PVA), Polymer maintenance orientation (PVA), polymer maintenance orientation (PVA), Polymer Unified Alignment (PSA) and Polymer Stabilized Vertical Alignment (PSVA) are present. Among them, PSA mode and PSVA mode are becoming mainstream because of their advantages such as high transmittance, high contrast, and fast response.

A Polymer Unified Alignment (PSA) type liquid crystal display device is a device having a structure in which a polymer structure is formed in a cell in order to control a pretilt angle of a liquid crystal molecule, and the speed thereof is high. It is applied as a liquid crystal display element because of its characteristics such as responsiveness and high contrast.

The PSA type liquid crystal display element is manufactured as follows.

A polymerizable composition composed of a liquid crystal compound and a polymerizable compound is injected between the substrates, and a voltage is applied to orient the liquid crystal molecules, and then the polymerizable compound is polymerized to fix the orientation of the liquid crystal molecules. do.

In the display device, due to the action of the electric field and the alignment layer, the charged particles in the liquid crystal molecule are separated according to the polarity and distributed on the two substrates, respectively, to form an internal electric field. When driving the display, the controllability of the liquid crystal molecules by the electric field is weakened, and even after the driving is stopped, the internal electric field still acts on the liquid crystal molecules, which affects the arrangement of the liquid crystal molecules. In addition, when driven for a long time, the internal electric field gradually increases, and even after the drive is stopped, the internal electric field can still maintain a certain degree of rotation of the liquid crystal molecules, so that the liquid crystal molecules cannot return to the initial state, and the image burn-in phenomenon. Occurs.

For liquid crystal displays, it is necessary to avoid the occurrence of image burn-in as much as possible.

In order to improve the image burn-in phenomenon in the liquid crystal display, it is necessary to reduce the content of impurities in the liquid crystal composition as much as possible and increase the voltage retention rate (that is, VHR) of the liquid crystal composition.

The PSVA liquid crystal composition is composed of both a stable liquid crystal compound and a polymerizable compound having optical activity. However, in the process of using the liquid crystal display, the residual polymerizable compound is inevitably irradiated with the backlight. Inevitably, as time goes by, the structure becomes more likely to change, ions are generated, an internal electric field is formed, which affects the arrangement of liquid crystal molecules, and display defects such as image burn-in occur. Therefore, by reducing the residue of the polymerizable compound as much as possible, the image burn-in phenomenon of the PSVA liquid crystal display can be effectively improved.

In PSVA, the arrangement direction of liquid crystal molecules is controlled by using a polymerizable compound. That is, the ideal arrangement state of the liquid crystal is "fixed" by polymerizing the polymerizable compound in the mixed liquid crystal by UV exposure at the same time as the liquid crystal is brought into the ideal arrangement state by an external electric field. There is.

Further, since the PSVA mode does not require a rubbing alignment step, problems such as static electricity and contamination caused by rubbing in modes such as TN and IPS can be avoided.

Unfortunately, however, many defects still exist in current polymerizable liquid crystal monomers. For example, the polymerizable liquid crystal monomer described in Patent Document 1 has an excessively high melting point and cannot be handled unless the temperature condition is 80 to 90 ° C. in actual production, so that energy consumption is significantly increased and the temperature is high. This causes defects such as non-uniform orientation and abnormal polymerization that greatly impair the optical quality.

Therefore, attempts have been made to improve the performance of the polymerizable liquid crystal by using a method for preparing a polymerizable liquid crystal composition. Patent Document 2 proposes a polymerizable liquid crystal composition having a low melting point, but there is a serious problem of non-uniform orientation. Further, although Patent Document 3 proposes a polymerizable liquid crystal composition having a low melting point, there is a problem that its stability is poor and it is easy to crystallize at a low temperature.

In the prior art, commonly used polymerizable liquid crystal compositions have, for example, slow or fast polymerization rates that are difficult to control, large changes in pretilt angle, too much residual amount after polymerization, and poor UV resistance. There are various problems such as low reliability. In addition, various display defect phenomena such as burn-in and non-uniform display have also occurred.

Therefore, there is a great need for novel polymerizable liquid crystal compositions that can reduce or significantly reduce the above defects.

U.S. Pat. No. 6,136,225 Japanese Patent Application Laid-Open No. 2003-193053 U.S. Pat. No. 6,090,308

An object of the present invention is to have good stability and high reliability, specifically good UV resistance and high voltage retention, with little or no problems in the prior art, and at the same time the polymerizable property. A liquid crystal display device comprising a liquid crystal composition is intended to provide a polymerizable liquid crystal composition in which the occurrence of image burn-in phenomenon is extremely small or almost nonexistent.

Another object of the present invention is a liquid crystal display device provided with the polymerizable liquid crystal composition.

In order to achieve the above object of the invention, the present invention
At least one compound of the general formula I and

少なくとも１種類の、一般式ＩＩの化合物と、

At least one compound of the general formula II and

少なくとも１種類の、一般式ＩＩＩの化合物と、

At least one compound of the general formula III and

を含む重合性液晶組成物を提供する。
（ただし、
前記Ｐ_１およびＰ_２は、同じまたは異なり、それぞれ独立して重合可能基を示し、
前記Ｙ_１およびＹ_２は、同じまたは異なり、それぞれ独立して炭素原子１～２０個の直鎖または分枝鎖のアルキル基を示し、
前記Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、同じまたは異なり、それぞれ独立して、－Ｈ、炭素数が１～１２の直鎖または分枝鎖のアルキル基またはアルコキシ基、炭素数が２～１２のアルケニル基またはアルケニルオキシ基を示し、ただし、１～１２の直鎖または分枝鎖のアルキル基またはアルコキシ基中の１つまたは複数の－ＣＨ_２－は、－Ｏ－に置換されてもよく、炭素数が２～１２のアルケニル基またはアルケニルオキシ基中の１つまたは複数の－ＣＨ_２－が、－Ｏ－と直接に結合しない前提で－Ｏ－に置換されてもよく、
前記環Ａは、

To provide a polymerizable liquid crystal composition containing the above.
(However,
The P ₁ and P ₂ are the same or different, and each independently exhibits a polymerizable group.
The Y ₁ and Y ₂ are the same or different, and each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms.
The R ₁ , R ₂ , R ₃ and R ₄ are the same or different, respectively, and are independently −H, a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms, and 2 carbon atoms. Representing alkenyl or alkenyloxy groups of -12, where one or more -CH _2- in the alkyl or alkoxy groups of 1-12 linear or branched chains are substituted with -O-. Also, one or more -CH _2- in an alkoxy group or an alkoxyoxy group having 2 to 12 carbon atoms may be replaced with -O- on the assumption that it does not directly bind to -O-.
The ring A is

を示し、ただし、

However,

の環中の１つまたは複数の－ＣＨ_２－は、－Ｏ－または－Ｓ－に代替されてもよく、

One or more -CH _2- in the ring of may be replaced by -O- or -S-.

の環中の１つまたは複数の－Ｈは、－Ｆまたは－ＣＨ_３に置換されてもよく、
環Ｂ、環Ｃおよび環Ｄは、同じまたは異なり、それぞれ独立して

One or more -Hs in the ring of may be replaced with -F or -CH ₃ .
Ring B, Ring C and Ring D are the same or different and are independent of each other.

を示し、ただし、

However,

中の１つまたは複数の－Ｈは、－Ｆに置換されてもよく、

One or more of -H in may be replaced with -F.

中の１つまたは複数の－ＣＨ_２－は、－Ｏ－に置換されてもよく、
環Ｅ、環Ｆ、環Ｇおよび環Ｈは、同じまたは異なり、それぞれ独立して

One or more of -CH _2- may be replaced with -O-.
Ring E, Ring F, Ring G and Ring H are the same or different and are independent of each other.

を示し、ただし、

However,

中の１つまたは複数の－Ｈは、置換箇所が隣接しない前提で、－Ｆに置換されてもよく、

One or more of -H may be replaced with -F on the assumption that the replacement points are not adjacent to each other.

中の１つまたは複数の－ＣＨ_２－は、－Ｏ－に置換されてもよく、
前記Ｌ_１～Ｌ_１２は、同じまたは異なり、それぞれ独立して－Ｈ、－Ｆまたは－ＣＨ_３を示し、
前記ＺおよびＺ^１は、同じまたは異なり、それぞれ独立して単結合、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ_２Ｏ－または－ＯＣＦ_２－を示し、
前記Ｚ^２およびＺ^３は、同じまたは異なり、それぞれ独立して単結合、－Ｏ－、－ＯＣＯ－、－ＣＯＯ－または－Ｏ－ＣＯＯ－を示し、
前記Ｚ_１、Ｚ_２、Ｚ_３、Ｚ_４、Ｚ_５およびＺ_６は、同じまたは異なり、それぞれ独立して単結合、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ_２Ｏ－または－ＯＣＦ_２－を示し、
前記ｎ、ｎ_１およびｎ_２は、同じまたは異なり、それぞれ独立して０または１を示し、
前記ｂ、ｃおよびｄは、同じまたは異なり、それぞれ独立して０、１または２を示し、
前記ｅ、ｆ、ｇおよびｈは、同じまたは異なり、それぞれ独立して０、１または２を示し、ただし、ｅ＋ｆ＋ｇ＋ｈ≧２である。）

One or more of -CH _2- may be replaced with -O-.
The L ₁ to L ₁₂ are the same or different, and independently indicate -H, -F or -CH ₃ , respectively.
The Z and Z ¹ are the same or different, and are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O- or. -OCF ₂ -indicates
Z ² and Z ³ are the same or different and independently represent single bonds, -O-, -OCO-, -COO- or -O-COO-, respectively.
The Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ are the same or different, and are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH ₂ -,-, respectively. COO-, -OCO-, -CF ₂ O- or -OCF _2- , indicating
The n, n ₁ and n ₂ are the same or different, and independently indicate 0 or 1, respectively.
The b, c and d are the same or different and independently indicate 0, 1 or 2, respectively.
The e, f, g and h are the same or different and independently indicate 0, 1 or 2, respectively, where e + f + g + h ≧ 2. )

In some embodiments of the invention, Z and Z ¹ are not single bonds at the same time.

In some embodiments of the invention, only one of Z and Z ¹ is a single bond.

In some embodiments of the invention, P1 and P2 _are the same or different and are independent of _each other.

、または－ＳＨを示す。

, Or -SH.

In some embodiments of the invention, preferably P1 and P2 _are the same or different and are independent of _each other.

、または－ＳＨを示す。

, Or -SH.

More preferably, in some embodiments of the invention, P1 and P2 _are the same or different and are independent of _each other.

、または－ＳＨを示す。

, Or -SH.

More preferably, in some embodiments of the invention, P1 and P2 _are the same or different and are independent of _each other.

を示す。

Is shown.

In some embodiments of the invention, the compound of the general formula I accounts for 0.01-30% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of the general formula I accounts for 0.01-10% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of the general formula I accounts for 0.05-5% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of the general formula I accounts for 0.1-5% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of the general formula I accounts for 0.1-3% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of the general formula I accounts for 0.1-1% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of the general formula I is one or more selected from the compounds of the general formulas I-1 to I-3.

_In some embodiments of the present invention, at least _one of the above L1 to L16 is -F or -CH ₃ .

In some embodiments of the invention, Z represents -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO- or -OCO-.

_In some embodiments of the present invention, at _least one of L5 to L8 and / or _L13 to L16 _in the general formula I-1 is −F or _CH3 .

_In some embodiments of the present invention, in the general formula I-1 and the general formula I-2, at _least two of L1 to L16 are −F or _CH3 .

In some embodiments of the present invention, the compound of the general formula I-1 is one or more selected from the following compounds.

（ただし、
前記Ｘ_１およびＸ_２は、同じまたは異なり、それぞれ独立して－Ｈまたは－ＣＨ_３を示し、
前記ＺおよびＺ^１は、同じまたは異なり、それぞれ独立して－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－または－ＯＣＯ－を示す。）

(However,
The X ₁ and X ₂ are the same or different, and independently indicate -H or -CH ₃ , respectively.
The Z and Z ¹ are the same or different, and independently indicate -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO- or -OCO-, respectively. )

In some embodiments of the present invention, the compound of the general formula I-1 is more preferably one or more selected from the following compounds.

In some embodiments of the present invention, the compound of the general formula I-2 is one or more selected from the following compounds.

（ただし、
前記Ｘ_１およびＸ_２は、同じまたは異なり、それぞれ独立して－Ｈまたは－ＣＨ_３を示し、
前記Ｚは、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－または－ＯＣＯ－を示す。）

(However,
The X ₁ and X ₂ are the same or different, and independently indicate -H or -CH ₃ , respectively.
The Z indicates -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO- or -OCO-. )

In some embodiments of the present invention, the compound of the general formula I-2 is more preferably one or more selected from the following compounds.

In some embodiments of the present invention, the compound of the general formula I-3 is one or more selected from the following compounds.

（ただし、
前記Ｘ_１およびＸ_２は、同じまたは異なり、それぞれ独立して－Ｈまたは－ＣＨ_３を示し、
前記Ｚは、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－または－ＯＣＯ－を示す。）

(However,
The X ₁ and X ₂ are the same or different, and independently indicate -H or -CH ₃ , respectively.
The Z indicates -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO- or -OCO-. )

In some embodiments of the present invention, the compound of the general formula I-3 is more preferably one or more selected from the following compounds.

In some embodiments of the present invention, the compound of the general formula II is one or more selected from the following compounds.

In some embodiments of the invention, the compound of formula II accounts for 20-80% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula II accounts for 20-70% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula II accounts for 20-65% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula II accounts for 25-60% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula II accounts for 20-55% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula II accounts for 30-55% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the present invention, the compound of the general formula III is one or more selected from the following compounds.

In some embodiments of the invention, the compound of formula III accounts for 20-80% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula III accounts for 20-70% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula III accounts for 20-60% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula III accounts for 25-50% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compound of formula III accounts for 25-45% of the total weight of the polymerizable liquid crystal composition.

In some embodiments of the invention, the compounds of the general formula II are preferably I-1--8-1, I-1-2-1, I-1-29-1 and I-1-34. Selected from the group consisting of -2 compounds.

In some embodiments of the invention, the compounds of the general formula II are preferably compounds of II-1, II-2, II-4, II-7, II-8, II-13 and II-15. Selected from the group consisting of.

In some embodiments of the invention, the compound of formula III preferably comprises the group consisting of compounds of III-1, III-2, III-3, III-7, III-10 and III-13. To be elected.

The polymerizable liquid crystal composition of the present invention further comprises one or more additives known to those of skill in the art and described in the literature. For example, multicolor dyes and / or chiral dopants may be added in an amount of 0-15%.

The following show preferred dopants that can be added to the mixture according to the invention.

Hereinafter, stabilizers that may be added to the mixture according to the present invention, for example, will be described.

Hereinafter, stabilizers that may be added to the mixture according to the present invention, for example, will be described.

Preferably, the stabilizer is selected from the stabilizers shown below.

In embodiments of the invention, the stabilizer preferably accounts for 0-5% of the total weight of the liquid crystal composition, more preferably the stabilizer accounts for 0-1% of the total weight of the liquid crystal composition. In a particularly preferred embodiment, the stabilizer accounts for 0-0.1% of the total weight of the liquid crystal composition.

Another aspect of the present invention provides a liquid crystal display device comprising the polymerizable liquid crystal composition of the present invention.

Another aspect of the present invention provides an application of the polymerizable liquid crystal composition of the present invention in PSVA, PVA display modes.

The beneficial effects are as follows. Comparing the polymerizable liquid crystal composition provided in the present invention with other polymerizable liquid crystal compositions in the prior art, the polymerizable liquid crystal composition does not show or does not show the problems existing in the prior art. Many repeated experiments have revealed the following: The polymerizable liquid crystal composition of the present invention has less residual polymerizable compound under the same experimental conditions, and has good stability and high reliability, specifically good UV resistance and high voltage retention. At the same time as having a ratio, the liquid crystal display device provided with the polymerizable liquid crystal composition causes very little or almost no image burn-in phenomenon.

In general, the higher the number of biphenyl rings, the faster the polymerization rate and the better the seizure of the liquid crystal display device, but as the number of rings increases, the soluble content of the polymerizable compound in the liquid crystal display. The amount will be low.

The present invention has been found to be as follows by many repeated experiments. By inserting a spacer group between different rings, the problem of solubility of the polymerizable compound can be effectively solved. At the same time, the polymerizable liquid crystal composition of the present invention may have less residual polymerizable compound, better UV resistance stability, and better reliability, so that the image burning phenomenon of the liquid crystal display device can be achieved. Can be effectively improved.

Hereinafter, the present invention will be described with reference to specific embodiments. It should be noted that the following examples are merely for explaining the present invention as an example of the present invention, and do not limit the present invention. Other combinations and various improvements included in the idea of the present invention may be made on the premise that the purpose or scope of the present invention is not deviated.

The liquid crystal display used in each of the following embodiments is a VA mode display device having a cell thickness d = 4 μm, and is composed of members such as a polarizing device (polarizing plate) and an electrode substrate. The display device is in a normally white mode, that is, a mode in which no potential difference is applied between the electrodes in the rows and columns, and the color of the pixels appears white to the observer. The axes of the upper and lower polarizing plates on the substrate are at an angle of 90 ° with each other. Further, the space between the two substrates is filled with an optical liquid crystal material.

For convenience of explanation, in each of the following examples, the structure of the group in the liquid crystal composition is represented by the code shown in Table 1.

Table 1 Structural code of the group in the liquid crystal compound

A compound having the following structural formula is taken as an example.

The structural formula can be expressed as nCGUF as represented by the code shown in Table 1. In the code, n indicates the number of carbon atoms of the alkyl group on the left side, and for example, when n is "2", that is, the alkyl group is -C ₂ H ₅ . In the code, C represents "1,4-cyclohexylene group", G in the code represents "2-fluoro-1,4-phenylene group", and U in the code represents "2,5". -Difluoro-1,4-phenylene group ", and F in the code represents" fluorine substituent ".

The structural formula can be expressed as V (1) EPGE (1) V when expressed by the code shown in Table 1.

The abbreviated codes of the measurement items in the following examples are as follows.

In the table, the refractive index anisotropy was measured using an Abbe refractometer at a sodium lamp (589 nm) light source and 25 ° C. The dielectric measurement cell was a TN90 type with a cell thickness of 7 μm.

Δε ＝ ε ｜｜ －ε⊥. However, ε || is the permittivity parallel to the molecular axis, and ε⊥ is the permittivity perpendicular to the molecular axis. The measurement conditions were 25 ° C., 1 KHz, and the measurement cell was a TN90 type with a cell thickness of 7 μm.

For C, the initial content of the polymerizable compound was measured using high performance liquid chromatography.

For CUV, the content of the polymerizable compound after irradiation with _UV light for 180 seconds was measured by using high performance liquid chromatography.

As the measurement condition of the voltage retention rate of VHR ₁ , VHR was measured by a TOY06254 type liquid crystal characteristic evaluation system using a TN type measuring cell having a cell thickness of 9 μm at 5 V-6 Hz and 60 ° C.

As the measurement condition of the voltage retention rate of VHR ₂ , VHR was measured after irradiating 365 nm light beam at 6000 mJ using a TN type measurement cell having a cell thickness of 9 μm in a TOY06254 type liquid crystal characteristic evaluation system.

Example 1
The polymerizable liquid crystal composition of Example 1 was prepared according to each compound and weight percentage shown in Table 2, and the polymerized liquid crystal composition was filled between both substrates of the liquid crystal display to measure the performance. The measurement data is as shown in the table below.

Table 2 Formulation of liquid crystal composition and its measurement performance

The polymerizable liquid crystal composition RM-1 was formed by using the compound of the formula 1 instead of the compound I-1-29-1 without changing other compositions, and its voltage retention before and after UV light irradiation was measured. Then, it was compared with the measurement result of Example 1. Specifically, it is as shown in Table 3 below.

Table 3

Example 2
The polymerizable liquid crystal composition of Example 2 was prepared according to each compound and weight percentage shown in Table 4, and the polymerized liquid crystal composition was filled between both substrates of the liquid crystal display to measure the performance. The measurement data is as shown in the table below.

Table 4 Formulation of liquid crystal composition and its measurement performance

The polymerizable liquid crystal composition RM-2 was formed by using the compound of the formula 1 instead of the compound I-1-8-1 without changing other compositions, and its voltage retention before and after UV light irradiation was measured. Then, it was compared with the measurement result of Example 2. Specifically, it is as shown in Table 5 below.

Table 5

Example 3
The polymerizable liquid crystal composition of Example 3 was prepared according to each compound and weight percentage shown in Table 6, and the polymerized liquid crystal composition was filled between both substrates of the liquid crystal display to measure the performance. The measurement data is as shown in the table below.

Table 6 Formulation of liquid crystal composition and its measurement performance

The polymerizable liquid crystal composition RM-3 was formed by using the compound of the formula 1 instead of the compound I-1-34-2 without changing other compositions, and its voltage retention before and after UV light irradiation was measured. Then, it was compared with the measurement result of Example 3. Specifically, it is as shown in Table 7 below.

Table 7

Example 4
The polymerizable liquid crystal composition of Example 4 was prepared according to each compound and weight percentage shown in Table 8, and the polymerized liquid crystal composition was filled between both substrates of the liquid crystal display to measure the performance. The measurement data is as shown in the table below.

Table 8 Formulation of liquid crystal composition and its measurement performance

The polymerizable liquid crystal composition RM-4 was formed by using the compound of the formula 1 instead of the compound I-2-1-1 without changing other compositions, and its voltage retention before and after UV light irradiation was measured. Then, it was compared with the measurement result of Example 4. Specifically, it is as shown in Table 9 below.

Table 9

As can be seen from the data of Examples 1 to 4, the polymerizable liquid crystal composition of the present invention has good stability and high reliability, and specifically, the residue of the polymerizable compound is small and high. Due to the voltage retention, the liquid crystal display device provided with the polymerizable liquid crystal composition has very little or almost no image burn-in phenomenon.

The above description is merely a preferred embodiment of the present invention and is not a limitation in any form to the present invention. Although the present invention has been disclosed as described above using preferred embodiments, the disclosure is not intended to limit the invention. Any person skilled in the art who is familiar with the art will make use of the technical content disclosed above to the extent that it does not deviate from the technical configuration of the present invention, and will make some modifications or modifications equivalent as equivalent changes. Examples can be carried out. Any simple modifications, equivalent changes and modifications to the above embodiments made on the basis of the technical essence of the invention, as long as they do not deviate from the content of the technical configuration of the invention, are within the scope of the technical configuration of the invention. included.

The liquid crystal composition according to the present invention can be applied to the liquid crystal field.

Claims (6)

At least one compound of the general formula I and

At least one compound of the general formula II and

At least one compound of the general formula III and

A polymerizable liquid crystal composition containing
(However,
The P ₁ and P ₂ are the same or different, and each independently exhibits a polymerizable group.
The Y ₁ and Y ₂ are the same or different, and each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms.
The R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and are independently −H, a linear or branched alkyl or alkoxy group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms. It shows 12 alkenyl groups or alkenyloxy groups. However, one or more of the alkyl or alkoxy groups of the linear or branched chains of 1 to 12 may be substituted with -O-, and the alkenyl group having ₂ to 12 carbon atoms may be substituted. Alternatively, one or more -CH _2- of the alkoxyoxy groups may be replaced with -O- on the premise that they do not directly bind to -O-.
The ring A is

Is shown. However,

One or more of the rings of -CH _2- may be replaced by -O- or -S-.

One or more of the rings of -H may be replaced with -F or -CH ₃ .
Ring B, Ring C and Ring D are the same or different and are independent of each other.

Is shown. However,

One or more of -H may be replaced with -F.

One or more of -CH _2- may be replaced with -O-.
Ring E, Ring F, Ring G and Ring H are the same or different and are independent of each other.

Is shown. However,

One or more of -H may be replaced with -F on the assumption that the replacement points are not adjacent to each other.

One or more of -CH _2- may be replaced with -O-.
The L ₁ to L ₁₂ are the same or different, and independently indicate -H, -F or -CH ₃ , respectively.
The Z and Z ¹ are the same or different, and are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O- or. -OCF ₂ -indicates
Z ² and Z ³ are the same or different and independently represent single bonds, -O-, -OCO-, -COO- or -O-COO-, respectively.
The Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ are the same or different, and are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH ₂ -,-, respectively. COO-, -OCO-, -CF ₂ O- or -OCF _2- , indicating
The n, n ₁ and n ₂ are the same or different, and independently indicate 0 or 1, respectively.
The b, c and d are the same or different and independently indicate 0, 1 or 2, respectively.
The e, f, g and h are the same or different, and independently indicate 0, 1 or 2, respectively. However, e + f + g + h ≧ 2. )
However, P ₁ and P ₂ are the same or different, and are independent of each other.

, Or -SH,
The compound of the general formula I is one kind or a plurality of kinds selected from the compounds described in the general formula I-1 having four cyclic structures.

A polymerizable liquid crystal composition, wherein Z represents —CH ₂ O—, —OCH _2- , —CH ₂ CH _2- , —COO— or —OCO—. The polymerizable liquid crystal composition according to claim 1, wherein at least one of L ₁ to L ₁₆ is −F or —CH ₃ . The polymerizable liquid crystal composition according to claim 1, wherein the compound of the general formula I-1 is one kind or a plurality of kinds selected from the following compounds.

(However,
The X ₁ and X ₂ are the same or different, and independently indicate -H or -CH ₃ , respectively.
The Z and Z ¹ are the same or different, and independently indicate -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , -COO- or -OCO-, respectively. ) The polymerizable liquid crystal composition according to claim 1, wherein the compound of the general formula II is one kind or a plurality of kinds selected from the following compounds.

The polymerizable liquid crystal composition according to claim 1, wherein the compound of the general formula III is one kind or a plurality of kinds selected from the following compounds.

A liquid crystal display device comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.