PSA type liquid crystal composition and display device thereof

Abstract

The present invention discloses a PSA type liquid crystal composition, the PSA type liquid crystal composition comprises: a main liquid crystal A and a polymerizable component B, wherein the main liquid crystal A comprises one or more liquid crystal compounds, and the polymerizable component B comprises at least one compound selected from the group consisting of general formula I-1, general formula I-2 and general formula I-3. The present invention discloses a liquid crystal display device comprising the above-mentioned PSA type liquid crystal composition. The PSA type liquid crystal composition provided by the present invention has good mutual solubility, and will not crystallize under low temperature conditions. At the same time, the polymerizable component can form a relatively stable pre-tilt angle after polymerization, avoiding the occurrence of image retention, and will not form poor display conditions such as broken bright spots during the polymerization process. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of liquid crystal materials, in particular to a PSA type liquid crystal composition and a display device thereof. Background Art

[0002] Liquid Crystal Display (LCD) has developed rapidly due to its small size, light weight, low power consumption and excellent display quality, and has been widely used in portable electronic information products. According to the type of display mode, it is divided into PC (phase change), TN (twist nematic), STN (supertwisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), FFS (fringe field switching), VA (vertical alignment) and PSA (polymer stable alignment).

[0003] Among them, the PSA mode is to add a small amount (such as 0.3 wt%, more typically <1 wt%) of one or more polymerizable compounds to the liquid crystal composition, and after filling the liquid crystal box, apply a voltage between the electrodes or do not apply a voltage, so that the liquid crystal molecules have an initial orientation. In the state of polymerization or cross-linking (usually by UV light polymerization), the orientation of the liquid crystal molecules is fixed. The polymerization is carried out at a temperature at which the liquid crystal composition shows a liquid crystal phase (usually at room temperature). It has been proven that adding a polymerizable liquid crystal compound to a liquid crystal composition is particularly suitable, because the polymer structure formed in the unit can well control the tilt angle of the liquid crystal molecules, and the PSA type liquid crystal display element also has the effects of high-speed responsiveness and high contrast.

[0004] Therefore, PSA type liquid crystal display elements are continuously developed and the PSA principle is also used in various conventional liquid crystal displays, such as the known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays. Like conventional liquid crystal displays, PSA displays can be operated as active matrix or passive matrix displays. In the case of active matrix displays, the individual pixels are usually addressed by integrated non-linear active elements such as transistors, while in the case of passive matrix displays, the individual pixels are usually addressed according to multiplexing methods known in the prior art.

[0005] However, PSA-type liquid crystal display elements also have some display problems, such as image retention. Studies have shown that such problems are mostly caused by the presence of impurities and changes in the orientation of liquid crystal molecules (changes in pretilt angles), and the orientation of liquid crystal molecules is controlled by the polymer network formed after the polymerizable compounds are polymerized. If the structural rigidity of the polymerizable compounds constituting the polymer network is not enough, then when the PSA-type liquid crystal display element continuously displays the same pattern for a long time, the structure of the polymer network may change, which in turn causes the pretilt angle of the liquid crystal molecules to change. Therefore, it is usually necessary to select polymerizable compounds with a rigid structure.

[0006] In order to prevent image retention by improving the rigidity of the polymer, studies have been conducted on using a polymerizable compound having a structure such as 1,4-phenylene which has only a ring structure and a polymerizable functional group to form a display element (see patent document JP2003307720A) and a polymerizable compound having a biaryl structure to form a display element (see patent document JP2008116931A). However, these polymerizable compounds have low compatibility with liquid crystal compounds, and there is a problem that the polymerizable compounds are easily precipitated when preparing a liquid crystal composition containing the polymerizable compounds. Therefore, it is very necessary to improve the compatibility between the polymerizable compound and the liquid crystal compound.

[0007] In addition, it is proposed to use a mixed liquid crystal composition of a bifunctional polymerizable compound and a trifunctional or higher polymerizable compound such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate to form a display element (see patent document JP2004302096A). However, since dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate do not have a ring structure in the molecule, their affinity with liquid crystal compounds is weak, and the constraint force of orientation is also weak, and there is a problem that sufficient orientation stability cannot be obtained. In addition, these polymerizable compounds must be polymerized by adding a polymerization initiator during the polymerization process. If a polymerization initiator is not added, there will be a problem of residual polymerizable compounds after polymerization.

[0008] In order to further improve the response speed, various combinations of liquid crystal compositions and polymerizable compounds are disclosed in the prior art (see patent document WO2010084823A1). However, the relationship between the pretilt angle and the response speed is generally known, and it cannot be confirmed that there will be a significant improvement effect. In addition, the use of liquid crystal compounds containing alkenyl groups and chlorine atoms will increase the possibility of poor display, and there will also be environmental issues.

[0009] Therefore, it is expected to develop a PSA type liquid crystal composition and a liquid crystal display device containing the same that can simultaneously solve the problems of no precipitation of polymerizable compounds in a wide temperature range, fast response speed, and no image retention. Summary of the invention

[0010] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a PSA type liquid crystal composition with good mutual solubility, fast response speed, and no image retention and other undesirable display conditions. The purpose of the present invention is also to provide a display device comprising the above PSA type liquid crystal composition.

[0011] The technical solution of the present invention:

[0012] In order to achieve the above-mentioned object of the invention, the present invention provides a PSA type liquid crystal composition, wherein the PSA type liquid crystal composition comprises: a main liquid crystal A and a polymerizable component B, wherein the main liquid crystal A comprises one or more liquid crystal compounds, and the polymerizable component B comprises at least one compound selected from the group consisting of general formula I-1, general formula I-2 and general formula I-3:

[0013]

[0014]

[0015] in,

[0016] Ring A, ring B, ring C, ring D, ring E, ring F, ring G, ring H and ring I each independently represent a phenylene group or a naphthylene group;

[0017] X 1-1 , X 1-2 , X 1-3 , X 2-1 , X 2-2 , X 2-3 , X 2-4 , X 3-1 , X 3-2 , X 3-3 , X 3-4 and X 3-5Each independently represents a single bond, a straight or branched alkylene group containing 1 to 12 carbon atoms, one or more -CH2- in the straight or branched alkylene group containing 1 to 12 carbon atoms may be replaced by -O-, -S-, -NH-, -CO-, -CH=CH- or -C≡C- in a manner that heteroatoms are not directly connected to each other, and one or more -H in the -CH2- in the straight or branched alkylene group containing 1 to 12 carbon atoms may be replaced by halogen, and X 1-1 , X 1-2 , X 1-3 At least one of them represents a single bond, X 2-1 , X 2-2 , X 2-3 , X 2-4 At least one of them represents a single bond, X 3-1 , X 3-2 , X 3-3 , X 3-4 , X 3-5 At least one of them represents a single bond;

[0018] R A , R B , R C , R D , R E , R F , R G , R H and R I Each independently represents a halogen, a halogenated or unhalogenated straight-chain or branched alkyl or alkoxy group containing 1 to 5 carbon atoms;

[0019] P 1-1 , P 1-2 , P 2-1 , P 2-2 , P 3-1 and P 3-2 each independently represents a polymerizable group;

[0020] a, b, c, d, e, f, g, h and i each independently represent 0, 1, 2 or 3. When a is 2 or 3, R A can be the same or different; when b is 2 or 3, R B can be the same or different; when c is 2 or 3, R C can be the same or different; when d is 2 or 3, R D can be the same or different; when e is 2 or 3, R E can be the same or different; when f is 2 or 3, R F can be the same or different; when g is 2 or 3, R G can be the same or different; when h is 2 or 3, R Hcan be the same or different; when i is 2 or 3, R I Can be the same or different;

[0021] a+b+n1≥1, and n1≥1, n1 represents X 1-1 , X 1-2 , X 1-3 The number of non-single-bond groups in

[0022] c+d+e+n2≥2, and n2≥1, n2 represents X 2-1 , X 2-2 , X 2-3 , X 2-4 The number of non-single-bonded groups in

[0023] f+g+h+i+n3≥3, and n3≥1, n3 represents X 3-1 , X 3-2 , X 3-3 , X 3-4 , X 3-5 The number of non-single-bonded groups in the

[0024] In some embodiments of the present invention, ring A, ring B, ring C, ring D, ring E, ring F, ring G, ring H and ring I preferably each independently represent a phenylene group.

[0025] In some embodiments of the present invention, X 1-1 , X 1-2 , X 1-3 , X 2-1 , X 2-2 , X 2-3 , X 2-4 , X 3-1 , X 3-2 , X 3-3 , X 3-4 and X 3-5Preferably, each independently represents a single bond, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)2O-, -(CH2)3O-, -O(CH2)3-, -O-, -CF2-, -CF2O-, -OCF2-, -CH(CH3)CH2-, -C(CH3)2CH2-, -CH2C(CH3)2-, -C(CH3)2CH(CH3)-, -C(CH3)2C(CH3)2-, -C(CH3)2O-, -OC(CH3)2-, -CH(CH2CH3)CH2-, -O-, -S-, -NH-, -NH-CO-O-, -O-CO-NH-, -SCH2-, -CH2S-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH-.

[0026] In some embodiments of the present invention, R A , R B , R C , R D , R E , R F , R G , R H and R I Preferably, each independently represents -F, -CH2F, -CHF2, -CF3, -CH3, -OCH3, -CH2CH3 or -OCH2CH3.

[0027] In some embodiments of the present invention, P 1-1 , P 1-2 , P 2-1 , P 2-2 , P 3-1 and P 3-2 Preferably, each independently represents or -SH.

[0028] In some embodiments of the invention, a+b+n1≥2; c+d+e+n2≥3; f+g+h+i+n3≥4.

[0029] In some embodiments of the present invention, X 1-2 , X 2-2 , X 2-3 , X 3-2 , X 3-3 and X 3-4Each independently represents a single bond, -CH2O-, -OCH2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)3O-, -O(CH2)3-, -O-, -CF2-, -CF2O-, -OCF2-, -CH(CH3)CH2-, -C(CH3)2CH2-, -CH2C(CH3)2-, -C(CH3)2CH(CH3)-, -C(CH3)2C(CH3)2-, -C(CH3)2O-, -OC(CH3)2-, -CH(CH2CH3)CH2-, -S-, -NH-, -NH-CO-O-, -O-CO-NH-, -SCH2-, -CH2S-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH-.

[0030] In some embodiments of the present invention, X 1-2 represents -CO-O- or -O-CO-, then a+b≠0; X 2-2 and X 2-3 All represent -CO-O- or -O-CO-, then c+d+e≠0; X 3-2 , X 3-3 and X 3-4 Both represent -CO-O- or -O-CO-, then f+g+h+i≠0.

[0031] In some embodiments of the present invention, X 1-1 and X 1-3 All represent single bonds, X 1-2 Indicates -CH2O-, -OCH2-, -CO-O-, -O-CO-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)3O-, -O(CH2)3-, -O-, -CF2-, -CF2O-, -OCF2-, -CH(CH3)CH2-, -C(CH3)2CH2-, -CH2C(CH3)2-, -C(CH3)2CH(CH3)-, -C(CH3)2C(CH3)2-, -C(CH3)2O-, -OC(CH3)2-, -CH(CH2CH3)CH2-, -S-, -NH-, -NH-CO-O-, -O-CO-NH-, -SCH2-, -CH2S-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH-.

[0032] In some embodiments of the present invention, the polymerizable component B contains only one compound of the general formula I-1, wherein X 1-1 and X 1-3 All represent single bonds, X 1-2Indicates -CH2O-, -OCH2-, -CO-O-, -O-CO-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)3O-, -O(CH2)3-, -O-, -CF2-, -CF2O-, -OCF2-, -CH(CH3)CH2-, -CH2C(CH3)2-, -C(CH3)2CH2-, -C(CH3)2CH(CH3)-, -C(CH3)2C(CH3)2-, -C(CH3)2O-, -OC(CH3)2-, -CH(CH2CH3)CH2-, -S-, -NH-, -NH-CO-O-, -O-CO-NH-, -SCH2-, -CH2S-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH-, and a+b≠0.

[0033] In some embodiments of the present invention, if the polymerizable component B contains one compound of the general formula I-1 where a+b+n1=1, it also contains at least another compound selected from the group consisting of the general formula I-1, the general formula I-2 and the general formula I-3.

[0034] In some embodiments of the present invention, X 2-1 and X 2-4 At least one of them represents a single bond, and when X 2-1 and X 2-4 When both represent single bonds, X 2-2 and X 2-3 At least one of them is not a single bond, and c+d+e≥1.

[0035] In some embodiments of the present invention, if the polymerizable component B contains 2 or 3 polymerizable compounds, and at least one of the 2 or 3 polymerizable compounds is selected from the compounds of formula I-2, then X 2-1 and X 2-4 At least one of them represents a single bond, and when X 2-1 and X 2-4 When both represent single bonds, X 2-2 and X 2-3 At least one of them is not a single bond, and c+d+e≥1.

[0036] In some embodiments of the present invention, X 3-1 and X 3-5 At least one of them represents a single bond, and when X 3-1 and X 3-5 When both are single bonds, X 3-2 , X 3-3 and X 3-4 At least one of them is not a single bond, and f+g+h+i≥2; when X 3-1 and X3-5 When only one of the X represents a single bond, 3-2 , X 3-3 and X 3-4 At most one of them is not a single bond, and f+g+h+i≥2.

[0037] In some embodiments of the present invention, the polymerizable component B contains 2 or 3 polymerizable compounds, and at least one of the 2 or 3 polymerizable compounds is selected from the compound of formula I-3, then X 3-1 and X 3-5 At least one of them represents a single bond, and when X 3-1 and X 3-5 When both are single bonds, X 3-2 , X 3-3 and X 3-4 At least one of them is not a single bond, and f+g+h+i≥2; when X 3-1 and X 3-5 When only one of the X represents a single bond, 3-2 , X 3-3 and X 3-4 At most one of them is not a single bond, and f+g+h+i≥2.

[0038] In some embodiments of the present invention, the compound of formula I-1 is selected from the group consisting of the following compounds:

[0039]

[0040]

[0041]

[0042] as well as

[0043]

[0044] Among them, R A , R B , a and b have, at each occurrence, the same or different meanings as indicated above or below. In some embodiments of the present invention, the compound of formula I-2 is selected from the group consisting of the following compounds:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] as well as

[0053]

[0054] Among them, R C , R D , R E , c, d and e have on each occurrence, identically or differently, one of the meanings indicated above or below.

[0055] In some embodiments of the present invention, the compound of formula I-3 is selected from the group consisting of the following compounds:

[0056]

[0057]

[0058] as well as

[0059]

[0060] Among them, R F , R G , R H , R I , f, g, h and i have on each occurrence, identically or differently, one of the meanings indicated above or below.

[0061] In the above general formulas I-1-1 to I-1-24, general formulas I-2-1 to I-2-56 and general formulas I-3-1 to I-3-20, Preferably each independently represents a group selected from the group consisting of: and

[0062] In some embodiments of the present invention, the polymerizable component B accounts for 0.01-5% of the total weight of the PSA type liquid crystal composition, preferably, the polymerizable component B accounts for 0.05-4% of the total weight of the PSA type liquid crystal composition, and further preferably, the polymerizable component B accounts for 0.1-3% of the total weight of the PSA type liquid crystal composition.

[0063] In some embodiments of the present invention, the host liquid crystal A comprises one or more compounds of the general formula M:

[0064]

[0065] in,

[0066] R M1 and R M2 Each independently represents a straight or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0067] Ring M1, ring M2 and ring M3 each independently represent in, One or more -CH2- in may be replaced by -O-, At most one -H in may be replaced by halogen;

[0068] Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -CF2O-, -OCF2- or -CF2CF2-; and

[0069] n M1 represents 0, 1, 2, or 3, and when n M1 =2 or 3, the rings M2 may be the same or different, Z M2 Can be the same or different.

[0070] In some embodiments of the present invention, in the compound of formula M, R M1 and R M2 Preferably, each is independently a straight-chain alkyl group containing 1 to 10 carbon atoms, a straight-chain alkoxy group containing 1 to 9 carbon atoms, or a straight-chain alkenyl group containing 2 to 10 carbon atoms; more preferably, each is independently a straight-chain alkyl group containing 1 to 8 carbon atoms, a straight-chain alkoxy group containing 1 to 7 carbon atoms, or a straight-chain alkenyl group containing 2 to 8 carbon atoms; and even more preferably, each is independently a straight-chain alkyl group containing 1 to 5 carbon atoms, a straight-chain alkoxy group containing 1 to 4 carbon atoms, or a straight-chain alkenyl group containing 2 to 5 carbon atoms.

[0071] In some embodiments of the present invention, preferably, R M1 and / or R M2 Each independently is a straight-chain alkenyl group having 2 to 8 carbon atoms, and more preferably each independently is a straight-chain alkenyl group having 2 to 5 carbon atoms.

[0072] In some embodiments of the present invention, preferably, R M1 and R M2 One of them is a straight-chain alkenyl group having 2 to 5 carbon atoms, and the other is a straight-chain alkyl group having 1 to 5 carbon atoms.

[0073] In some embodiments of the present invention, preferably, R M1 and R M2 Both are straight-chain alkyl groups containing 1 to 8 carbon atoms, or straight-chain alkoxy groups containing 1 to 7 carbon atoms; more preferably, both are straight-chain alkyl groups containing 1 to 5 carbon atoms, or straight-chain alkoxy groups containing 1 to 4 carbon atoms.

[0074] In some embodiments of the present invention, preferably, R M1 and R M2 Any one of them is a straight-chain alkyl group containing 1 to 5 carbon atoms, and the other is a straight-chain alkyl group containing 1 to 5 carbon atoms, or a straight-chain alkoxy group containing 1 to 4 carbon atoms; more preferably, R M1 and R M2 Both are straight-chain alkyl groups having 1 to 5 carbon atoms.

[0075] The alkenyl group in the present invention is preferably selected from the group represented by any one of formula (V1) to formula (V9), and is particularly preferably formula (V1), formula (V2), formula (V8) or (V9). The groups represented by formula (V1) to formula (V9) are as follows:

[0076]

[0077] Here, * represents the carbon atom in the ring structure to which it is bonded.

[0078] The alkenyloxy group in the present invention is preferably selected from the group represented by any one of formula (OV1) to formula (OV9), and is particularly preferably the group represented by formula (OV1), formula (OV2), formula (OV8) or (OV9). The groups represented by formula (OV1) to formula (OV9) are as follows:

[0079]

[0080] Here, * represents the carbon atom in the ring structure to which it is bonded.

[0081] In some embodiments of the present invention, the compound of formula M is selected from the group consisting of:

[0082]

[0083]

[0084]

[0085] as well as

[0086]

[0087] In some embodiments of the present invention, the compound of formula M is preferably selected from the group consisting of compounds of formula M1, formula M2, formula M4, formula M9, ​​formula M11, formula M20 and formula M21.

[0088] Relative to the total weight of the PSA liquid crystal composition of the present invention, the preferred lower limit of the content of the compound of general formula M is 1%, 10%, 20%, 30%, 40% or 50%; relative to the total weight of the PSA liquid crystal composition of the present invention, the preferred upper limit of the content of the compound of general formula M is 95%, 85%, 75%, 65%, 60%, 55%, 45%, 35% or 25%.

[0089] Regarding the content of the compound of general formula M, when it is necessary to keep the viscosity of the PSA liquid crystal composition of the present invention low and the response time short, the lower limit is preferably higher and the upper limit is higher; further, when it is necessary to keep the clearing point of the PSA liquid crystal composition of the present invention high and the temperature stability good, the lower limit is preferably higher and the upper limit is higher; in order to keep the driving voltage low and the absolute value of the dielectric anisotropy large, it is preferred to make the lower limit lower and the upper limit lower.

[0090] When reliability is important, R M1 and R M2 are each independently an alkyl group; when it is important to reduce the volatility of the compound, preferably R M1 and R M2 are each independently an alkoxy group; when the viscosity reduction is important, preferably R M1 and R M2 At least one of them is alkenyl.

[0091] In some embodiments of the present invention, the host liquid crystal A contains at least one or more compounds selected from the group consisting of general formula M1-a, general formula M1-b and general formula M1-c:

[0092]

[0093] as well as

[0094]

[0095] In some embodiments of the present invention, the host liquid crystal A further comprises one or more compounds of the general formula N:

[0096]

[0097] in,

[0098] R N1 and R N2 Each independently represents a straight or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the straight or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H in these groups may be independently replaced by -F or -Cl;

[0099] ring and ring Each independently expresses in, One or more -CH2- in the ring may be replaced by -O-, one or at most two single bonds in the ring may be replaced by double bonds, One or more -H in the ring may be replaced by -F or -Cl, and one or more -CH= in the ring may be replaced by -N=;

[0100] Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -CF2O-, -OCF2- or -CF2CF2-; and

[0101] n N1 Indicates 0, 1, 2, or 3, n N2 Represents 0 or 1, and 0≤n N1 +n N2 ≤3, when n N1 =2 or 3, the ring Can be the same or different, Z N1 Can be the same or different.

[0102] In some embodiments of the present invention, in the compound of formula N, R N1 and R N2Preferably, each independently is an alkyl or alkoxy group containing 1 to 8 carbon atoms, or an alkenyl or alkenyloxy group containing 2 to 8 carbon atoms, and more preferably, each independently is an alkyl or alkoxy group containing 1 to 5 carbon atoms, or an alkenyl or alkenyloxy group containing 2 to 5 carbon atoms;

[0103] R N1 More preferably, it is an alkyl group containing 1 to 5 carbon atoms, or an alkenyl group containing 2 to 5 carbon atoms, and still more preferably, it is an alkyl group containing 2 to 5 carbon atoms, or an alkenyl group containing 2 to 3 carbon atoms;

[0104] R N2 More preferably, it is an alkoxy group containing 1 to 4 carbon atoms;

[0105] ring and ring Preferably

[0106] In some embodiments of the present invention, the compound of formula N is selected from the group consisting of:

[0107]

[0108]

[0109] as well as

[0110]

[0111] In some embodiments of the present invention, the compound of formula N is preferably selected from the group consisting of compounds of formula N2, formula N3, formula N5, formula N8, formula N12 and formula N14.

[0112] In some embodiments of the present invention, the PSA liquid crystal composition of the present invention preferably contains one or more compounds of the general formula N, preferably contains one or more compounds selected from the group consisting of the general formulas N2 to N7 and the general formulas N10 to N21, and more preferably contains 2 to 10 compounds selected from the group consisting of the general formulas N2 to N7 and the general formulas N10 to N21.

[0113] Regarding the preferred content of the compound of general formula N: relative to the total weight of the PSA liquid crystal composition of the present invention, the preferred lower limit of the content of the compound of general formula N is 0.1%, 0.5%, 1%, 3%, 5%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38% or 40%; relative to the total weight of the PSA liquid crystal composition of the present invention, the preferred upper limit of the content of the compound of general formula N is 95%, 90%, 88%, 85%, 83%, 80%, 78%, 75%, 73%, 70%, 68%, 65%, 63%, 60%, 55%, 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15% or 10%.

[0114] Regarding the preferred content of the compound of general formula N, when it is necessary to keep the viscosity of the PSA type liquid crystal composition of the present invention low and the response time short, the lower limit is preferably low and the upper limit is preferably low; further, when it is necessary to keep the clearing point of the PSA type liquid crystal composition of the present invention high and the temperature stability good, the lower limit is preferably low and the upper limit is preferably low; in addition, when the absolute value of the dielectric anisotropy is increased in order to keep the driving voltage low, the lower limit is preferably high and the upper limit is relatively high.

[0115] In some embodiments of the present invention, the PSA type liquid crystal composition further comprises one or more additives known to those skilled in the art and described in the literature.

[0116] The stabilizer which can be added to the PSA type liquid crystal composition according to the present invention, for example, is mentioned below.

[0117]

[0118]

[0119]

[0120]

[0121] Preferably, the stabilizer is selected from the stabilizers listed below.

[0122]

[0123] In some embodiments of the present invention, preferably, the stabilizer accounts for 0-5wt% of the total weight of the PAS type liquid crystal composition; more preferably, the stabilizer accounts for 0-1wt% of the total weight of the PAS type liquid crystal composition; particularly preferably, the stabilizer accounts for 0.01-0.1wt% of the total weight of the PAS type liquid crystal composition.

[0124] Another aspect of the present invention provides a liquid crystal display device, which comprises the PSA type liquid crystal composition provided by the present invention.

[0125] Beneficial effects:

[0126] The PSA liquid crystal composition provided by the present invention improves the functional groups of the polymerizable compound (including the connecting groups between the rings, the substituent groups on the rings, and the connecting groups between the polymerizable groups and the rings) to effectively improve the mutual solubility between the polymerizable component and the main liquid crystal, so that the liquid crystal composition can also maintain the nematic phase state in a low temperature environment without crystallization, so that crystallization will not occur during transportation and manufacturing to cause performance changes. The viscosity of the PSA liquid crystal composition of the present invention is also very low, which can meet the requirements of liquid crystal display devices (such as 3D displays) with fast response speed. In addition, the polymerization speed of the polymerizable compound of the present invention during photopolymerization is neither too fast nor too slow, which is appropriate, so that uniform and stable orientation control can be achieved, and a liquid crystal display device with less or no image retention and uneven display can be provided. In summary, the PSA liquid crystal composition provided by the present invention has good mutual solubility, does not crystallize in a low temperature environment, can also form a stable pre-tilt angle, and the polymerization process will not form poor display conditions such as broken bright spots. DETAILED DESCRIPTION

[0127] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0128] Unless otherwise specified in the present invention, all ratios are weight ratios and all temperatures are degrees Celsius.

[0129] For ease of expression, in the following embodiments, the group structure of the liquid crystal composition is represented by the codes listed in Table 1':

[0130] Table 1' Group structure code of liquid crystal compounds

[0131]

[0132]

[0133] Take the following compound as an example:

[0134]

[0135] If the structural formula is represented by the codes listed in Table 1', it can be expressed as: nCCGF, where n in the code represents the number of C atoms in the left-hand alkyl group, for example, n is "3", which means that the alkyl group is -C3H7; C in the code represents cyclohexyl, G represents 2-fluoro-1,4-phenylene, and F represents fluorine.

[0136] The abbreviated codes for the test items in the following embodiments are as follows:

[0137] Cp(℃) Clearing point (nematic-isotropic phase transition temperature)

[0138] Δn optical anisotropy (589nm, 25℃)

[0139] Δε Dielectric anisotropy (1KHz, 25℃)

[0140] γ1 Rotational viscosity (mPa*s, at 25°C)

[0141] LTS Low temperature storage stability (℃, temperature at which no crystallization occurs after storage for 500 hours)

[0142] in,

[0143] The optical anisotropy was measured using an Abbe refractometer under a sodium lamp (589 nm) at 25°C.

[0144] Δε=ε ‖ -ε ⊥ , where ε ‖ is the dielectric constant parallel to the molecular axis, ε ⊥ is the dielectric constant perpendicular to the molecular axis. Test conditions: 25°C, 1KHz, TN90 test box, 7μm thickness.

[0145] γ1 was obtained by testing using the TOYO6254 liquid crystal property evaluation system; the test temperature was 25°C and the test voltage was 90V.

[0146] Each component used in the following examples can be synthesized by a known method or obtained through commercial channels. These synthesis techniques are conventional, and each liquid crystal compound obtained meets the standards of electronic compounds after testing.

[0147] Host Liquid Crystal Example 1

[0148] A nematic phase host liquid crystal Host 1 was prepared as shown in Table 1 below.

[0149] Table 1 Composition and performance parameters of Host 1

[0150]

[0151]

[0152] Host Liquid Crystal Example 2

[0153] The nematic phase host liquid crystal Host 2 was prepared as shown in Table 2 below.

[0154] Table 2 Composition and performance parameters of Host 2

[0155]

[0156] Host Liquid Crystal Example 3

[0157] The nematic phase host liquid crystal Host 3 was prepared as shown in Table 3 below.

[0158] Table 3 Composition and performance parameters of Host 3

[0159]

[0160]

[0161] Host Liquid Crystal Example 4

[0162] The nematic phase host liquid crystal Host 4 was prepared as shown in Table 4 below.

[0163] Table 4 Composition and performance parameters of Host 4

[0164]

[0165] Host Liquid Crystal Example 5

[0166] The nematic phase host liquid crystal Host 5 was prepared as shown in Table 5 below.

[0167] Table 5 Composition and performance parameters of Host 5

[0168]

[0169]

[0170] Host Liquid Crystal Example 6

[0171] The nematic phase host liquid crystal Host 6 was prepared as shown in Table 6 below.

[0172] Table 6 Composition and performance parameters of Host 6

[0173]

[0174] Host Liquid Crystal Example 7

[0175] The nematic phase host liquid crystal Host 7 was prepared as shown in Table 7 below.

[0176] Table 7 Composition and performance parameters of Host 7

[0177]

[0178] Host Liquid Crystal Example 8

[0179] The nematic phase host liquid crystal Host 8 was prepared as shown in Table 8 below.

[0180] Table 8 Composition and performance parameters of Host 8

[0181]

[0182]

[0183] Host Liquid Crystal Example 9

[0184] The nematic phase host liquid crystal Host 9 is prepared as shown in Table 9 below.

[0185] Table 9 Composition and performance parameters of Host 9

[0186]

[0187] Host Liquid Crystal Example 10

[0188] A nematic phase host liquid crystal Host 10 was prepared as shown in Table 10 below.

[0189] Table 10 Composition and performance parameters of Host 10

[0190]

[0191] Host Liquid Crystal Example 11

[0192] A nematic phase host liquid crystal Host 11 was prepared as shown in Table 11 below.

[0193] Table 11 Composition and performance parameters of Host 11

[0194]

[0195] Host Liquid Crystal Example 12

[0196] The nematic phase host liquid crystal Host 12 is prepared as shown in Table 12 below.

[0197] Table 12 Composition and performance parameters of Host 12

[0198]

[0199]

[0200] Host Liquid Crystal Example 13

[0201] The nematic phase host liquid crystal Host 13 is prepared as shown in Table 13 below.

[0202] Table 13 Composition and performance parameters of Host 13

[0203]

[0204] Host Liquid Crystal Example 14

[0205] The nematic phase host liquid crystal Host 14 was prepared as shown in Table 14 below.

[0206] Table 14 Composition and performance parameters of Host 14

[0207]

[0208]

[0209] PSA type liquid crystal composition example

[0210] The PSA liquid crystal compositions of Examples 1 to 308 were prepared by adding the compounds in Table 15 below to the nematic host liquid crystals Host 1 to Host 14 at the concentrations in Tables 17 to 30 below, and injected into a vertically aligned test box to test relevant performance parameters.

[0211] Table 15

[0212]

[0213]

[0214]

[0215] For the purpose of comparison, the polymerizable compounds M1 and M2 in the prior art were added to the nematic phase host liquid crystals Host 1 to Host 14 at the concentrations shown in Table 16 to prepare PSA liquid crystal compositions of Comparative Examples 1 to 39, and injected into a vertically aligned test box to test relevant performance parameters.

[0216]

[0217] Comparative Example 1-Comparative Example 39

[0218] Table 16

[0219]

[0220]

[0221]

[0222] “-” means it cannot be detected.

[0223] Example 1-Example 22

[0224] Table 17

[0225]

[0226]

[0227] Example 23-Example 44

[0228] Table 18

[0229]

[0230]

[0231]

[0232] Example 45-Example 66

[0233] Table 19

[0234]

[0235]

[0236] Example 67-Example 88

[0237] Table 20

[0238]

[0239]

[0240] Example 89-Example 110

[0241] Table 21

[0242]

[0243]

[0244] Example 111-Example 132

[0245] Table 22

[0246]

[0247]

[0248] Example 133-Example 154

[0249] Table 23

[0250]

[0251]

[0252] Example 155-Example 176

[0253] Table 24

[0254]

[0255]

[0256] Example 177-Example 198

[0257] Table 25

[0258]

[0259]

[0260] Example 199-Example 220

[0261] Table 26

[0262]

[0263]

[0264]

[0265] Example 221-Example 242

[0266] Table 27

[0267]

[0268]

[0269] Example 243-Example 264

[0270] Table 28

[0271]

[0272]

[0273] Example 265-Example 286

[0274] Table 29

[0275]

[0276]

[0277] Example 287-Example 308

[0278] Table 30

[0279]

[0280]

[0281] From the data of the above comparative examples and embodiments, it can be seen that the PSA liquid crystal composition provided by the present invention has good mutual solubility, does not crystallize in a low temperature environment, can form a stable pretilt angle, and the polymerization process does not form poor display conditions such as broken bright spots.

[0282] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A PSA type liquid crystal composition, comprising: a main liquid crystal A and a polymerizable component B accounting for 0.1% to 3% of the total weight of the PSA type liquid crystal composition, wherein: The host liquid crystal A comprises one or more liquid crystal compounds, and the polymerizable component B comprises at least one compound selected from the group consisting of general formula I-1, general formula I-2 and general formula I-3: in, Ring A, ring B, ring C, ring D, ring E, ring F, ring G, ring H and ring I each independently represent a phenylene group or a naphthylene group; X 1-1 , X 1-2 , X 1-3 , X 2-1 , X 2-2 , X 2-3 , X 2-4 , X 3-1 , X 3-2 , X 3-3 , X 3-4 and X 3-5 Each independently represents a single bond, a straight or branched alkylene group containing 1 to 12 carbon atoms, one or more -CH2- in the straight or branched alkylene group containing 1 to 12 carbon atoms may be replaced by -O-, -S-, -NH-, -CO-, -CH=CH- or -C≡C- in a manner that heteroatoms are not directly connected to each other, and one or more -H in the -CH2- in the straight or branched alkylene group containing 1 to 12 carbon atoms may be replaced by halogen, and X 1-1 , X 1-2 , X 1-3 At least one of them represents a single bond, X 2-1 , X 2-2 , X 2-3 , X 2-4 At least one of them represents a single bond, X 3-1 , X 3-2 , X 3-3 , X 3-4 , X 3-5 At least one of them represents a single bond; R A , R B , R C , R D , R E , R F , R G , R H and R I Each independently represents a halogen, a halogenated or unhalogenated straight-chain or branched alkyl or alkoxy group containing 1 to 5 carbon atoms; P 1-1 , P 1-2 , P 2-1 , P 2-2 , P 3-1 and P 3-2 Each independently expresses a, b, c, d, e, f, g, h and i each independently represent 0, 1, 2 or 3. When a is 2 or 3, R A can be the same or different; when b is 2 or 3, R B can be the same or different; when c is 2 or 3, R C can be the same or different; when d is 2 or 3, R D can be the same or different; when e is 2 or 3, R E can be the same or different; when f is 2 or 3, R F can be the same or different; when g is 2 or 3, R G can be the same or different; when h is 2 or 3, R H can be the same or different; when i is 2 or 3, R I Can be the same or different; a+b+n1≥1, and n1≥1, n1 represents X 1-1 , X 1-2 , X 1-3 The number of non-single-bond groups in c+d+e+n2≥2, and n2≥1, n2 represents X 2-1 , X 2-2 , X 2-3 , X 2-4 The number of non-single-bond groups in f+g+h+i+n3≥3, and n3≥1, n3 represents X 3-1 , X 3-2 , X 3-3 , X 3-4 , X 3-5 The number of non-single-bond groups in The compound of formula I-1 is selected from the group consisting of the following compounds: as well as The compound of formula I-2 is selected from the group consisting of the following compounds: as well as And the compound of formula I-3 is selected from the group consisting of the following compounds: as well as The host liquid crystal A comprises one or more compounds of the general formula M: in, R M1 and R M2 Each independently represents a straight or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the straight-chain or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-; Ring M1, ring M2 and ring M3 each independently represent in, One or more -CH2- in may be replaced by -O-, At most one -H in may be replaced by halogen; Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -CF2O-, -OCF2- or -CF2CF2-; and n M1 represents 0, 1, 2, or 3, and when n M1 =2 or 3, the rings M2 may be the same or different, Z M2 Can be the same or different; The host liquid crystal A further comprises one or more compounds of the general formula N: in, R N1 and R N2 Each independently represents a straight or branched alkyl group containing 1 to 12 carbon atoms, One or more non-adjacent -CH2- in the straight or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H in these groups may be independently replaced by -F or -Cl; ring and ring Each independently expresses in, One or more -CH2- in the ring may be replaced by -O-, one or at most two single bonds in the ring may be replaced by double bonds, One or more -H in the ring may be replaced by -F or -Cl, and one or more -CH= in the ring may be replaced by -N=; Z N1 and Z N2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -CF2O-, -OCF2- or -CF2CF2-; and n N1 Represents 0, 1, 2, or 3, n N2 Represents 0 or 1, and 0≤n N1 +n N2 ≤3, when n N1 =2 or 3, the ring Can be the same or different, Z N1 Can be the same or different; The lower limit of the content of the compound of the general formula M is 25%, and the upper limit of the content of the compound of the general formula M is 75%; The lower limit of the content of the compound of the general formula N is 25%, and the upper limit of the content of the compound of the general formula N is 65%; If the polymerizable component B contains one compound of the general formula I-1 where a+b+n1=1, it also contains at least another compound selected from the group consisting of the general formula I-1, the general formula I-2 and the general formula I-3.

2. The PSA type liquid crystal composition according to claim 1, characterized in that: a+b+n1≥2; c+d+e+n2≥3; f+g+h+i+n3≥4.

3. The PSA type liquid crystal composition according to claim 1, characterized in that: The polymerizable component B contains only one compound of the general formula I-1, wherein a+b≠0.

4. The PSA type liquid crystal composition according to claim 1, characterized in that: When X 2-1 and X 2-4 When both represent single bonds, c+d+e≥1.

5. The PSA type liquid crystal composition according to claim 1, characterized in that: If the polymerizable component B contains 2 or 3 polymerizable compounds, and at least one of the 2 or 3 polymerizable compounds is selected from the compound of formula I-2, then when X 2-1 and X 2-4 When both represent single bonds, c+d+e≥1.

6. The PSA type liquid crystal composition according to claim 1, characterized in that: When X 3-1 and X 3-5 When all are single bonds, f+g+h+i≥2; when X 3-1 and X 3-5 When only one of them represents a single bond, f+g+h+i≥2.

7. The PSA type liquid crystal composition according to claim 1, characterized in that: If the polymerizable component B contains 2 or 3 polymerizable compounds, and at least one of the 2 or 3 polymerizable compounds is selected from the compound of formula I-3, then when X 3-1 and X 3-5 When all are single bonds, f+g+h+i≥2; when X 3-1 and X 3-5 When only one of them represents a single bond, f+g+h+i≥2.

8. The PSA type liquid crystal composition according to claim 1, characterized in that: The host liquid crystal A contains at least one or more compounds selected from the group consisting of general formula M1-a, general formula M1-b and general formula M1-c: as well as 9. A liquid crystal display device comprising the PSA type liquid crystal composition according to any one of claims 1 to 8.

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