TWI238186B - Liquid crystal compounds with optical activities, method for preparing the same, and liquid crystal compositions containing the compounds - Google Patents

Abstract

The invention relates to the development of the liquid crystal compounds with optical activities. The structure of the liquid crystal compounds is the ester compound with optical activities. The derivatives of Tartaric acid, Erythritol, Arabitol and Mannitol as starting materials reacted with other reactants whose core structures are similar with the liquid crystal compounds. The compounds are highly dissolved with liquid crystal host and the liquid crystal composition with the compounds can get larger helical twisting power and better light stability.

Description

1238186 _Case No. 91137449_ Revised Year of the Month _5. Description of the Invention (1) Technical Field to which the Invention belongs: The present invention relates to an optically active liquid crystal additive, and in particular, to a compound obtained by using the compound and its derivative as ingredients. The liquid crystal composition is suitable for a traditional transmissive display (TN, STN, TFT), a reflective SSCT display, and a cholesterol-type reflective polarizing plate having a wide reflection wavelength range. Prior technology: The cholesteric liquid crystal display is a bistable display. It has the characteristics of low power consumption, high reflectivity, and can reflect different wavelengths and wide viewing angles. It can be applied to e-books and other types of products. The cholesteric liquid crystal molecules have a spiral structure in the arrangement, and can reflect circularly polarized light in a specific direction at a wavelength close to the pitch of the liquid crystal, and circularly polarized light in the other direction passes through. According to the Bragg reflection principle, its reflection wavelength (λ) and reflected wave width (△ again) are λ = ρ X nave and Δλ = χ Δη, respectively, where nav (and Δ η are the average refractive index and double Refractive index, P is the pitch of the cholesteric liquid crystal phase. There are two ways to generate the cholesteric liquid crystal phase. The first is that the nematic liquid crystal molecules have optically active groups, and the other is that the optically active Optically active molecules are mixed with non-optically active nematic liquid crystal formulas. Generally, the second method is the main method, and the pitch is controlled by the mixing ratio of optically active molecules and non-optically active nematic liquid crystal formulas. The molecular helix twist power (HTP) of the cholesteric liquid crystal phase is related to the pitch of the molecule (Pitch, P) and the concentration of the optically active substance in the nematic liquid crystal mixture.

1238186 _ Case No. 91137449_ Year Month and Day _i ± L · _ V. Description of the invention (2) The short form of the column indicates: HTP II (PX c) _l where t P is the pitch of the cholesterol liquid crystal molecules, c is the addition of optically active molecules In terms of the weight percentage concentration of the liquid crystal mixture, HTP is the helix twisting force (he 1 ica 1 twist ρ ower), which represents the ability of optically active molecules to rotate the liquid crystal molecules.

Currently, the HTP value of the optically active substance (chira 1 d 〇pant) commonly used in LCD panels is about 8 ~ 1 2 // nr1. In order to achieve the bi-stable state requirements of cholesterol liquid crystal panels, a nematic liquid crystal combination is required. Adding 20-30 wt% of the optically active substance to the bi-stable state. However, most optically active materials are solid at room temperature. Adding so much amount to the nematic liquid crystal composition will greatly increase the viscosity of the overall composition, resulting in an increase in driving voltage and a decrease in reflectance, and also increase the material cost.

On the other hand, the optically active liquid crystal molecules are added to the liquid crystal formulation. Due to the special spiral structure of the optically active liquid crystal molecules, when the weight percentage of the optically active high-twisting liquid crystal molecules gradually increases, the liquid crystal matrix (multilayer nematic liquid crystal) The solubility of the optically active liquid crystal molecules is poor, so that when formulating a 'cholesterol liquid crystal composition, its weight percentage concentration will be limited by the configuration of the optically active high-twisting liquid crystal molecules. SUMMARY OF THE INVENTION In view of this, the object of the present invention is to provide an optically active liquid crystal additive, which uses its optically active optical rotation and high helix twisting force to make the liquid crystal composition reflect a specific wavelength, and uses its structure similar to a liquid crystal ( core structure) to increase solubility in liquid crystals. Another object of the present invention is to provide the above-mentioned optically active liquid crystal additive.

Page 8 1238186 Case No. 91137449 Amendment V. Description of the Invention (3) Method for making a compound a c i d) derivative SKArabitol) or organic acid compound additive. The liquid crystal combination of the additive liquid crystal of the present invention and the super-twisted direction (CSTN) liquid crystal display is to achieve the above-mentioned early special liquid crystal adding formula (I) in the formula (I) (tartaric ac (Erythritol) (A rabit ο 1) derivatization, which includes performing optically active tartaric erythritol (Ery ΐ hrito 1) derivatives, gum arabic derivatives, or mannitol (ma η nit ο 1) and other alcohol derivatives Reaction to form the above-mentioned optically active liquid crystal. Another object is to provide the optically active liquid crystal additive as a traditional twisted nematic (TN) liquid crystal display nematic (STN) liquid crystal display, color super twisted nematic. Suitable for thin-film displays or thin-film transistor-type (TFT) liquid crystal displays. Purpose, the present invention relates to optically active high-helix twisted objects having a structure as shown in formula (I), GMX-z-) m, z-: compounds in which (T is the structure of an optically active tartaric acid derivative), the structure of an optically active erythritol derivative, the biological structure of optically active arabinol, or the optically active mannitol (m annitol) derivative structure; X is 〇II or -〇-c- x 〇II c-〇 one is hydrogen, halogen, alkyl, thioalkyl, alkoxy, alkynyl, alkynyl, Alkenyloxy or alkynyloxy, in which alkyl, sulfanyl, alkoxy, alkenyl, from fast, dilute or fast oxy contain 1-12 carbon atoms, are straight or branched And more than one of them can be taken by the halogen atom

1238186 _ Case No. 91137449_ 年月 日 _ί ± ^ _ V. Description of the invention (4) Generation; Z is cycloalkyl, heterocyclyl, cycloalkyl and heterocyclyl having one or more unsaturated bonds, Aryl, heteroaryl, aralkyl, or heteroaralkyl, and wherein the hydrogen on the ring atom can be optionally an alkyl group containing 1 to 12 carbon atoms, an alkane containing 1 to 12 carbon atoms Oxy or halogen atom is substituted; η is 1, 2 or 3, if η is 2 or 3, each Z system is the same or different cycloalkyl, heterocyclic group, having one or more unsaturated bonds "Cycloalkyl and heterocyclyl, aryl, heteroaryl, aryl, or heteroaryl" and wherein the hydrogen on the ring atom can be optionally an alkyl group containing 1 to 12 carbon atoms, Substituted by an alkoxy or halogen atom of 2 carbon atoms; m is 1, 2, 3 or 4; if m is 2, 3 or 4, each X is the same or different corresponding chemical structure , And each Z ′ is the same or different corresponding chemical structure. The feature of the present invention is the design of optically active liquid crystal additives, using optically active tartaricacid, erythritol, arabitol, and mannitol (ma η nit ο 1) The derivative is a new optically active molecular center, and a rod-like structure similar to the liquid crystal molecule is added as a side portion to develop an optically active high-helix twisting liquid crystal additive. The focus of its implementation is: maintaining the optical activity and a large number of chiral centers in the molecule, and then introducing a functional group similar to the liquid crystal structure, and the imported liquid crystal-like structure is a less polar ring function. When the liquid crystal composition with the optically active, high-helix torsional force is mixed with the liquid crystal matrix, the viscosity of the overall liquid crystal composition can be reduced and the response time can be effectively reduced. The present invention also relates to a method for manufacturing an optically active liquid crystal additive conforming to the structure of formula (I), which includes optically active tartaric acid.

Page 10 1238186 _tS 91137449_Yueyue; p _ V. Description of the invention (5) (tartaric acid) alcohol derivatives, erythritol alcohol derivatives, Arab itol derivatives Or mannitol (in a η nit ο 1) alcohol derivative reacts with the organic acid compound of formula (X IV) to form an optically active liquid crystal additive conforming to formula (I) as described above, formula (X IV ) HO—C- (Z ^ -Ri The definition of the center & Z is the same as the formula (I); η is 1, 2 or 3; if η is 2 or 3, each Z is the same or different Cyclohexyl, heterocyclyl, cycloalkynyl with one or more unsaturated bonds, and heterocyclyl, aryl, heteroaryl, aryl, or heteroaralkyl, and wherein the hydrogen on the ring atom is It needs to be substituted by a radical containing 12 back atoms, a radical containing oxygen or halogen atoms with 1-12 hind atoms. The present invention relates to the above-mentioned optically active liquid crystal additive conforming to the structure of formula (I). The production method also includes an optically active tartaric acid derivative and an erythritol derivative , Arabitol derivative or mannitol derivative react with the organic acid or alcohol compound of formula (XV) to form the liquid crystal additive formula with optical activity in accordance with formula (I) ( XV) The definition of its center is the same as that of formula (I); when n is 1, 2 or 3, where is R? Or 3, each Z is the same or different cycloalkyl, heterocyclyl, Or one

1238186 Case No. 91137449 _η Amendment V. Description of the Invention (6) Cycloalkyl and heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl with unsaturated bonds above, and the ring atom Hydrogen may be substituted with a carbyl group containing 12 carbon atoms, a alkoxy group containing 1 -12 carbon atoms, or a halogen atom, if necessary. The reaction formula of the compound of the above formula (I) structure is shown in formula (XVI): Formula (X V I),-(OH) m + mHO-C'tZiirRi

DCC, DMAP

CH2ci > H O * Ten O — C Ten Z) m H20 DCC, DMAP OH) m + mH〇— ~ _ CH2C1 ^

C ^ + ΗΪ: — CHZkHRA H20 In the formula (XVI), G * is the structure of an optically active tartaricacid derivative, and the optically active erythri 糠 o 1) derivative structure and optically active The structure of a derivative of arabinol (Arabi tol) or the derivative structure of optically active mannitol (ma η nit ο 1). & is hydrogen, halogen, alkynyl, sulfanyl, alkynyl, alkynyl, alkynyl, alkenyloxy, or alkynyloxy, of which alkyl, sulfanyl, alkoxy, alkenyl , Alkynyl, alkenyloxy or alkynyloxy contains a carbon atom of 12 and is linear or branched, and more than one of them can be replaced by a halogen atom; Z is a cycloalkyl, Heterocyclyl, cycloalkyl and heterocyclyl with one or more unsaturated bonds, aryl, heteroaryl, aralkyl, or heteroaralkyl, and wherein the hydrogen on the ring atom can be contained as needed Substituted by an alkyl group of 1 -1 2 carbon atoms, an alkoxy group containing 1 -12 carbon atoms, or a halogen atom; η is 1, 2 or 3; if η is 2 or 3, each Z is The same or different cycloalkyl, heterocyclyl, with-· or

1238186 on page 12 _Case No. 91137449 _ Revised Year of the Year __ 5. Description of the invention (7) Cycloalkyl and heterocyclyl, aryl, heteroaryl, aralkyl or heteroarane with one or more unsaturated bonds And the hydrogen on the ring atom may be substituted by an alkyl group containing 1 to 12 carbon atoms, an alkoxy group containing 12 carbon atoms, or a halogen atom if necessary; m is 1, 2, 3 Or 4, if m is 2, 3 or 4, the organic acid compound (or organic alcohol compound) may be the same or different organic acid (or organic alcohol compound) compound. Another feature of the present invention is to use a simple compounding step to utilize optically active tartaricacid, erythritol, arabitol, or mannitol (M a η nitoi). Alcohols or acid derivatives react with organic acids or alcohols similar to a liquid crystal core structure to obtain optically active functional liquid crystal compounds with high helical twisting force. This reaction step has the advantages of easy control of the synthesis process, high reactivity, and easy purification of the product. With this reaction, optically active compounds can be easily introduced into the liquid crystal molecules to form the required optically active high-twisting liquid crystal additives. . The present invention also relates to a liquid crystal composition having an optically active high-helix twisting liquid crystal additive, which is characterized by including the compound described in the above formula (I), and its composition includes at least: (a) 0.5 wt% to 3 wt% based on the total weight of the liquid crystal composition as a basis of at least one optically active liquid crystal additive as described in the above formula (I); and (b) 65wt% to 99.5 wt% to the liquid crystal composition of The liquid crystal based on the total weight is different from the component (a). The liquid crystal composition of the optically active high-helix twist liquid crystal additive of the present invention, at least one of the component (a) is as described in the above formula (I)

Page 13 1238186 Case No. 91137449 _η Revision V. Invention Description (8) Optically active high-helix twist liquid crystal additive, the preferred ratio of this component is 5 wt% to 20 wt% Based on the total weight of the liquid crystal composition. The liquid crystal composition may further include a liquid crystal additive of another component (c), which is different from the component (a) and the component (b). The liquid crystal composition of the optically active high-helix twist liquid crystal additive not only has excellent high-helix twist force, but also has low temperature dependence, high light and stability, and can be used as a liquid crystal composition required for a liquid crystal display. It is suitable for making liquid crystal display devices, especially for twisted nematic (TN) displays, super twisted nematic (STN). Monitors, color super twisted nematic (CSTN) displays and films. Transistor (TFT) display. The liquid crystal composition of the optically active high-helix twist liquid crystal additive of the present invention can also be used to make a liquid crystal display device including a cholesterol-type liquid crystal polarizing plate, a reflecting plate, or a color filter, if it has a reactive double bond It can also be applied to reactive liquid crystals. It can be used as a polarizing plate or color filter by polymerization. The alcohol (G *-(OH) m) or acid (G *-(COOH), n) derivative of the optically active tartaric acid according to the present invention may have the following structure% G2 R2 where r2 and r3 are Self-contained alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl, alkynyloxy, cycloalkyl, heterocyclyl, cycloalkanes having one or more unsaturated bonds And heterocyclyl, aryl, heteroaryl, arane

1 ^ 1 Page 14 1238186 Case No. 91137449 Amendment V. Description of the Invention (9) A radical or heteroaralkyl radical, in which alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl An oxy or alkynyloxy group contains 1 to 12 carbon atoms, is a straight chain or branched one, and more than one of the hydrogen atoms may be replaced by a halogen atom; of which cycloalkyl, heterocyclyl, Or more than one unsaturated cycloalkyl and heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl, the hydrogen on the ring atom can be 1-12 carbon atoms as required It is substituted by an alkyl group, a oxo group containing 1 to 12 carbon atoms, or a halogen atom. The alcohols (G *-(Ο Η),: |) or acids (0 *-((: 001001)) derivatives having optically active erythritol according to the present invention, where (^ may have the following structure

; The alcohol (G *-(0H) m) or acid (G *-(C00H) m) derivatives of the present invention having optically active arabinyl alcohol (Arab i to 1), the G * may have the following structure

; The alcohol (G * _ (0H), n) or acid (G * _ (C00H) m) derivatives of the present invention having optically active mannitol (mannitol) can have the following structure G *

Page 15 1238186 _ Case No. 91137449 _ Month and Day _ V. Description of the invention (10)

. As shown above, in the tartaricacid, erythritol, arabitol, and mannitol (ma η nit ο i) derivative structure, the hydrogen on each carbon atom can be as needed Substituted by halogen, alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl or fastoxy, among which alkyl, thioalkyl, thioalkyl, thioalkyl, alkynyl Group, alkenyloxy or alkynyloxy contains 1 -1 2 carbon atoms, is a straight chain or branched, and more than one of the hydrogen atoms can be affected by the halogen atom. According to the present invention, the formula (XV I ) An organic acid or organic alcohol having a liquid crystal core structure (cor estructure) may be an organic acid or organic alcohol compound having the following structure

Page 16 1238186 _ Case No. 91137449 _ Month and Day _ V. Description of the invention (11)

Where & is hydrogen, halogen, alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, dilute or alkynyl, among which alkynyl, sulfonyl, alkoxy, and alkene Alkynyl, alkynyl, alkenyloxy or alkynyloxy contains a carbon atom of 12 and is linear or branched, and more than one of its hydrogen atoms may be replaced by a halogen atom; as shown above In the structure of an organic acid or organic alcohol compound, hydrogen at each carbon atom may be optionally substituted by halogen, alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl, or alkynyloxy. Substitution, in which alkyl, sulfanyl, oxo, dilute, alkoxy, fine or oxy contain 1 to 12 carbon atoms, are straight or branched, and 1 More than one hydrogen atom may be replaced by a halogen atom.

Page 17 1238186 __Case No. 91137449__Year Month Chromium 丨 Next_ V. Description of the Invention (12) The optically active liquid crystal additive of the structure of formula (I) described in the present invention will have multiple asymmetric centers ( (chiral center) is introduced on the carbon chain or polycyclic structure to achieve the development of optically active compounds with high HTP values. At present, it is known that the HTp value of the optically active liquid crystal additive having the formula (I) structure is about 5 to 30 / z nr1, and the preferred embodiment can reach 3 5 // nr1 or more. If it is added to the liquid crystal composition, the amount of addition only needs to be less than 20%, and the effect of the double and stable state of the liquid crystal arrangement can be achieved. In order to make the above and other objects and features of the present invention more comprehensible, the following describes specific examples, and describes them in detail as follows: "Implementation method: Synthesis of compounds (I) Structure of the optically active liquid crystal additive, the synthesis steps are detailed later. Test method: Pitch and helical rotation force HTP test part: We use 0 1 y m p u s MX X 50 optical polarization microscope to measure the pitch. The measurement method is to mix our new type of optically active molecules at a concentration of 1 wt% into ZL I-1132 provided by Merck, raise the temperature to I SO, and fill it into the wedge-shaped liquid crystal cell with a capillary action to perform the pitch. The standard scale (0 · 0 1 mm) is used to determine the unit scale length in the microscope. Remove the standard scale (0 · 0 1 mm) on the microscope stage and focus through the eyepiece. The distance between two liquid crystal defect lines can be used to obtain the pitch. We can weigh

1238186 ___Case No. 91137449_year month__iL £ _ 5. Description of the invention (13) Observe the value obtained three times after this step and average the pitch. The pitch value obtained through the above steps is then brought into the formula HTP = (P X C) -1, and the HTP value can be obtained through conversion. Synthesis of Liquid Crystal Additives: [Example 1] Synthesis of (+)-di, ethylbis-4-hexylbenzylcarbonyloxy tartrate ((+)-Diethyl di-4-hexylphenylcarbony loxy tartarate) Synthesis: In Krypton Gas Under the system, 1 g (4.85 mmol) of 4-hexylbenzoic acid (4-hex y 1 ben zo ic ac id) and 0.5 g (2.42 mmo 1) (+) -diethyltartaric acid ( (+)-Diethyl-tartaric acid) was placed in a reaction flask, and 0.5 g (2.42 mmol) of N, N'-dicyclohexylcarbodiimide (N, N'-Dicyclohexyl carbodimide, DCC)) and 0.3 g (2.46 mmol) of Ν, Ν-dimethylaminopyridine (N, N- (dimethyl amino) -pyri dine, DMAP) 'was then added to 70 mL of dichloromethane and reacted at room temperature for 2 4 hours . The reaction was cooled to room temperature. After filtration, the filtrate was drained off, extracted with n-hexane, and then the organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. (EA / n-Hex = 1: 8) Purified and isolated 'to obtain 0.80 g of white solid with a yield of 56%. Using a 01ympus Μχ50 optical polarization microscope to measure the pitch value (P1tch length, P) is 17. 丨, the above is obtained, and the pitch value is then banded, the formula HTP = (Px〇-lt, the spiral load force can be obtained ΗTP = 5.85 β m ~ {〇

Page 12 1238186

_ Case No. 91137449_ Year J_fUL V. Description of Invention (14)

[Example 2] (+)-Diethylbis-4-propylcyclohexylcarbonyloxy tartrate ((+)-Diethy1 di-4-propylcyclohexy lcarbonyloxy tartarate) Synthesis: Under a nitrogen system, 1.01 5.88 mmol of 4-propylcyclohexyl carboxylic acid and 0.5 g (2.42 mmol) of (+)-diethyltartaric acid ((+) _ Diethyl-tartaric acid) in a reaction flask 0.5 g (2.42 mmol) of N, N'-dicyclohexylcarbodiimide (N, N'-Di cyclohexyl carbodimide, DCC)) and 0.3 g (2.46 mmol) of N, N-di Methylaminopyridine (N, N- (dimethylamino) -pyridine, DMAP), and then added 7 ml of dichloromethane, and reacted at room temperature for 24 hours. The reaction was cooled to room temperature. After filtration, the filtrate was drained off and extracted with n-hexane. Then the organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. The water was removed with magnesium sulfate, filtered and drained off, and then subjected to column chromatography. (EA / η-H e X = 1 ·· 8) was purified and separated to obtain 0.92 g of a white solid with a yield of 75%. Use the Olympus MX50 optical polarization microscope to measure the pitch length (Pitch length, P) is 4 · 2 3 / zm, and then bring the pitch value obtained in the above steps into the formula HTP = (P xc) -1 to obtain the spiral twist Force HTP = 23 · 64 // nr1.

Page 20 1238186 ___— Case No. 91137449_Year_Month_Fifth, description of the invention (15)

[Example 3] (+)-Diethylbis-4-pentylcyclohexylcarbonyloxy tartrate ((+)-Diethyl di ^ 4-pentylcyclohexylcarbonyloxy tartarate) Synthesis:

Under a nitrogen system, 1.02 g (5.05 mmol) of 4-pentylcyclohexyl carboxylic acid and 0.5 g (2.42 mmol) (+)-diethyltartaric acid ((+) _ Diethyl-tartaric acid) is placed in a reaction flask 'and 0.5 g (2.24 mmol) of Ν, Ν'-dicyclohexylcarbodiimide (N, N'-Dicyclohexyl carbodimide, DCC)) and 0.3 g are added. (2.46 ininol) N'N-dimethylamino-D ratio (N, N- (dimethyl amino) -pyridine, DMAP), and then 70 mL of digas methane was added and reacted at room temperature for 24 hours. The reaction was cooled to room temperature. After filtration, the filtrate was drained off and extracted with n-hexane. Then the organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. The water was removed with magnesium sulfate, filtered and drained off, and then subjected to column chromatography. (EA / η-H e X = 1: 8) was purified and separated to obtain 0.87 g of a white solid with a yield of 63%. Use the Olympus MX50 optical polarizing microscope to measure the pitch value (pitch length, P) is 5. 7 3 // m, and then bring the pitch value obtained in the above steps into the formula HTP = (PX c) -1, and the spiral can be obtained. Torsion force HTP = 17 · 46 // nr1.

Page 21 1238186 Case No. 91137449_Year Month Day Amendment V. Description of Invention (16)

[Example 4] (+)-Diethyldi-4-propyldiphenylcarbonyloxy tartarate ((+)-Diethyldi-4-propylbiphenylcarbonyloxy tartarate) Synthesis:

Under a nitrogen system, 1.2 g (5 mmol) of 4'-propyl-biphenyl-4-carboxylic acid and 0.5 g (2.42 mmol) of ) (+) -Diethyl-tartaric acid ((+)-Diethyl-tartaric acid) in a reaction flask 'and then add 0.5 g (2.42 mmol) Ν, Ν'-dicyclohexylcarbodiimide (N, Ν '-Di cyclohexyl carbodimide (DCC)) and 0.3 g (2.46 mmol) of N'N-diamidinoamino [[than 0ding (N, N- (dimethyl amino) -pyridine, DMAP), then 70 mL of dioxane was added and reacted at room temperature for 24 hours. The reaction was cooled to room overflow. After filtration, the filtrate was drained off and extracted with n-hexane. The organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. The water was removed with sulfuric acid scale. After the transition, it was drained and then subjected to column chromatography. (EA / η-H e X = 1: 8). Purification and separation yielded 0.84 g of a white solid with a yield of 53%. Use a 01 ympus MX50 optical polarizing microscope to measure the pitch value (Pitch length, P) is 11. 2 0 gm, and then bring the pitch value obtained in the above steps into the formula HT p = (Px c) -1 to obtain the spiral Torsion force HTP = 8.93 / znr1.

Page 22 1238186 __ prime number 91137449_ car moon day _ 5. Description of the invention (17)

[Example 5] (+)-Diethylbis-4-propyldicyclohexylcarbonyloxytartrate ((+)-Diethy 1 di-4-propylbicyclohexylcarbonyloxy tar tar ate) Synthesis: Under a nitrogen system, Add 1.3 grams (5.16 mmo 1) of 4'-propyldicyclohexyl + carboxylic acid (4,-propy, bicyclohexyl + carboxylic acid) and 0.5 grams (2.42 mmol) (+)-diethyltartaric acid ((+)-Diethyl-tartaric acid) was placed in a reaction flask, and 0.5 g (2.42 mmol) of N, N'-dicyclohexylcarbodiimide (DC, DC)) and 0 were added. · 3 g (2.46 m mol) of N, N-dimethylamino-D (N, N- (dimethyl amino) -pyridine, DMAP), then 70 mL of dichloromethane is added and reacted at room temperature 24 hours. The reaction was cooled to room temperature. After filtration, the filtrate was drained off, extracted with n-hexane, and then the organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. (£ 4 / 11-Hex = 1: 8). Purified and isolated, 0.85 g of white solid was obtained with a yield of 52%. Use the Olympus MX50 optical polarizing microscope to measure the pitch length (Pitch length, P) is 6.22 // m, and then bring the pitch value obtained in the above steps into the formula HTP = (PX c) _ 〖, you can obtain the spiral torsion force HTp = 16 · 12 // nr1.

Page 23 1238186 Case No. 91137449 Λ_ Name Amendment V. Description of Invention (18) 〇 〇

[Example 6] (+)-Diethylbis-4-propylcyclohexylphenylcarbonyloxy tartarate ((+)-Diesthylyl-4-propylcyclohexylphenylcarbonyloxy tartarate) Synthesis: Under a nitrogen system, 1 · 2 g (4 · 8 7 mmo 1) 4-propylcyclohexylphenyl-4-carboxylic acid (4'-propylylcyclohexyl phenyl-4-carboxylic acid) and 0.5 g (2.42 mmol) (+)- Diethyl tartaric acid ((+)-Diethyl-tartaric acid) was placed in a reaction flask, and 0.5 g (2.42 mmol) of N, N'-dicyclohexylcarbodiimide (N, N'-Dicyclohexyl carbodimide, DCC) was added. )) And 0.3 g (2.46 mmol) N, N-dimethylaminopyridine (dimethyl ami no) -pyr idi ne (DMAP), then 70 mL of digas methane was added, and the reaction was performed at room temperature for 2 4 hours . The reaction was cooled to room temperature. After filtration, the filtrate was drained off and extracted with n-hexane. Then the organic layer was washed with water and dilute hydrochloric acid aqueous solution 2 to 3 times. The water was removed with magnesium sulfate, filtered off, and then dried by column chromatography. (EA / n_

Hex 2: 1) was purified and isolated to obtain 0.79 g of a white solid in a yield of 49%. Use a 0 1 ympus MX X 50 optical polarization microscope to measure the pitch value (pi tch length, P) as 1 5 · 33 # m, and then bring the pitch value obtained in the above steps into the formula HTP = (PX c) ~ l , We can find the spiral torsion force HTP = 6.57 ^ m'1 〇

Page 24 1238186 __Case No. 91137449_Year_Month_Fifth, the description of the invention (19)

B0 _Λ-〇〇 ^ ° 〇 [Example 7] 1,3: 2,4-bis-oxy- (P-propylbenzylidene) -erythritol (1,3: 2,4-Bis -O- (p-propylbenzylidene) -Erythritol) Synthesis:

Under a nitrogen system, put 1.4 g (9.46 mmol) of 4-propylbenzadehyde and 0.5 g (4.10 mmol) of erythritol in a reaction flask, and add 50 mL of DMF, and a catalytic amount of sulfuric acid was added, followed by stirring at room temperature for 48 hours. The carbon solution of potassium and potassium was added to adjust the solution to neutrality, and then the solid was filtered, washed with water and ethanol several times, and the solid was pumped to obtain a white solid, 0.96 g, with a yield of 61%. Use the Olympus MX50 optical polarizing microscope to measure the pitch length (Pitch length, P) is 4 · 12 / zm, and then bring the pitch value obtained in the above steps into the formula HTP = (PX c) -1, and the spiral twisting force can be obtained. HTP = 24 · 27 // nr! 〇

[Example 8] 4-propylphenylcarbonyl-1,3: 2,4-bis-oxy- (P-propylbenzylidene) -D-arabin gum (4-propylphenyl carbonyl-1,3: 2 , 4- Bis-O-

Page 25 1238186 _Case No. 91137449_year month__ ±± _ V. Description of the invention (20) (p-propylbenzy 1 idene) -D- arabitol) Synthesis: Under a nitrogen system, 0.6 g (2 (43 mmol) 4'-propylbenzyl-4-juni (4'-propyl phenyl—4-carboxylic acid) and 0.96 g (2.42 mmol) 1,3 ·· 2,4-bis-oxy- ( p-propylbenzylidene

Page 26 1238186 __Case No. 91137449_ Year a. Zuo Zuo. V. Description of the Invention (21) -D-arabinol (1,3: 2,4- Bis-0_ (p-propylbenzylidene) -D-arabitol) in a reaction flask 'Add 0.5 g (2.42 mmol) of N, N, -dicyclohexylcarbodiimide (N, N' —

Dicyclohexyi carbodimide (DCC)) and 0.3 g (2.46 mmoUN'N-dimethylaminopyridine (N, N- (dimethyl amino) -pyridine, DMAP)), then add 70 mL of digas methane at room temperature It was stirred for 1 hour, and then heated under reflux for two days. The reaction was cooled to room temperature, filtered, and the filtrate was drained, extracted with n-hexane, and then the organic layer was washed with water and a dilute hydrochloric acid aqueous solution 2 to 3 times. The water was removed with magnesium sulfate, and filtered. After drying, it was then purified and separated by column chromatography (EA / η-H e X = 1 ·· 4). 0.65 g of white solid was obtained with a yield of 46%. Using an Olympus MX50 optical polarization microscope The measured pitch value (pitch 1 ength, P) is 5 · 0 2 # m. The pitch value obtained in the above steps is then brought into the formula HTP = (P xc) -1, and the spiral torsion force HTP = 19. 92 can be obtained. μπτ1.

Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be determined by the scope of the attached patent application. In summary, compared with the conventional technology, the present invention has the following

Page 27 1238186 ___ Case No. 91137449 Main month—J_ϋ V. Description of the invention (22) Advantages: (1) The present invention mainly uses the concept of multiple asymmetric centers (chiral centers) to integrate multiple asymmetric centers (chiral centers) Introduced on the carbon gap or multi-bad structure to achieve the development of HTP-value optically active compounds, the ， TP value of these compounds can now reach around # nr1. (2) The present invention specifically refers to the structure of the liquid crystal molecule as part of the new optically active molecule in the design of the molecule, so as to improve the mutual solubility between the new optically active molecule and the nematic liquid crystal. When the novel optically active molecule of the present invention is added to a liquid crystal composition, even when it is added to 30%, no precipitation occurs. (3) The optically active functional group raw material is easy to obtain, and is also a feature of the present invention. The liquid crystal additive of the present invention has optical properties and optical purity, and is often easy to obtain 'and conventionally known liquid crystal additives. Its optically active functional group is better used in the chemical industry. Compared with a large number of raw materials, it can be greatly reduced. (4) The display will be oriented towards the ten-table device. Therefore, the display is required for reflective display for temperature II and outdoor use. The novel optical activity retention and light stability of the present invention are extremely high and have low dependence on temperature. The second son is light stable to liquid crystal formulations. (5) The optical activity of the present invention is very suitable for use in reflective displays. Materials, if the terminal has a reactive south spiral twisting force, and the liquid crystal is added with polymerization reaction, it can be made to have reverse 2 and more applicable to reactive liquid crystals. These films can be applied to reflective polarizing plates ② ": optical films, (6) Conventional Liquid Crystal Additives ^ Production of Color Filters ^

-------- The low twisting torque of the fork is due to 1238186 _ Case No. 91137449_ Year and month correction_ V. Description of the invention (23) This requires a larger amount to be added to the liquid crystal formulation for display to achieve Display performance. The liquid crystal additive of the present invention has a high spiral twisting force, and can be used in traditional transmissive displays (TN, STN, TFT). It can reduce the amount of liquid crystal additive in the entire liquid crystal composition and effectively control the direction of liquid crystal molecule twist. And LCD panel requirements to achieve a reduction in the overall liquid crystal composition and even the price of the panel.

Page 29 1238186 _Case No. 91137449_ Year Month Day _ Amendment

Page 30

Claims (1)

ri ^ rJ Ί238186 \ 十 / Ά ?. Case No. 91137449 [J ^ r Jt Belliming j Day_ Amendment VI. Application for Patent Scope 1. An optically active liquid crystal additive, including the following as shown in formula (I) Organic compound with optically active structure, formula (I) GMX-ZT) m, ZT: Compound in formula (I), where G is an optically active erythritol derivative structure, and optically active arabinol (A rabit ο 1) Derivative structure; 〇 x is II—o—c- or a 疋 〇 II; Ri is argon, i-turbine, alkane-C-10- oxenyloxy and its, hetero, If necessary, each L is not a heterocarbon radical, a sulfur radical, a radical, a dilute radical, a radical, a dilute oxygen radical, or an alkynyl radical, among which the radical, the sulfur radical, the radical, or the alkynyl radical. Radical, alkynyl, alkynyl or alkynyloxy contains 1 to 12 carbon atoms and is a straight chain or branched one, in which more than one hydrogen atom may be replaced by a halogen atom; Z is a cycloalkyl ring group , Cycloalkyl and heterocyclyl with one or more unsaturated bonds, arylheteroaryl, aralkyl, or heteroaralkyl, and wherein the ring atom Hydrogen can be substituted by an alkyl group containing 1 to 12 carbon atoms, an oxygen group containing 1 to 12 carbon atoms, or a halogen atom; η is 1, 2 or 3; if η is 2 or 3, a Z is the same or different ring alkyl group, heterocyclic group, cycloalkyl and heterocyclic group with one or one saturated bond, aryl, heteroaryl, aralkyl or aralkyl, and the ring Atomic hydrogen can be optionally replaced by an alkyl group containing 1 to 12 members, an alkoxy group containing 1 to 12 carbon atoms, or a halogen atom. Page 31 1238186 Case No. 91137449 Amendment VI. Patent application scope generation; in is 1, 2, 3, or 4, if m is 2, 3, or 4, each X is the same or different. Chemical structure, and each Z 'is the same or different corresponding chemical structure. 2. The optically active liquid crystal additive as described in item 1 of the scope of the patent application, wherein G in the compound of formula (I) is the structure of an optically active erythritol (E rythrit ο 1) derivative, selected from The optically active erythritol listed in formula (II). (Erythrit ο 1) derivative structure, and m of the compound of formula (I) is 1, formula (m) _ Among them are independent alkyl, thioalkyl, alkoxy, alkynyl, alkynyl, alkenyl, alkynyloxy, cycloalkyl, heterocyclyl, having one or more unsaturated bonds Cycloalkyl and heterocyclyl, aryl, heteroaryl, arane Page 32 1238186 Case No. 91137449 a Amendment 6. The scope of patent application is heteroarylalkyl, in which alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl or alkynyl contains 1-1 2 carbon atoms, which are straight-chain or branched, and more than one of them can be replaced by a hydrogen atom; of which cycloalkyl, heterocyclyl, one or more unsaturated bonds Cycloalkyl and heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl, the hydrogen on the ring atom can be optionally an alkyl group containing 1 to 12 carbon atoms, containing 1 -1 2 carbon atom alkoxy group 3. If applying for an adduct, in which Erythritol may be substituted by halogen, alkyloxy or alkynyloxy, alkynyl, alkene or branched . 4. If applying for a special substance, where the m of the erythritol alcohol derivative of formula (Erythritol) is 2, the formula (IV) or the nanin atom is substituted. In the biological structure of the optically active erythritol represented by the optically active liquid crystal additive formula (m) described in Item 2, the hydrogen on each carbon atom, if necessary, Alkenyl, alkynyl, and olefin substitution, in which the alkyl, sulfanyl, alkoxy, alkoxy, or alkynyloxy contain 1 to 12 carbon atoms, and are described in the first paragraph of the straight-chain profit range. G in the optically active liquid crystal additive (I) compound is the structure of the optically active erythritol organism, which is selected from the light (Erythrit ο 1) derivative structure listed in formula (IV), and the formula ( I) turn « Page 33 1238186 Case No. 91137449 Amendment VI. Scope of patent application Where R # is alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl, alkynyloxy, cycloalkyl, heterocyclyl, cycloalkane with one or more unsaturated bonds And heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl, in which alkyl, sulfanyl, alkyl, alkynyl, alkyl, alkenyl, or alkynyl 1-1 2 carbon atoms, which are straight-chain or branched, and one or more of the argon atoms may be replaced by halogen atoms; of which cycloalkyl, heterocyclic, and one or more unsaturated bonds Cyclic alkyl groups and heterocyclic groups, aryl groups, heteroaryl groups, aralkyl groups, or heteroaralkyl groups. The hydrogen on the ring atom can be optionally an alkyl group containing 1 to 12 carbon atoms, containing 1 -12 carbon atoms are substituted by alkoxy or i element atoms. 5. The optically active liquid crystal additive as described in item 4 of the scope of the patent application, wherein each carbon in the optically active erythritol (E Γ ythrit ο 1) derivative structure represented by formula (IV) Atomic hydrogen may be substituted by hydrogen, alkyl, sulfanyl, alkynyl, alkenyl, alkynyl, alkenyloxy or alkynyloxy, as required, among which alkyl, sulfanyl, alkoxy , Alkenyl, alkynyl, alkenyloxy or alkynyloxy contains 1-12 carbon atoms and is linear Page 34 1238186 Case No. 91137449 Amendment 6. Scope of patent application or with support key. 6. The optically active liquid crystal additive as described in item 1 of the scope of the patent application, wherein G * in the compound of formula (I) is the structure of an optically active erythritol (Ery 1: hrit ο 1) derivative Is selected from the structure of the optically active erythritol (E rythrit ο 1) derivative listed in formula (V), and the in of the compound of formula (I) is 3, formula (V) _ 7. If applying for a special substance, which can be derivatized by halogen, alkynyl or alkynyloxy, alkynyl, alkenyl or branched in Erythritol. 8. If you apply for a special product, the formula (A rabit ο 1) is derived from the optical activity shown in the optically active liquid crystal additive formula (V) described in item 6 of the range of active arabinol, and erythritol bio In the structure, hydrogen on each carbon atom is optionally substituted by sulfanyl, alkoxy, alkenyl, alkynyl, or alkene, in which alkyl, sulfanyl, alkynyl, alkynyl or The alkynyloxy group contains 1 to 12 carbon atoms, which is the structure of the optically active liquid crystal additive (I) compound described in item 1 of the straight-chain profit range. G is a structure of optically active acacia. The optical (A rabit ο 1) derivative structure listed in formula (W), and formula (I) is combined Page 35 1238186 Case No. 91137449 Amendment 6. Scope of patent application: η is 1 -r2 formula (νπ) where R ^ R is an independent alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl, alkynyloxy, cycloalkyl, heterocyclic group , Cycloalkyl and heterocyclyl with one or more unsaturated bonds, aryl, heteroaryl, aralkyl, or heteroaralkyl, of which alkyl, sulfanyl, alkoxy, and alkenyl , Alkynyl, alkenyloxy or alkynyloxy contain 1 to 12 carbon atoms, are linear or branched, and more than one of them can be replaced by a halogen atom; wherein cycloalkyl, Heterocyclyl, cycloalkyl and heterocyclyl with one or more unsaturated bonds, aryl, heteroaryl, aralkyl, or heteroaralkyl. The hydrogen on the ring atom can be contained as required. -It is substituted by an alkyl group of 12 carbon atoms, an alkoxy group or a prime atom containing 12 carbon atoms. 9. The optically active liquid crystal additive as described in item 8 of the scope of the patent application, wherein in the structure of the optically active arabinyl alcohol (A rabit ο 1) derivative represented by the formula (YU), each carbon atom Argon, if necessary, may be substituted with halogen, alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkenyl, or alkynyloxy, wherein alkyl, sulfanyl, alkoxy, Alkenyl, alkynyl, alkenyloxy or alkynyloxy contains 1 to 12 carbon atoms and is straight chain Page 36 1238186 Case No. 9i 137449 A_Ά said Amendment 6. Scope of patent application or with support key. 10. The optically active liquid crystal additive as described in item 1 of the scope of the patent application, wherein G in the compound of formula (I) is a structure of an optically active arabinol (Arab i to 1) derivative, selected from The structure of the optically active arabinol (Arabit ο 1) derivative listed in formula (M), and m of the compound of formula (I) is 2, Formula (shan) υ v R2 where R # is an alkyl group, a sulfanyl group, an alkoxy group, an alkenyl group, an alkynyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, Or cycloalkyl and heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl with one or more unsaturated bonds, of which alkyl, sulfanyl, alkoxy, alkenyl, alkyne Group, alkenyloxy group or alkynyloxy group contains 1 to 12 carbon atoms, is a straight chain or branched one, and more than one of them can be replaced by a halogen atom; of which cycloalkyl, heterocyclic group , Cycloalkyl and heterocyclyl with one or more unsaturated bonds, aryl \ heteroaryl, aralkyl or heteroaralkyl, the hydrogen on the ring atom can be contained as needed 1-1 2 A carbon atom alkyl group, an alkoxy group containing 1 to 12 carbon atoms, or a halogen atom is substituted. 1 1. Optically active liquid crystal as described in item 10 of the scope of patent application Page 37 1238186 Case No. 91137449 a Amendment 6. Additives in the scope of patent application, where in the structure of the optically active arabinol (Arab i to 1) derivative represented by formula (M), each carbon atom Hydrogen, if necessary, may be substituted with halogen, alkyl, thio, alkoxy, alkynyl, alkynyl, dilute or alkynyloxy, of which alkyl, sulfanyl, alkoxy, alkoxy Alkenyl, alkynyl, alkenyloxy or alkynyloxy contain 1 to 12 carbon atoms and are straight or branched. 1 2. The optically active liquid crystal additive as described in item 1 of the scope of the patent application, wherein G in the compound of formula (I) is the structure of an optically active Arab i to 1 derivative, selected from The structure of the optically active arabinol (Arabit ο 1) derivative listed in formula (IX), and the m of the compound of formula (I) is 3. Formula (IX) is B 1 3. The optically active liquid additive as described in Item 12 of the scope of the patent application, wherein the optically active Arab i nose alcohol derivative structure shown in formula (IX) In the formula, hydrogen on each carbon atom may be substituted by halogen, alkyl, sulfanyl, alkoxy, alkenyl, alkynyl, alkynyl or alkynyloxy, if necessary. Alkyl, alkoxy, alkenyl, alkynyl, alkenyl or alkynyloxy contain 1 to 12 carbon atoms and are straight or branched. 1 4. A method for manufacturing an optically active liquid crystal additive, comprising Page 38 1238186 Case No. 91137449 _ Yue Yue Amendment 6. The scope of the patent application will be optically active erythrit (E rythrit ο 1) alcohol derivatives, Arab i nose alcohol derivatives and formula ( XIV) organic acid compound is subjected to esterification reaction to form an optically active liquid crystal additive according to formula (I) described in item 1 of the scope of the patent application. Formula (xiv) 〇HO where R and Z are defined and formula ( I) are the same; η is 1, 2 or 3; if η is 2 or 3, each Z system is the same or different cycloalkyl, heterocyclyl, cycloalkyl having one or more unsaturated bonds, and Heterocyclyl, aryl, heteroaryl, aralkyl, or heteroaralkyl, and wherein the hydrogen on the ring atom can be optionally an alkyl group containing 1-12 carbon atoms, containing 1 -1 2 carbons Atomic alkoxy or halogen atoms are substituted. 15. A liquid crystal composition comprising at least: (a) 0.5 wt% to 35 wt% of at least one optically active as described in item 1 of the patent application range based on the total weight of the liquid crystal composition. A liquid crystal additive; and (b) 65 to 99.5 wt% liquid crystals based on the total weight of the liquid crystal composition, which is different from the component (a). 16. A liquid crystal composition according to item 15 of the scope of patent application, wherein the t component (a) optically active liquid crystal additive system accounts for 5wt0 / ^ 2 0wt% of the liquid crystal composition. 17. The liquid crystal composition according to item 15 of the scope of patent application, wherein the liquid crystal composition may further include a liquid crystal additive of component (c), and Page 39 1238186 Case No. 91137449 Amendment VI. Scope of Patent Application Part (a) and component (b) are different. 18. The liquid crystal composition according to item 19 of the scope of patent application, wherein the liquid crystal is a twisted nematic (TN) liquid crystal, a super twisted nematic (STN) liquid crystal, or a color super twisted nematic (SSTN) ) Liquid crystal or thin film transistor (TFT) liquid crystal. 19. The optically active liquid crystal additive as described in item 1 of the scope of patent application, which can be used for forming a polarizing plate or a color filter. 20. The optically active liquid additive as described in item 19 of the scope of application for a patent, wherein the polarizing plate is a cholesterol-type reflective polarizing plate. Page 40