TWI300775B - Chiral Compounds II - Google Patents

Description

1300775 A 7 B7 V. INSTRUCTION DESCRIPTION (1) The present invention relates to a palmitic compound, relating to a liquid crystal mixture comprising the pair of palm compounds, relating to a polymerization derived from the pair of palm compounds and 'liquid crystal germanium compounds a mixture of the palm compound and the polymer obtained therefrom in a liquid crystal display, active and passive optical components such as a polarizing plate, a compensator, a calibration layer, a color filter or a hologram element, an adhesive, each having Synthetic resin, cosmetic and pharmaceutical compositions for heterogeneous mechanical properties 'diagnostics, liquid crystal pigments, decorative and anti-counterfeiting applications, nonlinear optical instruments, optical data storage or as a palmitic dopant. The palm compound can act as a dopant to induce or increase the helical twist that can be used in liquid crystal mixtures, for example, in liquid crystal displays. In the first evaluation, the molecular spiral pitch p series, which is the most practical for practical use, is inversely proportional to the palmitic dopant concentration in the main mixture of liquid crystals of formula (1): 0 2 1 P_HTP'c (1) The proportional coefficient is The helical torsional force (HTP) of the palmitic dopant. In many applications, an LC mixture with a torsional phase is desired. Among them are, for example, phase change displays, host and guest displays, passive and active array type TN and STN displays such as AMD-TN, strong inducer displays and cholesterol displays such as SSCT (surface stabilized cholesterol structure) or PSCT (polymer stabilized) Cholesterol structure) displays, including displays having temperature-compensating properties, such as the cholesterol compounds suitably selected in accordance with the present invention, either alone or in combination with other pairs of palmitic dopants. For such applications, it is preferred to have a high HTP for the palm dopant to reduce the dopant-induced paper size for the Chinese National Standard (CNS) A4 specification (210X297 mm) ---- ------- (Please read the notes on the back and fill out this page)

Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives -4- 1300775 A7 B7 V. INSTRUCTIONS (2) The required amount of pitch required. (Please read the notes on the back and fill out this page.) For some applications, it is desirable to have an LC blend with a strong helical twist and therefore a short pitch length. For example, for use in a liquid crystal mixture in a selective reflective cholesteric display such as SSCT or PSCT, the pitch is selected such that the maximum wavelength of the wavelength reflected by the cholesterol helix is in the visible range. Another possible application is for the optical element to use a polymeric film having a palmitic liquid crystalline phase, such as a cholesterol broad spectrum polarizer or a palmitic liquid crystal retardation film. As shown in the formula (1), a high amount of dopant or a dopant having a high HTP can be used to achieve a short pitch. The palmitic compounds are disclosed, for example, in WO 95/16007, W〇 98/00428 and GB 2 328 207 A. However, prior art palm-type dopants have low 値HTP and require high amounts of dopants. Since the palm dopant is only a pure mirror image isomer and is therefore expensive and difficult to synthesize, it is disadvantageous.

In addition, when using high amounts of prior art on palm-type dopants, it often has a negative impact on the properties of the main mixture of liquid crystals, such as, for example, clear points, dielectric anisotropy. ε, viscosity, drive voltage or switching time. Another disadvantage of prior art techniques for palm compounds is that they often exhibit low solubility in the primary mixture of liquid crystals, resulting in undesired crystallization at low temperatures. To overcome this disadvantage, it is generally necessary to add two or more different pairs of palmitic dopants to the primary mixture. This situation implies a higher cost, and the mixture also requires additional temperature compensation because different dopants are selected to compensate for their torsional temperature coefficients. This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) -5- 1300775 A7 _________B7 _ V. Invention description (3) The result 'requires an easy to synthesize, low dosage, temperature stability improvement of cholesterol pitch ( For example, a fixed reflection wavelength is used, a high HTP-to-palm compound that does not affect the properties of the liquid crystal primary mixture and exhibits good solubility in the primary mixture. SUMMARY OF THE INVENTION It is an object of the present invention to provide a palm-like compound having such properties but which does not have the disadvantages of the prior art for palm powder dopants. Another aspect of the present invention expands the range of palm-like compounds that can be used as dopants for experts. It has been found that these objectives can be achieved by providing a palm compound of formula I.

R1-X1-(A1-Z1)mG-(Z2-A2)n-X2-R2 I The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, printing R1 and R2 are F, Π, Br, CN, SCN, SF5 Or a palmitic or non-preferable alkyl group having up to 30 C atoms which may be unsubstituted or mono- or polysubstituted by F, cn, Br or CN, wherein one or more non-adjacent CH2 groups The group may also be _〇_, _s_, -NH-, -C(CH3)-, -C〇-, -C〇〇-, -〇c〇-, _〇c〇-〇·, -S- CO-, -CO-S- ' -CH = CH-, or C- is substituted so that the oxygen atoms are not directly bonded to each other, or the polymerizable group |, X1, X2, Z1 and Z2 are -〇- , -S-, -C0·, the paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -6 - 1300775 A7 B7 V. Invention description (4) -C〇〇-,-0C〇-, -0-C〇〇-, -C〇-N(R3)-,-N(R3)-C〇' -och2-,-ch2〇-, -sch2-, -ch2s-, -cf2o-,-〇 Cf2-, -CF2S-, -SCFr, -CH2CHr, -CF2CHr, -CH2CF2-, (please read the notes on the back and fill out this page) • CF2CF2·*, ~CH=CH-I -CF=CH-, -GH=CF-} -CF=CF-, -C=C-, -CH=CH-COO-, -OCO-CH=GH- or ~One-click, R3 H or an alkyl group having 1 to 4 C atoms. The Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives, printing A1 and A2, each of which is a 1,4-phenylene group in which one or more CH groups can be N. Substituted by 1,4-cyclohexylene, wherein one or more non-adjacent CH2 groups may be replaced by hydrazine and/or S, 1,3-di Df-mer-4,5-diyl, 1,4 -Extension of the ring, 1,4·bicyclo-(2, 2,2)-exetylene, _steep-1,4-diyl, naphthalene_2,6-diyl, decalin-2 , 6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or indane-2,5-diyl, all of which may be unsubstituted, halogen, cyanide a mono- or poly-substituted group or a nitro group, or an alkyl group, an alkoxy group, an alkylcarbonyl group or an alkoxy group having from 丨 to 7 C atoms, wherein one or more of the ruthenium atoms may be substituted by F or C1, m and η are each 〇, 1, 2, 3 or 4, and G is a pair of palmity groups, wherein at least one of X1, X2, Ζ1 and Ζ2 is a c F 2〇1, a 0 CF 2 — 'a CF 2 S one' — SCF 2 — ?

A CF2CH2 -, - CH2CF2 - ? ~~ C F 2 C F - CH = CF -, -CF = CH - or -CF = CF - 另一 Another object of the invention is a liquid crystal mixture containing at least one compound of formula I. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1300775 A7 _ B7 V. Inventive Note (5) Another object of the invention is a polymerizable liquid crystal mixture comprising at least one compound of formula I And at least one polymerizable mesophase-forming compound having at least one polymerizable functional group. Another object of the invention is a palmitic linear or crosslinked liquid crystal polymer which can be prepared by polymerization of a polymerizable liquid crystal mixture comprising one or more compounds of formula I. Another object of the invention is the aforementioned palm compound, mixture or polymer in a liquid crystal display such as STN, TN, AMD-TN, temperature compensation, strong induction, host-type, phase change or surface stabilization or polymerization. Solidified cholesterol structure (SSCT, PSCT) display, active and passive optical components such as polarizers, compensation films, calibration layers, color filters or holograms, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics and pharmaceuticals The composition is used, for example, as a UV filter, diagnostic, liquid crystal pigment, for decorative and anti-counterfeiting applications, in non-linear optical instruments, in optical data storage or as a palmitic dopant. Printed by the Intellectual Property Intelligence Bureau of the Ministry of Economic Affairs, another object of the present invention is a liquid crystal display comprising a liquid crystal mixture or a polymerizable liquid crystal mixture comprising at least one palm compound of the formula I. The invention has several advantages for the palm compound; it has good solubility in the liquid crystal mixture, ♦ it has a wide liquid crystal phase, • can obtain high torsion ability by changing the palm group R1 and/or R2 HTP compound, • When using the compound of the invention as a palmitic dopant in a liquid crystal mixture, the paper size is suitable for the product (CNS) A4 specification (21GX297 mm) -8 - 1300775 A7 B7 V. Description of invention ( 6) Because of its high solubility, a higher amount of dopant can be used to produce a high degree of twist (=low pitch). Please read the back i item and fill out this page. • When high amount of dopant is required, the present invention The wide liquid crystal phase of the dopant 'the liquid crystal phase of the main mixture is less adversely affected'. • If the compound having a high HTP in the present invention requires a lower amount to reach a high pitch, the liquid crystal properties of the mixture are less affected. Negative effects, • The palmitic compound with mirror image purity is easy to prepare from the cheap, easy-to-obtain starting materials. • It can be prepared simultaneously with R and S mirror isomers. The cholesterol phase of the right hand or left hand cholesterol helix, • The presence of two helices is an important advantage, for example, for anti-counterfeiting applications, so that it can produce a circular film or coating with a single hardness and a circular polarized light with a single hardness. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Employees' Consumption Cooperative, which is a mesophase or even liquid crystal, that is, it can induce or increase mesophase behavior, for example, blending with other compounds, or even one or more Intermediate phase. The compound of the present invention may also exhibit mesophase behavior only when it is mixed with other compounds, or if it is a polymerizable compound, it is (co)polymerization. Intermediate Phase The present invention is particularly preferred for palm compounds. The groups R1, R2, X1, X2 and the mesophase groups (ALZ^m and (Α2·Ζ2)η) located on both sides of G may be the same or different. Preferred embodiments of the invention are related to The mesophase groups on both sides are different compounds. Excellent compounds are those in which at least one of Ζ1 and Ζ2 is <1〇-, -〇CF2- '-CF2S-, -SCF2 - or - CF2CF2-. In other preferred compounds, the paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1300775 A7 ______B7_ V. Description of invention (7) At least one of X1 and X2 is -CF2〇- or -OCF2-. In other preferred compounds, at least one of X1, X2, Z1 and Z2 is -CF2〇-, -〇CF2-, -CFaS-, -SCF2-, -CF2CF2- or -CF=CF- Another group is -(:〇〇-, -〇C〇-, -CH2-CH or single bond. Another preferred embodiment relates to wherein at least one of Z1 and Z2 is not - Compounds of C.C.C. These compounds are particularly suitable for applications requiring highly birefringent materials. Other preferred compounds are compounds of formula I wherein the mesophase group (Α^Ζ2:^ & (A, Z2) n series mixed with one or two Or three, especially two five- or six-membered rings. Particularly preferred compounds are those in which m and η are 1 or 2, and A1 and A2 are selected from 1,4-phenyl and trans-1. , 4-cyclohexylene, these rings are unsubstituted or substituted at 1, 4 positions by F, Cl, CN or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group having 1 to 4 C-atoms Substituted. According to these preferred compounds, particularly preferred are those comprising dicyclohexyl or cyclohexylphenyl. Preferred intermediate phase groups of smaller groups (Α^Ζ2) and (Α2-Ζ2)η series For the sake of simplicity, the Phe in these groups is 1,4-phenylene, which may also be substituted with at least one group L, which is F, Cl, CN or, optionally, fluorine. An alkyl group having 1 to 4 C atoms, an alkoxy group, an alkylcarbonyl group or an alkoxycarbonyl group, Cyc is a 1,4-cyclohexylene group, and Z is a definition of Z1 in the formula I. The list of phase groups includes the following formula and its mirror image. The paper size applies to the Chinese National Standard (CNS) A4 specification (21〇X29*7 mm). Please read the note on the back first.

Page Economy Ministry Intellectual Property Bureau Staff Consumer Cooperative Printed -10- 1300775 A7 B7 V. Invention Description (8) -2 -3 -4 -5 -6 -7 -8 -9 -10 •11 -Phe--Cyc- Please read the precautions on the back and fill in this - Phe-Z-Phe--Phe-Z-Cyc--Cyc-Z-Cyo-Phe-Z-Phe-Z-Phe--Phe-Z-Phe-Z- Cyc--Phe-Z-Cyc-Z-Phe--Cyc-Z-Phe-Z-Cyc--Cyc-Z-Cyc-Z-Phe--Cyc-Z-Cyc-Z-Cyc- The auxiliary forms II-3, Π-4, II-5, II-6, II-7 and 11-10' are especially II-4 and II-5. Other preferred are π·5, wherein lanthanide is -CF2CF2_, and auxiliaries II-3 and II-4, wherein Z is -CF2-. The Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives, print the other preferred ones as the auxiliary π_10 and 11-11 'where one or two of the two Ζ between the two 环 己 is -CF2CF2- 'and the auxiliary ΙΙ- 6. ΙΙ-7, 11-8, II-9 and 11-10, wherein one or two Z series between the two exfoliated benzene rings or between a stretched phenyl ring and a stretched ring ring are -0CF2 - or -CF2〇-, and the ruthenium atom is adjacent to the benzene ring. The other group Z is preferably -C00-, -0C0-, -CH2CH2- or a single bond. Preferably, the bicyclic and tricyclic mesophase groups are preferred. Other preferred compounds wherein the mesophase group comprises at least one group Phe, which is substituted by one or two groups L, preferably at the 3- and/or 5-position, and the L system is F, C 1 , CH3, 〇CH3, CF3, CHF2, CH2F, this paper scale applies to Chinese National Standard (CNS) A4 specification i210X297 mm) " — -11- 1300775 A7 B7 V. Invention description (9) 〇CF 3 ( :)CHF 2, 〇C Η 2 F or CN. L is preferably F, C 1 , C Ν, Ν 〇 2, C Η 3, C 2 Η 5 5 〇C Η 3, 〇C 2 Η 5 C〇C Η 3, C 〇C 2 Η 5 , CF 3 CHF 2,C Η 2 F 9 〇CF 3 0 CHF 2 ,〇C Η 2 F, 〇C 2 F 5 , especially F \ C 1 ' C Ν, C Η 3 , C 2 Η 5 ' 〇C Η 3, CF 3 and 〇CF 3, the best system is F, C Η 3 , CF 3 , 〇C Η 3 and 〇CF 3 〇 If R1 or R 2 in formula I is a hospital or a hospital oxygen, ie Wherein the terminal CH2 group is replaced by -0 - 5 of this: it may be a straight chain or a branched chain. It is preferably a straight chain having 2, 3, 4, 5 6, 或 or 8 carbon atoms, and thus is preferably ethyl, propyl, butylpentyl, hexyl, heptyl, octyl or ethoxy. a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group or an octyloxy group, and others having, for example, a methyl group, an alkyl group, a '-* group', a dodecyl group, a thirteen group ( Please read the notes on the back and fill out this page. Install and re-fill the Ministry of Commerce, Intellectual Property Bureau, Consumers' Cooperatives, 14th base, fifteen base, decyloxy, decyloxy, undecyl, ten Dioxy, trideoxy or tetradecyloxy. Oxaalkyl, i.e., wherein one CH2 group is replaced by -〇-, preferably such as linear 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or -oxobutyl 2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4- , 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6·, 7- Or 8-oxaindolyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxaindolyl. Halogen is preferably F or C1. R1 or R2 in formula I may be a polar or non-polar group. If it is a polar group, shell [J series is selected from CN, SF5, halogen, 〇CH3, SCN, COR5, C〇〇R5. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ' -12- 1300775 A7 B7 V. INSTRUCTIONS (10) or mono-oligo- or multi-gasification or 1-epoxy groups having 1 to 4 C atoms. R is optionally a fluorinated alkyl group having from 1 to 4, preferably from 1 to 3, C atoms. The particularly preferred polar group is selected from the group consisting of F, C 1 , CN, 〇C Η 3, c〇ch3, c〇c2h5, c〇〇ch3' c〇〇c2h5 , CF3, CHF2, CH2F, 〇CF3' OCHF2, 0 CH 2 F , C2F5 and 〇C2F5 and especially F, C 1 , CN, CFs, 〇CHF2 and 〇CF3. In the case of a non-polar group, R1 or R2 is preferably an alkyl group having up to 15 C atoms or an alkoxy group having 2 to 15 C atoms. R1 or R2 in formula I may be a non-preferential or palmitic group. If it is a palm group, it is preferably selected from the group III: _Q1-C Bu Q2 I , Q3

III wherein Q1 is a stretching group having 1 to 9 C atoms or an exomethoxy or single bond Q2 is an alkyl or alkoxy group having 1 to 10 C atoms, which may be unsubstituted or F, Cl, Br or CN may be mono- or polysubstituted, and one or more non-adjacent ch2 groups may also be individually _Ce C-, -〇·, _Hong, _N(CH3)-, -C〇-, - COO-, ·〇(:〇·, _〇C〇-〇-, _S_C〇_^ -C〇-S- are substituted so that oxygen atoms are not directly bonded to each other, and Q3 is F, Cl, Br, CN Or an alkyl or alkoxy group as defined in Q2, this paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and _ matters and fill in the page) Property Bureau Staff Consumer Cooperative Printed 13-1300775 A7 B7 V. Invention Note (11) But different from Q2. If Q1 in Formula III is an alkoxy group, the ruthenium atom is preferably a pair of palm atoms. Preferably, the palm of the formula III is 2-alkyl, 2-alkoxy, 2-methylalkyl, 2-methylalkoxy, 2-fluoroalkyl, 2-fluoroalkane. Oxyl, 2-(2-acetylene)-alkyl, 2-(2-acetylene)-alkoxy, 1,1,1-trifluoro-2-alkane And 1,1,1-trifluoro-2-alkoxy. A particularly preferred pair of palmitic groups are, for example, 2-butyl (=methylpropyl), 2-methylbutyl, 2-methyl Pentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, especially 2-methylbutyl, 2-methylbutoxy, 2-methylpentyloxy, 3- Methylpentyloxy, 2-ethylhexyloxy, 1-decylhexyloxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl , 4-mercaptohexyl, 2-hexyl, 2-octyl ' 2-indenyl, 2-indenyl, 2-dodecyyl, 6-methoxyoctyloxy, 6-methyloctyloxy, 6-Methyloctyloxy, 5-methylheptyloxycarbonyl, 2-methylbutanoxy, 3-methylpentyloxy, 4-methylhexyloxy, 2-chloropropoxy , 2-chloro-3-methylbutanoxy, 2-chloro-4-methylpentanyloxy, 2-chloro-3-methylpentyloxy, 2-methyl-3-oxa Pentyl, 2-methyl-3-oxahexyl, 1-methoxyprop-2-oxy, ethoxypropyl-2-oxy, 1-propoxyprop-2-oxy, 1-butyl Oxypropan-2-oxy, 2--octyloxy, 2-M-decyloxy, 1,1,1-difluoro-2-octyloxy, 1,1, trifluoro-2-octyl, 2-fluoromethyloctyloxy. Preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1 -Trifluoro-2-octyloxy. In addition, compounds containing a non-p-branched branched chain group R1 or R2 may be incidentally of importance because of, for example, a reduced tendency to crystallize. This type of paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm 1 ~" -14 - (please read the back note before you write this page). Install the Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 1300775 A 7 ____B7_ V. INSTRUCTIONS (12) Branching groups usually do not contain more than one chain branch. Preferred non-preferable groups are isopropyl and isobutyl (=methyl Propyl), isopentyl (=3-methylbutyl), isopropoxy, 2-methylpropoxy and 3-methylbutoxy. In another preferred embodiment, the formula I R1 and/or R2 represents a polymerizable group P-Sp-' 八P % M ch2=cw-co〇., wch=ch-o-, whc-ch- or CH2 = CH·phenyl·(〇 ), _, w is H, CH3 or Cl, k is 0 or 1, and

Sp is a spacer having 1 to 25 c atoms, or a single bond. P is preferably a vinyl group, an acrylate group, a methacrylate group, an propylene group or an epoxy group, especially an acrylate or methacrylate group. As far as the spacer Sp is concerned, it is known to those skilled in the art that all groups which are in such a situation can be used. The spacer Sp is preferably a linear or branched alkyl group having 1 to 20 C atoms, especially 1 to 12 C atoms, wherein one or more non-adjacent CH 2 groups may additionally pass - O-'-S-'-NH-, -N(CH3)·, -C〇-, -〇-C〇-, -S-CO-, -〇-C〇〇-, -CO-S-, -C〇-〇-, -CH(halogen)-, -CH(CN)-, -CH=CH- or -C tri-C-substituted o The general spacer system is, for example, -(CH2)P-, -( CH2CH2〇)r-CH2CH2-, -CH2CH2-S-CH2CH2- or -CH2CH2-NH-CH2CH2-, p is an integer from 2 to 12, and r is an integer from 1 to 3. Preferred spacers are, for example, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, thiol, thiol National Standard (CNS) A4 Specification (21〇><297 mm) Please read the notes on the back first. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Co., Ltd. 15 Q1 Q2 1300775 A7 B7 V. Invention Description (13) Base, extended dodecyl, extended octyl, extended ethyloxyethyl, methyleneoxybutyl, ethyl ethyl-thioethyl, ethyl-N-methylimidoethyl , 1-methylalkylene, vinyl, propylene, and butenyl. Particularly preferred is the palmitic compound of the formula I of the present invention, wherein the Sp system represents an alkyl group or alkoxy group having 2 to 6 C atoms. Linear alkyl or alkoxy is particularly preferred. In another preferred embodiment of the present invention, the palm compound comprises at least one spacer Sp which is a pair of palm groups of formula IV: -Q1-CH-Q2 wherein there are 1 to 10 The alkyl or alkyl-oxy group or single bond of the c atom is an alkyl group having 1 to 10 c atoms or an alkyl-oxy group or a single bond, which is different from Q1 and is halogen. A cyano group or an alkyl or alkoxy group having from 1 to 4 C atoms and different from Q2. If Q1 in the formula IV is an alkylene-oxy group, the ruthenium atom is preferably adjacent to the palmitic C atom. Preferably, it is a palm-derived divalent group derived from a sugar, a binaphthyl derivative, or an optically active diol, especially an ethane-1,2-diol, which has a 1- or 2-position alkyl group. Or substituted with an aryl group. If it is a glycosyl group, these are preferably selected from the standard of the paper. The Chinese National Standard (CNS) A4 specification (210X29*7 mm) Please read the notes on the back and write this page again. Q3 Ministry of Economic Affairs Intellectual Property Bureau Employee Consumption Cooperative Printed-16- 1300775 A7 B7 V. Invention Description (14)

Mono- and bicyclic groups including pentose or hexose rings. Particularly preferred are the following groups G -0 > Λ R - 〇

Phe FT 〇一 Phe P一 Phe 〇一 Phe 〇一 > » » ^ Ο. \ 〇 \ 〇 \ 〇

(Please read the precautions on the back and fill out this page): Installation · Booking Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -0

0 — 0— wherein Phe has the definition as defined above, R 4 is F or an alkyl group having 1 to 4 C atoms fluorinated as appropriate, and Y 1 , Y 2 , Y 3 and Y 4 have the definition of R 1 in formula I one. Preferably, the G system is a dianhydrohexitol such as hydrazine - 0 sorbitan water mannitol, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 1300775 A7 B7 V. Invention Description (15) Η

Η dehydrated imidacol, especially sorbitan, substituted ethanediol

The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, prints the R4 series as F, CH3 or CF: or as appropriate, the substituted naphthyl groups, wherein Y1, Y2, Y3 and Y4 are fluorene, F or, as the case may be, fluorinated and have An alkyl group of 1 to 8 C atoms. The best compound of formula I is as follows: This paper scale applies to China National Standard (CNS) Α4 specification (210Χ297 mm) -18- 1300775 A7 B7 V. Invention description (16) r〇cf2°-〇- coo

1-1

OOC-<\ /hOCFr >-~R

R-< Vcfxf2h —c〇〇

I-2 〇〇c ~0^cf0^r <y

RK VCFXF. COO

卜3 〇〇c 〇CF K> (Please read the notes on the back and fill out this page) - Install · Order

This paper scale applies to China National Standard (CNS) Α4 specification (210X297 mm) Μ -19- 1300775 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -20- 1300775 A7 B7 V. Inventive Note (18) where R has one of the definitions of R1 in Formula I, or the aforementioned preferred definition, and the piano The 1,4-phenylene ring may also be mono- or poly-substituted by L as described above. The palmitic compounds of the present invention can be synthesized according to or as in the following reaction schemes. Flowchart 1 Please read the back of the note first r-〇-

COOH a

Cf3s〇3-items

COOH

R propane dithiol, CF3S〇3H·toluene/isooctanol; water separator 1 · ethyl 4-hydroxybenzoate, · NEt3, CH2C12; -78 ° C; 2 · NEt3 3HF; 3 · NBS; °C to RT; 4 · K〇H, H2〇, Et〇H Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed r-^)"cf2〇~0~ r/^cf.o 1,4:3, 6-Dihydrohexitol, such as sorbitol, DCC, Flow Chart 2 This paper scale applies to China National Standard (CNS) A4 specification (210'乂297 mm) 21 1300775 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed

1300775 A7 _B7_____ — V. Description of invention (20)

a) H2, 5% Rh-C, isopropanol b) chlorochromic acid pyridine gun, CH2Cl2 c) 2,2-dimethyl-1,3-propane, cyclohexane, H2S〇4 d) 1 · bromine pentyl-PPh3, potassium t-butoxide, THF; 2 · H2 'Pd-C 'THF e) HC〇〇H, toluene f) methoxymethyl-PPh; potassium t-butoxide, THF g ) 1 · HCOOH, toluene; 2 · NaOH, methanol (isomerization) h) H2Cr〇4, acetone, isopropanol i) 1,4:3,6-dianhydrohexitol, such as sorbitol , DCC, CH2CI2 The novel ketamine economic department with the following formula is printed by the Intellectual Property Bureau employee consumption cooperatives as an intermediate compound, especially for the preparation of liquid crystal compounds. The ketal and its preparation are another object of the present invention. The ketal is preferably a bis-(4-hydroxyl ring) formed by hydrogenation of 1,2-bis(4-hydroxyphenyl)_1,1,2,2-tetrafluoroethane as described above. The hexyl compound is oxidized using a strong acid, especially a chromium (VI) derivative, particularly a chlorochromic acid pyridine key (PCC), which forms a bisketal with 2,2-dimethylpropane in the presence of an acid, especially sulfuric acid. Prepared by reacting. The paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -23- 1300775 A7 B7 V. Invention description (21) Flowchart 3 r-〇-

C〇〇H

Cf3so3·

C〇〇H R-

R a ) propane dithiol, CH 3 S 〇 3H, toluene / isooctanol; 7jc separator b) 1 · 4-hydroxybenzoic acid ethyl ester, NEt3, CH 2 Ch; -78 QC ; 2 · NEt: 3HF; 3 · NBS; -78〇C to RT;4 · K〇H,H2〇,Et〇H c )Phenylethanediol,DCC,CH2Cl2 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Paper Size Applicable to China National Standard (CNS A4 size (210X297 mm) -24- 1300775 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -25- 1300775 A7 B7 V. Description of invention (23)

a ) 1 · HS(CH2)3SH; 2 · CF3S〇3H, △ (Please read the notes on the back first\^Write this page) Pack· b ) 1 · NEt3, CH2C12, -78°C; 2 · NEt3 · 3HF; 3 · N-bromobutaneimine

A, B = cyclohexyl, phenyl, n = 0, 1, 2, 3; R = Cu. Alkyl J1·4: Η, F Other methods of preparing the compounds of the present invention are known from the Examples. The palm compound of the present invention can be used in a liquid crystal mixture for use in a display having a twisted molecular structure of a liquid crystal matrix, such as, for example, a super-twist or active array type liquid crystal display, or in a display including a liquid crystal mixture having a liquid crystal phase. For example, a palmitic smectic phase or a palmitic nematic phase (cholesterol) mixture for use in a strong electrical display or a cholesterol display. Therefore, another object of the present invention is a liquid crystal mixture, especially a cholesteric liquid crystal mixture, comprising At least one formula of the formula I of the formula I applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -26- 1300775 A7 ___B7_____ V. Invention Description (24) Another object of the present invention is a cholesteric liquid crystal display comprising a cholesteric liquid crystal medium containing at least one type of palm Compound. One feature of the invention is the high solubility in the primary mixture of liquid crystals. Therefore, it can be added to a liquid crystal main substance in a high amount as a doping agent without greatly affecting the phase behavior and photoelectric properties of the mixture. In addition, undesirable spontaneous crystallization at low temperatures is reduced and the operating temperature range of the mixture is broadened. Moreover, the palmitic compounds of the present invention having a low HTP enthalpy can be used to prepare highly twisted liquid crystal media because the dopant concentration can be increased to produce low pitch enthalpy (i.e., high twist) without affecting the properties of the mixture. Therefore, it is possible to avoid the use of a second dopant which is often added to avoid crystallization. In addition, many of the palmitic compounds of Formula I of the present invention have high HTP値. Thus, a liquid crystal mixture having a high helical twist--i.e., a low pitch can be prepared using the compound of the present invention, or a low amount of the compound of the present invention can be used as a dopant' to achieve a liquid crystal mixture having an appropriate helical twist. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, the high HTP of the compounds of the present invention is also suitable for use in combination with other compounds to provide temperature compensation for properties of liquid crystal mixtures such as cholesterol pitch and properties of the display such as, for example, threshold voltage. As mentioned above, another advantage of the compounds of the invention is that they have a very slight effect on the physical properties of the liquid crystal mixture. Therefore, when the palm compound of the formula I is incorporated into a liquid crystal mixture having positive dielectric anisotropy, for example, for use in a liquid crystal display, Δ ε is only slightly lowered, and the viscosity of the liquid crystal mixture is only slightly increased. This condition leads to the application of the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) to the paper scale. -27 - 1300775 A7 B7 V. Description of invention (25) Lower voltage, and in combination with customary dopants Improve display switching time when the display is compared. The liquid crystal mixture of the present invention comprises preferably from 0.1 to 30% by weight, particularly from 1 to 25% by weight, particularly from 2 to 15% by weight, of the formula I for the palm compound. The liquid crystal mixture of the present invention is preferably a compound of the formula 1 to 3 of the formula I. For the temperature compensation applications described above, the liquid crystal mixture preferably comprises a pair of palm components comprising at least one palm compound of formula I, and a collinear component comprising one or more nematics A phase or nematic phase-generating compound. In a preferred embodiment of the invention, the liquid crystal mixture is comprised of from 2 to 25, preferably from 3 to 15, compounds, at least one of which is a palmitic compound of formula I. The other compound forming the nematic component is preferably a low molecular weight liquid crystal compound selected from a nematic or nematic phase-generating material such as known azobenzene, benzylidene-aniline, biphenyl, lignin. Benzene, phenyl benzoate or cyclohexyl ester, phenyl ester or cyclohexyl ester of cyclohexanecarboxylic acid, phenyl ester or cyclohexyl cyclohexylbenzoic acid, phenyl ester or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid , benzoic acid, cyclohexanecarboxylic acid, cyclohexylphenyl cyclohexylcyclohexanecarboxylic acid, phenylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane, cyclohexylcyclohexane, cyclohexyl Cyclohexane, cyclohexylcyclohexylcyclohexane, 1' 4-bis-cyclohexylbenzene, 4,4'-bis-cyclohexylbiphenyl, phenyl- or cyclohexylpyrimidine, phenyl- or cyclohexylpyridine, Phenyl- or cyclohexyl morphine, phenyl- or cyclohexyldioxane, phenyl- or cyclohexyl-1,3-1,4-thiazide, 1 ' 2 -—^---- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back - write this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs -28- 1300775 A7 B7 V. INSTRUCTIONS (26) Dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethane, 1 · cyclohexyl-2-biphenyl-ethane, 1-phenyl-2-cyclohexyl-phenylethane, optionally halogenated hydrazine, benzylphenyl ether, diphenylacetylene, substituted cinnamic acid And other types of nematic or nematic material. The 1,4-phenylene group in such compounds may also be mono- or difluorinated laterally. Preferred liquid crystal mixtures of the specific examples are mainly such non-preferable compounds. The most important compound that can be used as a component of such liquid crystal mixtures can be represented by the following formula: R, -L, -G, -E-Rn Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer consortium, where L' and E can be the same or different. Individual is a divalent group formed by -Phe_, Cyc-, -Phe-Phe-'Phe-Cyc-, Cyc_Cyc_, -Pyr_, -Dio-, -B-Phe-, and -B-Cyc-, and A mirror image in which Phe is unsubstituted or fluorinated 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenyl, and Pyr is Pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dicrosin-2,5-diyl, and B is 2-(trans-1,4- Cyclohexyl)ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl. The G' in these compounds is selected from the following divalent groups -CH=CH-, -N(〇)N-, -CH=CY-, -CH=N(〇)·, -C 三C-, -CH2-CH2-, -C〇-〇-, -CH2-〇-, -C〇-S·, -CH2-S-, -CH = N-, -C〇〇-Phe-C〇〇- or Single bond, Y is halogen, preferably chlorine, or -CN. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -29- 1300775 A7 B7 V. Invention description (27) Please read the notes on the back first 1 Salty 2% loading 11' and RM individual system Is an alkyl, alkenyl, alkoxy, alkenyloxy, decyloxy, alkoxycarbonyl or alkoxycarbonyloxy group having from 1 to 18, preferably from 3 to 12, C atoms, or R' and R" One of them is F, CF3, OCF3, C1, NCS or CN. In most of these compounds, R' and R" are each an alkyl, alkenyl or alkoxy group having a different chain length, wherein the nematic The sum of the C atoms in the medium is usually between 2 and 9, preferably between 2 and 7. Many such compounds or mixtures thereof are commercially available. All such compounds are either known or can be prepared by known methods, as described in the literature (e.g., standard publications such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag:

Stuttgart) is carried out under the reaction conditions known and suitable for the reaction. In this case, a known method, but not described herein, may also be used. The compounds of the invention are particularly useful for use in cholesterol displays such as, for example, phase change displays or surface stabilized or polymer stabilized cholesterol structure displays (SSCT, PSCT), and low molecular weight or polymerizable. Or a mixture of cholesteric liquid crystals. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives. A particularly preferred embodiment of the present invention relates to a palmitic compound that exhibits low HTP temperature dependence in a nematic liquid crystal mixture. These compounds can be used in cholesteric liquid crystal mixtures and displays where the temperature dependence of the reflection wavelength (1λ / dT (T = temperature, λ = maximum reflection wavelength 値) is low. In particular, the use of the formula I is found in cholesteric liquid crystal media. For palm compounds, for example, when applied to SSCT or PSCT displays, it has good solubility in the main mixture of the nematic and induces low temperature. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 PCT) -30- 1300775 A7 B7 V. INSTRUCTIONS (28) Please read the precautions on the back and then the high pitch of the pitch and reflection wavelength of the page. Therefore, even if only one type I is used. The dopant can still achieve a mixture of cholesterol with high reflective color brightness and low temperature dependence, preferably at a low level. This is far superior to prior artists who require high amounts of dopants, which are often used by prior art practitioners. Two or more helically twisted dopants with opposite temperature dependence (eg one with positive temperature dependence and one with negative Degree dependence) to achieve good reflection wavelength temperature compensation. Therefore, a particularly preferred embodiment of the present invention relates to a cholesteric liquid crystal medium, particularly for use in SSCT and PSCT displays, including a palm-like compound of formula I, in an amount Preferably, 15% or less, especially 10% or less, especially 5% or less. Another preferred embodiment relates to a palm of the invention having a high temperature dependence in a nematic liquid crystal mixture. Compounds, which can be used in thermochromic media. Cholesterol display systems are described, for example, in WO 92/19695, W〇93/23496, US 5,453,863 or US 5,493,430, the entire disclosure of which is incorporated herein by reference. This document is incorporated by reference in its entirety. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. In addition, anisotropic polymer gels and displays, including the other, are disclosed in, for example, DE 195 04 224 and GB 2 279 659. SSC and PSCT displays including the compounds of the present invention were found to be sold with conventional dopants such as R 811 or CB 15-Merck KgaA (Darmstadt, Germany) In comparison, there is a shortened response time, a lower voltage, and a modified contrast ratio. For example, SSCT and PSCT displays... where the conventional dopant is replaced by the palm compound of the present invention - it is suitable for displaying a shorter paper scale. China National Standard (CNS) Α4 Specifications (210Χ297 mm) -31 - 1300775 A7 B7 V. INSTRUCTIONS (29) Switching time. Improvement of cholesterol film dopants prepared by replacing the prior art dopants with the compounds of the present invention. Brightness produces a better contrast between the color plane structure and the almost transparent focus cone state that is blacked out using a black back panel

The palmitic compound and the polymerizable liquid crystal mixture comprising the same are also particularly suitable for preparing an anisotropic polymer film having a palmitic liquid crystal phase, such as cholesterol or a palmitic nematic polymer film, especially having uniformity. A planarly oriented spiral twisted molecular structure film, i.e., wherein the helical axis is oriented perpendicular to the plane of the film. For example, oriented cholesterol polymers can be used as wide-band reflective polarizers, as described, for example, in EP 0 606 940, as color filters for security marking, or for use in preparing liquid crystal pigments. Heynderickx and D.J.

Broer, Mol. Cryst, Liq. Cryst. 203, 1 1 3- 1 26 (1 99 1) describes a crosslinked cholesterol polymer film made from liquid crystal dipropionate and containing a low molecular weight palm A dopant. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, it has been found that the cholesterol polymer film produced by using the palm compound of the present invention is more than the prior art dopant such as the above-mentioned R 8 11 or CB 15 film. When preparing an anisotropic polymer gel or an oriented polymer film, the liquid crystal mixture should comprise at least one polymerizable compound in addition to the palm compound of formula I, preferably a polymerizable mesophase-forming compound. 〇 Therefore, another object of the present invention is a polymerizable liquid crystal mixture. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 Gongdong-32-1300775 A7 B7. 5. Invention Description (3〇) Contains at least one formula A palmitic compound of I, and at least one polymerizable mesophase-forming compound. Examples of suitable polymerizable mesophase-forming compounds which can be used as a component of the polymerizable CLC material are disclosed, for example, in WO 93/22397; 0,261,712; DE 195,04,224; W〇95/22586 and W〇9 7/00600. However, the compounds disclosed in these documents are to be considered as examples only and not to limit the scope of the invention. Preferably, the polymerisable CLC mixture comprises at least one polymerizable mesophase-forming compound having one polymerizable functional group, and at least one polymerizable group having two or more polymerizable functional groups. Mesophase-forming compounds. Examples of single-reaction-to-palm and non-palphalinic polymerizable mesophase-forming compounds that can be used in particular are shown in the following list of compounds, however, they are intended to be illustrative, not limiting. Used to illustrate the invention: p-(ch2)x〇000 (Va) Please read the note on the back first

\ ρ-(〇η2)χ〇 coo

(Vb) Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed p-(CH2)x〇 COO Private Worker R1 p-(ch2)x〇 coo

(Vc) (Vd) This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -33- 1300775 A7 B7 V. Description of invention (31) P-(CH2)x〇ο- CH=CH — C 〇〇

Ru (Ve)

(Vf) (Vg) (Vh) (Please read the note on the back and fill out this page), install P-(CH2)x〇Pu COO-Ter (Vi)

P-(CH2)xO COO-Chol (Vk) P-(CH2)x〇 -o-

C〇CT (Vm) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

Wherein p has the above definition, X is an integer from i to 12, A and D are 1,4-phenylene or 1,4-cyclohexylene, v is 0 or 1, and lanthanide is polar a group, V is a non-polar alkyl or alkoxy group, Ter is an alkenyl group, such as a capping group, Choi is a cholesteryl group, and L1 and L2 are Η, F, Cl, CN, OH. And NCh or an alkyl group, an alkoxy group or a carbonyl group having 1 to 7 C atoms, optionally halogenated. The polar group YQ is preferably CN, Ν〇2, halogen, 〇CH3, 0CN, SCN, COR5, C00R5 or mono-, oligo- or polyfluorinated with 1 to 4 C paper scales applicable to Chinese national standards (CNS) A4 size (210X297 mm) -34 1300775 A/ B7 V. Description of invention (32) Alkyl or alkoxy. R5 is an alkyl group having from 1 to 4, preferably from 1 to 3, C atoms, optionally fluorinated. The particularly preferred polar group is selected from the group consisting of F, C1, CN, N〇2, 〇CH3, C〇CH3, c〇c2h5, c〇〇ch3, c〇〇c2h5, cf3, C2F5, OCFs, 〇CHF2, and 〇 C2F5, especially f, C1, CN, 〇CH3 and 〇CF3. The nonpolar group V is preferably an alkyl group having one or more, preferably 1 to 15 C atoms, or an alkoxy group having two or more, preferably 2 to 15 C atoms. Examples of the reactive compounds that can be used in the palm and non-palphalinic polymerizable mesophases are shown in the following list of compounds, however, they are intended to be illustrative, not limiting, to illustrate the invention. . Please read the note first.

Raise P(CH2)x〇 coo

Oco

Or

〇(CH2)yP (Via) P(CH2)x〇

CH2CH2nQ^〇(CH2)yP L1' (Vlb) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs

> OC02 02c 0 - (Vic) p(ch2)x〇

Or CH=CHC〇〇, f 〇

0 i ,

〇〇CCH=CH -0-°Wv (Vld) This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) 35 1300775 A7 B7 V. Invention description (33) p(ch2)x〇

HO

0(ch2)v (Vie) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed P, X, D, L1 and L2 with the above definition, and y is an integer from 1 to 12, the same as X or Different. The polymerizable CLc material of the first preferred embodiment comprises one or more pairs of doped dopants, which themselves do not necessarily exhibit a liquid crystal phase, which in itself produces good planar alignment, especially non-polymerizable versus palm doping. Agent. The mono- and difunctional polymerizable mesophase-forming compounds of the above formulae V and VI can be prepared by known methods and are described in the aforementioned documents, for example, standard publications of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme - Verlag, Stuttgart ° In a preferred embodiment of the invention, the polymerizable liquid crystal mixture comprises at least one of the palmitic compounds of the invention, at least one monofunctional compound of the formula Va-Vm, and at least one of the formulas Via-Vie Functional group polymerizable compound. In another preferred embodiment, the polymerizable liquid crystal mixture comprises at least one of the palmitic compounds of the present invention, and at least two monofunctional compounds of the formula Va-Vm. Another object of the present invention is to apply a Chinese National Standard (CNS) A4 specification (21〇><297 mm) -36-1300775 A7 __B7_ for a paper scale having a directional liquid crystal phase. (34) an anisotropic polymer film which can be selected from the group consisting of Formulas Va-Vm and Vla-VIe and/or by containing at least one of the palm-forming compound of Formula I and at least one polymerizable mesophase-forming compound. Or at least one polymerizable formula of the formula I is obtained by (co)polymerizing a liquid crystal mixture of the palm compound. When an anisotropic polymer film is prepared using a uniformly oriented palmitic liquid crystal phase, the liquid crystal mixture of the present invention is, for example, coated on a substrate, calibrated and polymerized in situ by exposure to heat or actinic radiation. . Calibration and curing are preferably carried out in the liquid crystal phase of the liquid crystal mixture. Actinic radiation means irradiating light such as UV light, IR light or visible light, illuminating X-rays or r-rays, or irradiating high energy particles such as ions or electrons. Sources of actinic radiation can use, for example, a single UV lamp or a UV lamp set. Other possible sources of actinic radiation are lasers such as, for example, UV lasers, IR lasers or visible light lasers. For example, when polymerization is carried out using UV light, a photoinitiator which is decomposed under υν radiation to generate radicals or ions which initiate the polymerization can be used. It is also possible to use a cationic photosensitive photoinitiator which is photo-cured by a cation, rather than by a radical, when a reactive mesophase former is cured using, for example, a vinyl group and an epoxy-based reactive group. For the photoinitiator used in the radical polymerization, for example, commercially available Irgacure 651, Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG) can be used, and if cationic photopolymerization is used, commercially available UVI 6974 (Union Carbide) can be used. The polymerizable liquid crystal mixture comprising the polymerizable palmitic compound of formula I and/or the polymerizable mesophase forming compound of formula V and VI is preferably in accordance with the Chinese National Standard (CNS) A4 specification (210X297 public).厘) (Please read the note on the back and fill out this page) Fill in the book - Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Print -37- 1300775 A7 B7 V. Invention Description (35) Containing 0.01 to 10% by weight, In particular, from 0.05 to 8 weight percent, in particular from 0.1 to 5% by weight, of a photosensitive starter, in particular a UV-photosensitive starter. In a preferred embodiment of the invention, the polymerization of the polymerizable mesophase-forming material is carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere. For the substrate, for example, a glass or quartz plate, and a plastic film or sheet can be used. The second substrate can also be placed on top of the coated mixture before, during and/or after polymerization. The substrate is removed or not removed after polymerization. When two substrates are used for curing by actinic radiation, at least one of the substrates needs to be allowed to penetrate the actinic radiation used in the polymerization. An isotropic or birefringent substrate can be used. If the substrate is removed from the polymerized film after polymerization, it is preferred to use an isotropic substrate. Preferably, at least one of the substrates is a plastic substrate such as, for example, a polyester film such as polyethylene terephthalate (PET), polyvinyl alcohol (PVA), polycarbonate (PC) or triethyl fluorenyl cellulose (TAC). ), especially PET film or TAC film. As the birefringent substrate, for example, a uniaxially stretched plastic film can be used. For example, PET film is available from ICI Corp. under the trademark Melinex. In a preferred embodiment of the invention, the inventive mixture comprising the polymerizable liquid crystal mixture of the palmitic compound of Formula I is applied as a thin layer on or between the substrates, preferably in the form of a palmitic intermediate phase. Lower calibration, such as cholesterol or palmitic smectic phase, produces a planar orientation, even if the molecular helix axis is oriented transversely to the layer. Planar orientation can be achieved, for example, by shearing the mixture, for example using a doctor blade. The calibration layer may also be applied on the top layer of at least one of the substrates, for example, the Chinese National Standard (CNS) A4 specification (210X297 mm) on the paper scale. Please read the back surface first.

Page Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -38- 1300775 A7 B7 V. INSTRUCTIONS (36) Rubbed polyimine or sputtered Si〇x layer. In another preferred embodiment, the second substrate is placed on top of the coated material. In this case, the shear produced by combining the two substrates is sufficient to produce a good calibration. An electric or magnetic field can also be applied to the applied mixture. In some cases, it is preferred that the application of the second substrate not only aids in the calibration of the polymerizable mixture, but also excludes oxygen which may hinder polymerization. Or the curing can be carried out under an inert gas atmosphere. However, curing in air can also use suitable sensitizing initiators and high lamp energies. When a cationic photoinitiator is used, it is usually not necessary to exclude oxygen, but water should be excluded. A detailed description of the in-situ polymerization of the polymerizable mesophase-forming compound can be found in DJ Broer et al., Makromolekulare Chemie 190, 2255 (1989). The polymerizable liquid crystal mixture used to prepare the anisotropic polymer film comprises preferably 0.1. Up to 35 weight percent, especially 〇·5 to 15 weight percent, in particular one to five to five weight percent or a plurality of polymerizable palmitic compounds of the formula I. The polymerizable liquid crystal mixture preferably comprises from 1 to 3 of the palmitic compounds of formula I. The polymerizable liquid crystal mixture of the present invention may additionally comprise one or more other suitable components such as, for example, a catalyst, a sensitizer, a stabilizer, a co-reactive monomer or a surface-active compound. In a preferred embodiment of the present invention, the polymerizable liquid crystal mixture of the present invention is included to prevent undesired spontaneous polymerization. For example, the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) during storage of the composition. First read the notes on the back. Write this page Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -39 1300775 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (37) The occurrence of the stabilizer. Essentially all compounds known to the skilled artisan to be useful for this purpose are useful as stabilizers. There are a variety of commercially available types of these compounds. A typical example of a stabilizer is 'ethoxyphenol or butylated hydroxytoluene (BHT). In order to increase the cross-linking of the polymer, in addition to the polyfunctional polymerizable mesophase-forming compound, up to 20% of the non-intermediate phase having two or more polymerizable functional groups may be added alternately or additionally. The compound is in the polymerizable composition. A typical example of the difunctional non-mesophase-forming monomer is a diacrylate alkyl ester or an alkyl dimethacrylate having an alkyl group of 1 to 20 C atoms. A typical example of the non-mesophase-forming monomer having two or more polymerizable groups is trimethylpropane trimethacrylate or pentaerythritol tetraacrylate. Polymerization of a composition of the invention comprising a compound having only one polymerizable functional group produces a linear polymer, while a compound having more than one polymerizable functional group is present, resulting in a crosslinked polymer. In the preparation of the anisotropic polymer gel, the liquid crystal mixture can be polymerized in situ as described above, however, in this case, calibration of the polymerizable mixture is not necessary. The palmitic compound of the formula I of the present invention can also be used to prepare a thermochromic liquid crystal mixture. The mixture is characterized by having a palmitic liquid phase or a palmitic intermediate phase, such as, for example, a palmitic smectic phase or a palmitic nematic (=cholesterol) phase, having a helical torsion molecular structure, for a particular band of light Selectively reflective 'the pitch of the molecular spiral and the resulting wavelength and temperature of the reflection. Please read the back of the matter first I#! f Loading the paper size for the Chinese National Standard (CNS) A4 specification (210X297) -40- 1300775 A7 _____B7_ V. Description of the invention (3 pieces). Particularly preferred is a liquid crystal mixture of the present invention having thermochromism and having a cholesterol phase. Among these preferred compositions, other preferred ones are The composition having a cholesterol phase and a smectic phase at a temperature lower than the cholesterol phase is preferably a palmitic smectic phase. The liquid crystal mixture of the present invention having thermochromism may be polymerizable or non-polymerizable. The palmitic compound and the mixture and polymer comprising the same are also suitable for the preparation of liquid crystal pigments. Therefore, the oriented cholesterol polymer prepared as described above can be honed into small flake particles. Suitable as a pigment for selective reflection of light. Such pigments can be used, for example, in inks, coatings or coatings for cosmetics, pharmaceuticals, decoration or anti-counterfeiting. The preparation of liquid crystal pigments is described, for example, in EP 601. 483, WO 97/27252 or WO 9 7/301 36. A liquid crystal pigment comprising a palmitic compound of formula I is another object of the invention. A liquid crystal compound of the formula I and a liquid crystal mixture comprising the same, liquid crystal Polymers or liquid crystal pigments are also suitable for use in cosmetic and pharmaceutical compositions, for example as described in EP 8 1 5 826 for the protection of human skin or hair as described in, for example, DE 196 29 761 or EP 1 038 94 1 Ultraviolet UV filter, especially UV-A and UV-B-radiation. The dopant of the present invention has a high HTP, so only a small amount is required to produce a short pitch, resulting in a material that is reflective in the UV range, and Suitable as a UV filter. A liquid crystal mixture containing a formula I and reflecting UV light, especially a liquid crystal polymer having a wavelength of 200 to 400 nm, a liquid crystal polymer or a liquid crystal pigment is another object of the present invention. For a make-up Product composition, especially the paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Please read the note on the back first. Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed -41 - 1300775 A7 B7 V. Invention Description ( 39) is a cosmetic or pharmaceutical composition for protecting human skin or hair, comprising a liquid crystal mixture comprising a palm compound of formula I, a liquid crystal polymer or a liquid crystal pigment as a UV filter, and reflecting UV light, In particular, the wavelength range is 200-440 nm, in particular 280-400 nm, 200-230 nm (UV-C) and 280-330 nm (UV-B). Based on the foregoing description, those skilled in the art can readily determine the essential characteristics of the present invention without departing from the spirit and scope of the invention, and various changes and modifications may be made to suit various uses and conditions. Without further painstaking efforts, it is believed that those skilled in the art can use the present invention to the fullest extent. Therefore, the following examples are for illustrative purposes only and are not limiting of other disclosures. In the foregoing and following examples, all temperatures are uncorrected in degrees Celsius, and all parts and percentages are by weight unless otherwise stated. The enthalpy of the helical torsion force HTP of the palm compound in the main liquid crystal is based on the following formula HTP=(p · c), !! // m·1 represents, where p is the pitch of the molecular helix, expressed in // m, and c is the weight concentration in the body expressed as relative 値 (hence, for example, 1 weight percent concentration The system corresponds to c being 〇. 〇1 値). The following abbreviations are used to illustrate the liquid phase properties of the compound: K = crystal 'N = nematic phase; S = smectic phase; N*, Ch = palmitic nematic phase, cholesterol; I = isotropic. The numbers between these symbols represent the phase transition temperatures expressed in degrees Celsius. Further, An is birefringence at 5 89 nm and 20 ° C, and Δ ε is a dielectric anisotropy at 20 ° C. In the chemical formula, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Please read the note on the back first. Next to the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1300775 A 7 B7 V. Invention Description (4〇) The C* system represents the palm of the C atom. Unless otherwise stated, the HTP oxime of the examples was determined at a concentration of 1% and a temperature of 20 °C in a commercially available liquid crystal main mixture MLC-6260 (Merck Kga A, Darmstadt, Germany). Example 1 Compound (1) was prepared according to the following reaction scheme

Preparation of tris-fluoromethanesulfonate (1-2): 60.37 ml (0.69 mol) of tetrafluoromethanesulfonic acid was added dropwise to 63.02 g (0.23 mol) of benzoic acid (丨-丨) and 25.00 g (〇) • 23 moles in propane dithiol 'The mixture was heated to 12 CTC for 45 minutes. After cooling, 800 ml of diethyl ether was added and the solution was cooled to 〇 ° C for 5 hours. The precipitated product was filtered off and washed with diethyl ether and dried in vacuo. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back - _ matters and fill in. On this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -43- 1300775 A7 B7 Five , invention description (41) (1) Preparation: at -70 ° C, 5 · 727 grams (0.02 moles) [1,1 '] binaphthyl-2,2,-diol and 6.999 ml (0.044 A solution of triethylamine in 20 mL of DCM was added to 10.0 g (0.02 mol) of trifluoromethanesulfonate (1-1) in 150 ml of DCM. The mixture was stirred for 1 hour, and 28.593 g was added. A suspension of dimethyldibromoacetamidine in 50 ml of DCM. The orange suspension was heated to -20 ° C and poured onto a mixture of 500 ml of 1 NaOH solution and 50 ml of NaHS 〇3 solution. The separated aqueous phase was extracted with DCM, and the combined organic phase was dried using Na.sub.2</RTI> <RTI ID=0.0></RTI> <RTIgt; 1) has a HTP of 35.0 (20 ° C), and low temperature dependence (35.0 at 〇 °C and 5 at TC 34 .0). The solubility of the compound (1) in the nematic liquid crystal main mixture ZLI-4792 (Merck KgaA, Ddarmstadt, Germany) is 10%. The same formula is prepared by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printing this paper. The scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -44 - 1300775 A7 B7 V. Description of invention (42)

(3) HTP-18.2 (20 0C)

(4) HTP - 35.4 (20 °C) Example 2

The compound (2) was isolated from the by-product compound (1) by HPLC as described in Example 1.

(2) 11

The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed compound (2) has an HTP of 24.4 (20 ° C). The foregoing embodiments can be similarly described above using the reactants and/or operating conditions of the present invention, which are generally or specifically described, in place of the users of the prior embodiments. Those skilled in the art can readily determine the paper of the present invention. The scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -45- 1300775 A7 B7 V. OBJECT DESCRIPTION OF THE INVENTION (43) To the extent that the present invention can be carried out without departing from the spirit and scope of the present invention Changes and modifications to make it suitable for a variety of conditions and uses (please read the precautions on the back ^^ write this page)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -46-

Claims (1)

13 Shun 7 Qin% A8 B8 C8 D8 VI. Application for Patent Scope 2A Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printing 90 1 1 743 Patent Application No. 3 Chinese Patent Application Stomach Exchange: Republic of China 97 May丨2.曰1, a pair of palm compound R1-X1-(A1-Z1)mG-(Z2-A2)n-X2-R2 having formula I, wherein R1 and R2 are each independently F, CU , Br, CN, SCN, SF5 or a palmitic or non-preferable alkyl group having up to 30 C atoms, which may be unsubstituted or mono- or polysubstituted by F, CM, Br or CN, one of which Or a plurality of non-adjacent CH2 groups may also be independently independently in each case - 〇-, -3-, 11-, - (: 113)-, -C〇-, (: 〇〇 _,·〇(:〇, _〇c〇_〇_, _s_c〇_, _c〇_s-, -CH=CH-, or -c three C- replaced, so that oxygen atoms are not directly bonded to each other , or a polymerizable group P_Sp_, 八p 炫e CH2=CW-C0〇-, WCH=CH-0-, WHC^CH-ten p system is or ch2=ch-phenyl-(〇)k- , W is Η, CH3 or cn, k is 0 or i, and Sp is a spacer having 1 to 25 C atoms, or a single bond, X1, X2, each alone The land system is -CF2〇_, -OCF2- or single bond, and Z1 and Z2 are independently -〇-, -S-, -CO-, and the paper size is applicable to China National Standard (CNS) A4 specification ( 210X 297 mm) (Please read the notice on the back of the threat and fill out this page) 1300775 bs8 C8 D8 __ VI. Patent application scope 2 -COO-, -OCO-, -0-C00-, -CO-N(R3)-, -N(R3)-CO-, -〇CH2·,-CH2 〇·, -SCHr, -CH2S-, -CF2CK -〇CF2-, -CF2S-, -SCFr, -CH2CH2·, -CF2CHr, -CH2CF2-, -CF2CF2-, -CH=CH-, -CF=CH· , -CH=CF-, -CF=CF-, •CsC-,-CH=CH-C〇〇-, -〇C〇-CH=CH- or single bond, R3 is H or has 1 to 4 The alkyl group of the C atom, A1 and A2 are each independently 1,4-phenylene, wherein one or more CH groups are further replaceable by N, 1,4-cyclohexylene, one of which A plurality of non-adjacent CH2 groups may be further replaced by hydrazine and/or S, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetra Hydronaphthalene-2,6-diyl, all of which may be unsubstituted, by halogen, cyano or nitro or alkyl, alkoxy, alkylcarbonyl or alkoxy having from 1 to 7 C atoms The carbonyl group is mono- or polysubstituted, wherein one or more deuterium atoms can be replaced by F or C1, and m and η are each independently 0, 1, 2 or 3, and (please read the back note first) Fill in this page) Basic Palm, Pair Alcohol Sugar-based Lugan G water system, its alcoholic ground water, di-alcohol, alcohol-one-b 2 sugar, pear 1 I, butane water, ethyl bromide, 1-selection, de-economics, intellectual property bureau, employee consumption cooperative Printing a record of Η-alkanol phenyl alcohol • and Use .ii to prescribe the standard of the country. 7 9 2 1300775 I D8 VI. Patent scope 3 where R4 is F, CH3 or CF3, and Y1, Y2, Y3 and Y4 are Η, F or selectively An alkyl group having 1 to 8 C atoms, wherein at least one of the groups X1 and X2 is a CF 2 〇 or - 〇 CF 2 —, or at least one of Z 1 and Z 2 is a CF 2 0 —, —0 CF 2 — or —CF2CF2 —. 2. For the palm compound in the first paragraph of the patent application, it is selected from the following formula (please read the note on the back and then fill in the page). The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Print this paper scale for China. National Standard (CNS) A4 Specification (210X297 mm) -3- 1300775 b Ιο D8 Patent Application Range 4 coo Μ OOC 〇 CF Ο &lt;y cf2cf ο coo 〇 1-2 OOC OcfzCf〇-r (Please read the note on the back and fill out this page) RX &gt;cf2cfA rco° 1-3 OOC o 〇CF r〇CF2〇^q_ C〇〇/OOC ~^y 〇CF 1-4 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1-5 &lt;y ^CF2CF〆 ^C00x 'OOC 八 /Cp2CFi\ /~R This paper scale applies to Chinese national standard (cns) A4 specification (21 ox297 mm) -4- 1300775 b Co D8 VI. Patent application scope 5 R 6 - 〇〇 R R R R -7 -8 (Please read the notes on the back and fill out this page) 〇〇 R R -9 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed R The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 1300775 | D8 VI. Patent application scope 6 Wherein R has one of the definitions of R1 in formula I, and the 1,4-benzene-terminated ring may also be an alkyl, alkoxy group having from 1 to 4 C atoms via F, Cl, CN or optionally fluorinated. Or an alkylcarbonyl or alkoxycarbonyl group is mono- or polysubstituted. 3. A liquid crystal mixture comprising at least one palmitic compound of claim 1 or 2. 4. A liquid crystal mixture according to claim 3, which additionally comprises at least one polymerizable mesophase-forming compound having at least one polymerizable functional group. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. 5. A linear or cross-linked liquid crystal polymer, which can be obtained by polymerizing a mixture of the third or fourth patent application. 6. For palm-like compounds of the first or second patent application, for liquid crystal displays, active and passive optical components, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics and pharmaceutical compositions, non- Linear optical instruments, optical data storage or as a palm-shaped dopant. This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) -6- 1300775 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing VI. Patent application scope 7 7. If the patent application scope is 1 Or 2 pairs of palm compounds, which are used in STN, TN, AMD-TN, temperature compensation, strong induction, host-type, phase-change or surface stabilization, or polymer-stabilized cholesterol structure (SSCT) , PSCT) displays, polarizers, compensation films, alignment layers, color filters or holographic components, or as UV filters, diagnostics, liquid crystal pigments, decorative and anti-counterfeiting applications. 8. A mixture of the third or fourth aspect of the patent application, which is used in liquid crystal displays, active and passive optical components, adhesives, synthetic resins having anisotropic mechanical properties, cosmetic and pharmaceutical compositions, nonlinear Optical instruments, optical data storage or as a palm-shaped dopant. 9. For example, a mixture of patents No. 3 or 4 is used for STN, TN, AMD-TN, temperature compensation, strong induction, host-type, phase-change or surface stabilization, or polymer stabilization. Cholesterol structure (SSCT, PSCT) displays, polarizers, compensation films, calibration layers, color filters or holographic components, or as UV filters, diagnostics, liquid crystal pigments, for decorative and anti-counterfeiting applications. 1 〇, as in the patent application scope 5 of the polymer, for liquid crystal displays, active and passive optical components, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics and pharmaceutical compositions, nonlinear optical instruments , in the storage of optical data or as a palm dopant. 1 1. A polymer as claimed in item 5 of the patent application, which is used for STN, TN, AMD-TN, temperature compensation, strong induction, host-type, phase-change or surface stabilization or polymer stabilization Cholesterol structure (SSCT, PSCT) display, polarizing plate, compensation film, calibration layer, color filter or holographic paper scale applicable to China National Standard (CNS) A4 specification (210X297 mm) (please smell the ## back note) Fill in this page again) 1300775 b C8 D8 VI. Apply for patent range 8 components, or as UV filter, diagnostic, liquid crystal pigment, for decoration and anti-counterfeiting applications. 1 2. A liquid crystal display comprising a liquid crystal mixture of claim 3 or 4. 1 3. A cholesteric liquid crystal medium comprising a palmitic component, one or more palmitic compounds of claim 1 or 2, and a nematic component comprising one or more nematic or nematic Sex compounds. 14. An SSCT display comprising the medium of claim 13 of the patent application. (Please fill in the notice on the back of the department first.) Printed by the Intellectual Property Office of the Ministry of Economic Affairs. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-