TWI229766B - Guest-host liquid crystal display device and producing method thereof - Google Patents

Abstract

To provide a liquid crystalline display element which shows a sharp display contrast. The quest/host-type crystalline display element is provided with one pair of the oppositely located substrates at least one of which is a transparent electrode, and with a host liquid crystal and the liquid crystalline layer with contains a dichroic coloring matter having a substituent group expressed by the formula: -(Het)m-{(B1)p-(Q1)q-(B2)r}n-C1, the both of which are sandwiched between the above one pair of the substrates, with the above host liquid crystal being made to orient in an angle of 60 DEG to 90 DEG relative to the opposite surface of the above substrates. In the formula, Het is a sulfur atom or an oxygen atom; B1 and B2 are each a divalent aryl group, a heteroaryl group or a cycloaliphatic hydrocarbyl group; Q1 is a divalent linking group; C1 is a substituent group such as an alkyl group; m is 0 or 1; p, q and r are each 0 to 5; and n is 1 to 3, but (p+r)xn is 3 to 10.

Description

1229766 V. Description of the invention (1) Technical field The present invention relates to a technical field of a host-guest liquid crystal display element suitable for a liquid crystal display. Prior art There are many ways to propose liquid crystal display elements (such as the 142nd Committee of the Japan Society for the Promotion of Science, a manual for liquid crystal instruments, the Nikkan Kogyo Shimbun, i 989). For example, the host-guest liquid crystal display element is a liquid crystal composition in which a dichroic pigment is dissolved in a liquid crystal, and is enclosed in a unit cell to have an electric field. The liquid crystal is moved and combined by the electric field to change the orientation of the dichroic pigment. The change of the light absorption state of the unit cell is displayed. This host-guest method enables bright display, and requires reflective liquid crystal elements. Here, the subject and guest methods are, for example, "LCD Handbook" (by B. Bahadur, D. Demus, J. Goodby, GW Gray, HW Spiess, V. Vi 1 1 Ed., Vo 1.2 A, Wi i 1 ey-VCH Corporation (1998), chapters 3 and 4, and pages 257-302. The dichroic dyes used in liquid crystal elements are described in detail in "Dichroic Dyes for Liquid Crystal Displays" (by A. V. Ivashchenko, CRC, 1984). Generally speaking, the liquid crystal alignment method of a liquid crystal display cell is a horizontal alignment method parallel to the horizontal direction of the long axis of the molecules of the liquid crystal to the substrate in the state without an applied voltage, and a vertical direction of the long axis of the molecules of the liquid crystal to the substrate. Side-by-side vertical alignment. Among them, horizontal alignment methods have been widely studied since ancient times. The horizontal alignment method is to vertically align the main liquid crystal to the substrate by applying a voltage, and to display the dichroic pigments vertically to the substrate. 1229766 V. Description of the invention (6) The present invention will be described in detail below. In addition, the "~" table in this specification does not include the numbers described before and after as the minimum and maximum ranges. The liquid crystal display device of the present invention is a liquid crystal layer having a main liquid crystal and a dichroic dye, and A voltage applied to this liquid crystal layer changes the alignment direction of the main liquid crystal molecules, and is a host-guest liquid crystal display element that is absorbed by a dichroic dye and changes in light hue even when transmitted through the liquid crystal layer. First, a dichroic pigment used in the present invention will be described. The dichroic pigment used in the present invention may be any pigment having a chromophore. For example, an azo pigment, an anthraquinone pigment, a perylene pigment, a cyanine pigment, an azomethine pigment, a phthalocyanine pigment, and an indigo pigment can be used. , Chamomile pigment, dioxin pigment, polythiophene pigment, etc. Specifically, for example, a person who writes "Dichroic Dyes for Liquid Crystal Displays" (by A.V.Ivashchenko, CRC Corporation, 1984). Preferred are azo pigments, anthraquinone pigments, and perylene pigments, and more preferred are azo pigments and wake pigments. The azo pigment includes a monoazo pigment, a disazo pigment, a reference azo pigment, a azo pigment, a woody azo pigment, and the like, and a monoazo pigment, a disazo pigment, and a reference azo pigment are preferred. Azo pigments generally contain ring structures such as carbocyclic rings (benzene ring, naphthalene ring, etc.) and heterocyclic rings (quinoline ring, pyridine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxane Azole ring, imidazoline ring, benzimidazoline ring, pyrenyl ring, etc.). The above anthraquinone pigment is based on those containing an oxygen atom, a sulfur atom, or a nitrogen atom. 1229766 V. Description of the invention (7) Substituent groups are preferred, for example, alkoxy, aryloxy, alkylthio, arylthio, and alkylamines are included. Preferred are aryl and arylamine groups. The number of substitutions of the substituent may be arbitrary, but di-, tri-, and tetra-substituted are preferred, and di- and tri-substituted are more preferred. The substitution position of the substituent may be any position, and preferred are 1, 4-position di-substitution, 1, 5-position di-substitution, 1, 4, 5-position tri-substitution, 1, 2, 4-position tri-substitution, and 1, 2 , 5-position tri-substitution, 1, 2, 4, 5-position tetra-substitution, 1, 2, 5, 6-position tetra-substitution structure. The dichroic dye in the present invention has at least one substituent represented by the following general formula (a). -(Het LUBiViQ'dB2) 丄 -C1 wherein He t represents a sulfur atom or an oxygen atom. Here, each of B1 and B2 represents a divalent aryl group, a heterocyclic group or a cyclic aliphatic hydrocarbon group. The divalent aryl group is preferably an aryl group having 2 to 20 carbon atoms. Specifically, a divalent group of a benzene ring, a naphthalene ring, and an anthracene ring is preferred. The more preferable one is a benzene ring and a divalent group substituted for the benzene ring, and the most preferable one is 1,4-phenylene. B1 and B2 represent heterocyclic groups having 1 to 20 carbon atoms as the divalent heterocyclic group. Specific examples are pyridine ring, quinoline ring, isothialine ring, pyrimidine ring, pyridine ring, thiophene ring, furan ring, oxazole ring, thiazole ring, imidazoline ring, pyrazole ring, oxadiazole ring, thiadiazole Rings, triazole rings, and divalent heteroaryl ring groups formed by these condensed rings are preferred. Preferred examples of the divalent cyclic aliphatic hydrocarbon group represented by B1 and B2 are, for example, cyclohexane-1,2-difluorenyl, cyclohexane-i, 3-difluorenyl, and cyclohexane-1,4- Difluorenyl and cyclopentane-1,3-difluorenyl, more preferably (E) -cyclohexane-1,4-difluorenyl. I229766

5. Description of the invention (8) B1 and B2 may each have a substituent, and the substituent is selected from the following substituent group V, for example. Substituent group V: Sensein atom (such as chlorine, bromine, iodine, fluorine); fluorenyl group; cyano group; carboxyl group; phosphorus fee group, fine group, ^ number 丨 10, preferably carbon number 2 to 8, more Preferred are aminomethylamidino groups having 2 to 5 carbon atoms (for example, methylaminomethylamidino, ethylaminomethylamidino, morpholinylaminomethylamidino); carbon numbers of 0 to 10, preferably Those are amine sulfonyl groups having 2 to 8 carbon atoms, and more preferably 2 to 5 (for example, methylamine sulfonyl, ethylamine sulfonyl, piperazine sulfonyl); nitro; carbon number 1 to 20, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon alkoxy groups (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy Aryl); 6 to 20 carbons, preferably 6 to 12 carbons, and more preferably 6 to 10 aryloxy groups (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy , Naphthyloxy); a fluorenyl group having a carbon number of 1 to 20, preferably a carbon number of 2 to 12, and more preferably a carbon number of 2 to 8 (e.g., ethenyl, benzamyl, and trichloroethenyl); 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms (e.g., ethylacetoxy, benzyloxy); carbon number 1 ~ 20, preferably carbon atom 2 ~ 12, more preferably carbon atom 2 ~ 8 (such as acetamido); carbon number 1 ~ 20, preferably carbon number 1 ~ 10, more preferably Those with 1 to 8 carbon atoms (such as methanesulfonyl, ethanesulfonyl, and benzenesulfonyl); carbons 1 to 20, preferably carbons 1 to 10, and more preferably carbon 1 ~ 8 sulfinyl sulfonyl (such as methanesulfinyl sulfonyl, ethanesulfinyl sulfinyl, benzenesulfinyl sulfinyl); carbon number 1 to 20, preferably carbon number 1 to 10, more preferably carbon number 1 ~ 8 sulfonamido group (for example, methanesulfonamido group, ethanesulfonamido-10-I229766 V. Description of the invention (9) group, benzenesulfonamide group); carbon number 0 ~ 2 0, preferably Carbon number 0 ~ 1 2, more preferably substituted or unsubstituted amino group with carbon number 0-8 (such as unsubstituted amino group, methylamino group, dimethylamino group, benzylamino group , Aniline, diphenylamino, 4-methylphenylamino, 4-ethylphenylamino, 3-n-propylphenyl, 4-n-propylphenylamino, 3- N-butylphenylamino, 4-n-butylphenylamino, 3-IE-pentylphenylamino, 4-n-pentylphenylamino, 3-trifluoromethyl Phenyl monthanyl, 4-trifluoromethylphenylamino, 2-pyridylamino, 3-pyridylamino, 2-thiazolylamino, 2-oxazolylamino, N, N- Methylphenylamino, N, N-ethylphenylamino); ammonium (such as trimethylammonium) having 0 to 15, carbons preferably 3 to 10, more preferably 3 to 6 carbons , Triethylammonium group); carbon number 0 ~ 1 5, preferably carbon number 1 ~ 10, more preferably carbon number 1 ~ 6 (such as trimethyl hydrazine); carbon number 1 ~ 1 5. The preferred carbon number is 1 to 10, the more preferred is a ureido group with a carbon number of 1 to 6 (such as a ureido group, N, N-dimethylureido group); the carbon number is 1 to 1 5. The preferred one is Carbon number 1 to 10, more preferably carbon number 1 to 6 (for example, squalene imino group); carbon number 1 to 20, preferably carbon number 1 to 1, 2, more preferably carbon number Alkylthio groups of 1 to 8 (eg, methylthio, ethylthio, propylthio); arylthio groups having 6 to 80 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 6 to 30 carbon atoms; For example, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-Pit Dfluorenylthio, 1-naphthylthio, 2-naphthylthio, 4-propylcyclohexyl-4 -Biphenylthio, 4 -Butylcyclohexyl-4'-biphenylthio, 4-pentylcyclohexyl-4, -biphenylthio, 4-propylphenyl-2 -ethynyl-4'-biphenylthio Carbon number 1 to 80, preferably carbon number 1 to 40, more preferably carbon number 1 to 30 '-11-1229666 V. Description of the invention (10) Heteroarylthio group (eg 2-pyridylthio Group, 3-pyridylthio group, 4-D {± D sulfenylthio group, 2-quinolinylthio group, 2-furylthio group, 2-pyrrolylthio group); carbon number 2-20, preferably 2 to 1 carbon number 2, more preferably an alkoxycarbonyl group with 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl); 6 to 20 carbon atoms, preferably An aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably an aryloxycarbonyl group having 6 to 10 carbon atoms (for example, a phenoxycarbonyl group); 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 1 carbon atoms. ~ 5 unsubstituted alkyl (such as methyl, ethyl, propyl, butyl); substituted with 1 to 18 carbons, preferably 1 to 10 carbons, and more preferably 1 to 5 carbons Alkyl (e.g., hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, ethinoaminomethyl); this Unsaturated hydrocarbon groups having 2 to 18 carbons, preferably 3 to 10 carbons, and more preferably 3 to 5 carbons (e.g., vinyl, ethynyl, 丨 -cyclohexenyl, benzylidene, benzylidene Group) includes substituted alkyl); substituted or unsubstituted aryl groups (e.g. phenyl, naphthalene) having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms P-phenyl, p-nitrophenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl, 4-propylcyclohexyl- 4'-biphenyl, 4-butylcyclohexyl-4, -biphenyl, 4-pentylcyclohexyl-4'-biphenyl, 4-propylphenyl-2-ethynylbiphenyl); 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 6 carbon atoms, such as substituted or unsubstituted heterocyclic groups (e.g., pyridyl,% methylpropyl, ethynyl, furan Group, morpholinyl, tetrahydrofuranyl). These substituent groups v may have a structure of a benzene ring or a naphthalene ring. In addition, these substituents may be further substituted with any substituent selected from the substituent group V. -12- 1229766 V. Description of the invention (V) The substituent group V is the above-mentioned alkyl, aryl, alkoxy, aryloxy, halogen atom, unsubstituted amine, substituted amine, hydroxyl, alkylthio The arylthio group is preferably 'more preferably an alkyl group, an aryl group, or a halogen atom. In the general formula (a), Q1 represents a divalent bonding group. Preferably, it is a divalent bonding group formed from an atomic group consisting of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom. The above-mentioned divalent bonding group is, for example, an alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, propyl, butyl, pentyl, cyclohexyl-1,4-difluorenyl), Alkenyl group with 2 to 20 carbons (for example, vinylidene), Alkenyl group with 2 to 20 carbons (for example, ethynyl), amido, ether, ester, sulfonamido, sulfonate Group, urea group, sulfofluorenyl group, sulfinamilide group, thioether group, carbonyl group, -NR- group (where R represents a hydrogen atom, alkyl group or aryl group), azo group, azooxy group, heterocyclic ring A divalent group (such as piperin-1,4-difluorenyl), or a divalent bond group having 0 to 60 carbon atoms composed of two or more of these. Q1 is preferably a divalent bonding group formed by an alkylene group, an alkylene group, an alkylene group, an ether group, a thioether group, an amidino group, an ester group, a carbonyl group, and combinations thereof. Q1 may have another substituent, and the substituent is, for example, any one selected from the substituent group V described above. In the general formula (a), C1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a fluorenyl group, an alkoxycarbonyl group or a fluorenyloxy group. Preferably, for example, the number of carbons is 1 to 30, the more preferred number is 1 to 1, and the more preferred number is 1 to 8 and the base (such as methyl, ethyl, propyl, butyl, 3-butyl, isobutyl, 2-butyl, pentyl, 3-pentyl, hexyl, heptyl, octyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4 -Propylcyclohexyl, 4-butylcyclohexyl, 4-pentyl-13-1229766 V. Description of the invention (12) cyclohexyl, hydroxymethyl, trifluoromethyl, benzyl), carbon number 1 ~ 20 1, preferably carbon number 1 to 10, more preferably carbon number 丨 to 8 (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy) ; Carbon number 1 ~ 20, preferably carbon number 2 ~ 1 2, more preferably carbon number 2 ~ 8 (such as ethyl ethyl, propyl ethyl, methyl ethyl); carbon number 1 ~ 20, Preferred are alkoxy groups having 2 to 12 carbon atoms, and more preferred are alkoxy groups having 2 to 8 carbon atoms (such as ethoxylated and benzophenoxy groups); 2 to 20 carbon atoms are preferred, and 2 to 12 carbon atoms are preferred. More preferred are alkoxycarbonyl groups having 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, and 2-benzyloxycarbonyl). C1 is more preferably an alkyl group or an alkoxy group, and the most preferred is ethyl, propyl, butyl, pentyl, hexyl or trifluoromethoxy. C1 may have another substituent, and the substituent is selected from, for example, any one of the substituent groups V described above. In the general formula (a), m represents 0 or 1, and preferably 1 is. p, q, and r are each an integer of 0 to 5, each of which represents an integer of 1 to 3, and (P + r) xη may satisfy 3 to 10. When p, ^, Γ, and η are each 2 or more, the repeating units may be the same or different. The preferred combinations of p, q, r and η are described below. -14- 1229766 V. Description of the invention (13) (1) p 22 2, q = 0, r = 1, n = 1 (2) p = 3, q = 0, r two 0, η = 1 (3) p 2 4, q = 0, r 2 0, η = 1 (4) p 2 5, q = 0, r 2 0, η = 1 (5) p 24, q = 1, r = 1, η = 1 (6) p = 1, q = 1, r = 2, η = 1 (7) p two 3, q = 1, r = 1, η = 1 (8) p = 1, q = 1, r = 3, η = 1 (9) p 22, q = 1, r = 2, η = 1 (10) p = 1 \ q = 1, r = 1, η = 3 (11) p = 0, q = 1, Γ = 3, η = 1 (12) ρ 〇, q = 1, r = 2, η = 2 (13) ρ = 1, q = 1, r = 2, η = 2 (14) ρ two 2. q = l, r = 1, η = 2 (1) P = 2, Q = 0, r: = 1, n = l; (2) p = 3, q = 〇 'n = l; (3) a combination of p = 4, q = 〇, r = 0, n = l; (5) p = 2, q = l, r = n = 1. In addition,-{(B ^ pJQ ^ q ^ BMrU-C1 is preferably a structure containing liquid crystallinity. The liquid crystal referred to here may be any type, preferably a nematic liquid crystal, a smectic liquid crystal, a butterfly Liquid crystals, more preferably nematic liquid crystals. Specific examples of liquid crystal compounds, such as those compiled by the LCD Fact Sheet Compilation Committee, LCD Stomach, Jiushan, 2000, are described in Chapter 3, "Molecular Structure and Liquid Crystallinity". The above description is not restricted by these (the wavy line in the figure indicates the position of the bond). -15-1212766 Fifth, the description of the invention (14)

~ n-CgHy

~ n-C4Hg

n-CsH "

n-C6Hi3

-16- 1229766 V. Description of the invention (15) [化 7]

η-〇3Η7

-n-C3H7

-17- 1229766 V. Description of the invention (【化 8】

y-OCgH ^ -n

Ο—η-Βυ

Λ 〇 χ-π-Bu

The number of substituents represented by the general formula (a) in the dichroic dye is preferably 1 to 8, more preferably 1 to 4, and most preferably 1 or 2. Among the dichroic pigments, anthraquinone compounds represented by the following general formula (1) are preferred. -18- 1229766 V. Description of the invention (1 7 [化 9]

R F

RR (Ql) f (B2) J h-C1's substituents' P, Q, r and η are each with the general formula U) where R1 represents, S represents a sulfur atom, b1, B2, qi, synonymous, more The same is true of the good fan. Each R8 represents an independent hydrogen atom or a group, for example, selected from the substituent group R2, R3, R4, R5, R6, R7, and a substituent. R2 to R8 each represents a substituent of V. In the above general formula (1), p =: 2, q = 〇, r = 1, and n = 1 are preferred. B1 represents an aryl group, B2 represents 1,4 · cyclohexyldifluorenyl group, and ci represents an alkyl group. . Among the anthracene pigments represented by the general formula (1), anthraquinone pigments represented by any of the following general formulae (2) to (4) are more preferred. [Chemical 1] 〇R1 〇R9 -19-1229766 V. Description of the invention (18) In the above general formula (2), R1 represents a substituent represented by -'S represents a sulfur atom, B1, B2, Q1, P, q, 1., and η are each synonymous with the above-mentioned general formula (a), and preferred ranges are also the same. In the general formula (2), R9 represents an arylthio group or a heterocyclic thio group. Arylthio groups with 6 to 80 carbon atoms are preferred, 6 to 40 carbon atoms are more preferred, and arylthio groups with 6 to 30 carbon atoms are most preferred (e.g., phenylthio, p-methylphenylthio, p-chlorobenzenesulfur). Methyl, 4-methylphenylthio, 4-ethylphenylthio, 4-n-propylphenylthio, 2-n-butylphenylthio, 3-n-butylphenylthio, 4-n-butyl Phenylthio, 2- 3rd-Butylphenylthio, 3- 3rd-Butylphenylthio, 4- 3rd-Butylphenylthio, 3-n-pentylphenylthio, 4-n-pentyl Phenylthio, 4-pentylphenylthio, 4-hexylphenylthio, 4-heptylphenylthio, 4-octylphenylthio, 4-trifluoromethylphenylthio, 3-trifluoromethylphenylthio Fluorinated methylphenylthio, 2-pyridylthio, 1-naphthylthio, 2-naphthylthio, 4-propylcyclohexyl-4, -biphenylthio, 4-butylcyclohexyl-4 , -Biphenylthio, 4-pentylcyclohexyl-4, -biphenylthio 4-propylphenyl-2 -ethynyl-4 '-biphenylthio); preferably carbon number 1 to 8 〇 Heteroarylthio having a carbon number of 1 to 4 and more preferably having a carbon number of 1 to 30 (for example, pyridylthio, 3-pyridylthio, 4-pyridylthio, 2-quinolinylthio, 2-furanthio, 2-pyrrolethio). R9 may have another substituent, and the substituent is selected from, for example, any of the substituents of the above-mentioned substituent group V. R9 is preferably an arylthio group, more preferably a square thio group having an alkyl group at the 3 or 4 position. The following are specific examples of the anthraquinone compound represented by the general formula (2), but the present invention is not limited by the specific examples. -20- 1229766

1229766 V. Description of the invention (20) [化 1 2]

Compound 1 -7

Compound 1-8 t-C4H9

Compound 1 -9 compound 1 -10

Compound 1 -11 -22-1229766

1229766 V. Description of the invention (22) In the following, the purchase of anthracene compounds represented by the following general formula (3) will be described in detail. [Chemical 1 4] rvvx R11

In the above general formula, R1 is a substituent shown, S represents a sulfur atom, and B1, β2, q1, p, q, and n are each synonymous with the formula (1), and RU, R11, and The Rl2 series each represent an independent arylthio group or a heteroarylthio group. In the general formula (3), R1Q, RU, and ri2 each represent an independent arylthio group or heteroarylthio group. Each arylthio group or heteroarylthio group represented by R1 () to R12 has the same meaning as that represented by R9 in the above-mentioned general formula (2), and a preferable range is also the same.

The following are specific examples of the anthraquinone compound represented by the general formula (3), but the present invention is not limited by the specific examples. -24- 1229766 V. Description of the invention (μ) [化 1 5]

Compound 2-1 compound 2-2

Compound 2-3 compound 2-4

Compound 2-5 -25-1229766 V. Description of the invention (24)

Compound 2-6

Compound 2-7

Compound 2-8

C5Hn Dagger Compound 2-9 The anthraquinone compound represented by the following general formula (4) will be described in detail below. -26-1229766

V. Description of the invention (25) [Chem. 1 7] R15 0 R1

In the substituents represented by the above general formula (4) and C1, S represents a sulfur atom, and Bi, r2, v, P, and q ^ are each synonymous with the above general formula (a), and preferred ranges are also the same. In the above general formula (4), R13, 1 ^, and ri5, and 一, y and κ are independent arylthio groups, heteroarylthio groups, substituted or unsubstituted amine groups, and test groups. At least one of R13, R14 and R15 represents a substituted or unsubstituted amine group, amidino group or a hydroxyl group. Each of the arylthio group and the heteroarylthio group is synonymous with R9 in the general formula (2), and preferred ranges are also the same. The substituted amino group represented by R13 to R15 is preferably an amino group substituted with an alkyl group, an aryl group or a heteroaryl group. Specific examples are methylamino, dimethylamino, benzylamino, aniline, diphenylamino, 4-methylaniline, 4-ethylaniline, 3-n-propylaniline, 4-n-propyl Aniline, 3-n-butylaniline, 4-n-butylaniline, 3-n-pentylaniline, 4-n-pentylaniline, 3-trifluoromethylaniline, 4-trifluoromethyl Aniline, 2-pyridylamino, 3-pyridylamino, 2-thiazolylamino, 2-oxazolylamino, N, N-methylaniline, N, N-ethylaniline. -27-1229766 V. Description of the invention (26) R14 and R15 are preferably unsubstituted amine or arylamine group, more preferably arylamine group. The amidino group represented by R13 to R15 is preferably an amidino group substituted with an alkyl group, an aryl group or a heterocyclic group. Specific examples of the anthraquinone compound represented by the general formula (4) are shown below, but the present invention is not limited to the specific examples. -28-1229766 V. Description of the invention (π [化 1 8]

CsH!

C5H11 Compound 3-1 C5Hv

C3H7 C4H9 (t) Compound 3-2

NH 0 S

〇5Hii C5H11 Compound 3-3

C5Hn compound 3-4 -29-1229766 V. Description of the invention (28) [Chem. 1 9]

Compound 3 — 5

Compound 3 — 7

-30-1229766 V. Description of the Invention (29) [化 20]

The following are specific examples of other dichroic pigments that can be used in the present invention (x-1 is a specific example of an anthraquinone pigment, azo-1 to 8 are specific examples of an azo pigment, and me s 0 to 1 to 4 Are specific examples of phthalocyanine pigments), but the present invention is not limited to these specific examples. -31-1229766 V. Description of the invention (30) [化 2 1]

Compound X-1 -32-1229766 V. Description of the invention (31 【化 22] Compound azoH C5Hn Compound azo-2 -N = N—N = Ν— ^ ~~ Νχ 一 广 C4H9

CsH "

N-N

〇—ί? Ν = ν— ^ Z ^ ~ 〇 C3Hr H3C compound azo-6 h3c 〇 P2H5 c2h5

, C2H5, c2h5

u ~ 9r ^ / > ~ 〇C4H9 Η H2 -33-1229766 V. Description of the invention (32) [化 2 3]

Compound mero-2

C5Hh compound mero * ~ 3

C5H "

Compound mero-4 C5H "For the dichroic pigments used in the present invention, please refer to" Dichroic Dyes for Liquid Crystal Displays "(A.V. Ivashchenko, CRC, 1994)," General Synthetic Dyes "(Hirakuchi Hiroguchi Author, Sankyo Publishing, 1988) and the methods described in the cited literature. In the present invention, the liquid crystal layer preferably contains one or more yellow pigments, one or more magenta pigments, and one or more cyan pigments, and the form of forming a neutral black is better than -34-1229766. V. Invention Description (33). When performing full color, there are additive color mixing of mixed red (R), green (G), and blue (B), and subtractive color mixing of superimposed yellow (Y), magenta (M), and cyan (C). It is better to make the black form by subtraction. It is described in detail in "Color Chemistry" (by Toshiko Masuda, Jiu Shan, 1982). Generally, yellow pigment exists in the range of 430 to 490 nm, magenta pigment is in the range of 500 to 580 nm, and cyan pigment is in the range of 60 to 700 nm. The anthraquinone compounds represented by the general formula (2) are mostly yellow pigment examples, and the anthraquinone compounds represented by the general formula (3) are changed by changing the maximum absorption wavelength and changing the hue according to the type and substitution position of the substituents contained in the pigment. Many examples are magenta pigments, and most of the anthraquinone compounds represented by the general formula (4) are examples of cyan pigments. The following describes the main liquid crystal used in the present invention. The coexistence of the main liquid crystal used in the present invention and a dichroic dye having a substituent represented by the general formula (a) (hereinafter referred to as "dichroic dye of the present invention") is not particularly limited. Liquid crystal compounds in nematic or smectic phase. Specific examples include azomethine compounds, cyanobiphenyl compounds, cyanophenyl esters, fluorine-substituted phenylesters, phenyl cyclohexanecarboxylate, fluorosubstituted cyclohexanephenylphenyl, cyanophenylcyclohexyl Alkane, fluorine-substituted phenylcyclohexane, cyano-substituted phenylpyrimidine, fluorine-substituted phenylpyrimidine, alkoxy-substituted phenylpyrimidine, fluorine-substituted alkoxy-substituted phenylpyrimidine, phenyldioxane, diphenyl Acetylene-based compounds, fluorine-substituted diphenylacetylene-based compounds, alkenylcyclohexylbenzonitrile, and the like. "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, the Nikkan Kogyo Shimbun, 1989) on pages 154 to 192 and pages 715 to 722 of liquid crystal compounds. May also be suitable for using TFT-driven fluorine -35-1229766 V. Description of the invention (34) The main liquid crystal. In the present invention, it is preferable to use a main liquid crystal having a negative dielectric anisotropy. Liquid crystals with negative dielectric anisotropy, in general, the short axis of the liquid crystal molecules must have a structure that makes the dielectric anisotropy large, for example, Γ Monthly Display (2000, April issue), pages 4 ~ 9 Page writer Synlett., Vol. 4, 389-396, writer of 999. Among these, a liquid crystal having a negative dielectric anisotropy having a fluorine-based substituent is preferred in terms of voltage holding ratio. The following are typical examples of liquid crystals with negative dielectric anisotropy ', but the present invention is not limited to these. -36-1229766 V. Description of the invention (π) [化 24]

irn

; Η1Γη CsH-n-n η-〇5Η ^ Ο

〇Et

F F -37-1229766 V. Description of the invention (36) [化 2 5]

A dichroic dye having a substituent represented by the above-mentioned general formula (a) (hereinafter referred to simply as "dichroic dye of the present invention") has a dielectric anisotropy of the main liquid crystal (especially the dielectric anisotropy as exemplified above). Negative liquid crystal) has high solubility and can improve the order parameter of the liquid crystal composition. In particular, it has a feature of high solubility in a fluorine-based main liquid crystal suitable for TFT driving. When the liquid crystal layer aims to change the physical properties of the main liquid crystal within a desired range (for example, when the temperature range of the liquid crystal phase is a desired range), a compound having no liquid crystal properties may be added. In addition, it can also contain palsy compound -38-1229766 V. Description of invention (39) 80. ~ 90 °. The preferred form of the present invention is a host-guest type liquid crystal display element having positive display characteristics using a liquid crystal having a negative dielectric anisotropy as a main liquid crystal and a pigment having a large absorption effect in a long axis direction as a dichroic pigment. . This state is because the liquid crystal is at an angle of 60 when no voltage is applied. ~ 9 0. It is vertically aligned, and the dichroic pigment is vertically aligned in the same way as the main liquid crystal. Therefore, the dichroic pigment cannot absorb and transmit incident light. In addition, since the liquid crystal molecules are anisotropically aligned when they are applied with a voltage, they form parallel alignment, and as a result, the incident light is absorbed by the dichroic dye. In other words, it has the positive display characteristics of displaying in white when no voltage is applied and displaying in black when voltage is applied. In addition, other forms include, for example, a host-guest display element having negative display characteristics in combination with a main liquid crystal having a negative dielectric anisotropy and a dichroic dye having a large absorption effect in the short axis direction. The display element of the present invention can be driven using a simple matrix driving method or an active matrix driving method using a thin film converter (TFT) or the like. Driving method For example, the driving method of the liquid crystal display device of the present invention, which is described in detail in pages 387 to 460 of the "Liquid Crystal Device Handbook" (edited by the Japan Society for the Promotion of Science 42nd Committee, the Nikkan Shimbun, 1989), is used. The liquid crystal display which can use the liquid crystal display element of the present invention is not limited in its mode, for example, the subject-guest method description on page 309 of the "Liquid Crystal Device Handbook" (edited by the Japan Society for the Promotion of Science, Committee No. 142, Nippon Shimbun, 1989). (1) homogeneous alignment, (2) homogeneous alignment, Whit-Taylor type (phase transfer type), (3) focus alignment and (4) homogeneous alignment, and (5) super-twisted nematic -41-1229766 V. Description of the Invention (4) (STN) method combination, (6) Ferroelectric Liquid Crystal (FLC) combination, and "Reflective color LCD synthesis technology" (Supervisor, Uchida Ryuu, Siemsey (Transliteration ) Company, 1999) Chapter 2-1 (GH-type reflective color LCD), (a) Heilmeier-type GH type, (b) 1/2 / wavelength plate-type GH type, (c ) 2-layer type GH type, (d) phase transfer type Gh type, (e) polymer dispersed liquid crystal (PDLC) type GH type, and the like. In addition, the liquid crystal display device of the present invention can use JP-A No. 10-67990, the same as No. 10-239702, the same as No. 10-133226, the same as No. 10-339881, the same as 1 1-524 1 1 and the same 1 1-64. Laminated GH type described in various publications such as 880, Japanese Patent Application Laid-Open No. 2000-22 1 538, and GH type liquid crystal display using microgels described in Japanese Patent Application Publication No. 1-24090. In addition, JP 6-235931, the same as 6-125940, the same as 6-265859, the same as 7-56 1 74, the same as 9-1 46 1 24, the same as 9-1 97388, and the same 0 -No. 23 346, No. 10-3 1 207, No. 10-31216, No. 10-31231, No. 10-31232, No. 10-31233, No. 10-31234, No. 10-82986, Same as 10-90674, same as 10-111513, same as 10-111523, same as 10-123509, same as 10-123510, same as 10-206851, same as 10-253993, same as 10-268300, same The reflection type liquid crystal display described in the publications of 11 -1 492 52 and JP 2000-2874. In addition, JP-A No. 5-6 1 025, No. 5-26505 No. 3, No. 6-3691, No. 6-23061, No. 5-203940, No. 6-242423, No. 6-289376, No. 8 -Polymer-dispersed liquid crystal type GH type as described in the Gazettes No. 278490 and 9-813174. -42-1229766 V. Description of the invention (41) Examples The following describes the present invention in more detail with examples. The materials, reagents, substance amounts, ratios, operations, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention, but the scope of the present invention is not limited by the following specific examples. [Production of liquid crystal cell] (1) The surface of the glass substrate on which ITO was vapor-deposited was coated with a polyimide alignment film "JALS-682-R3" made of SR (strand), and then sintered at 180 ° C. This substrate was subjected to a rubbing treatment (parallel alignment), and then a pitch-controlling plate (6.5 μm) made by Catalytic Chemical Industries, Ltd. and an epoxy adhesive were used to produce a sandwich-shaped liquid crystal cell A. The pretilt angle of the liquid crystal alignment in the alignment film is 88 °. In addition, a liquid crystal cell B was produced in the same manner as described above using a polyimide alignment film "AL3046" made of JSR (horizontal) alignment film. The pretilt angle of the alignment film is 2 °. (2) Preparation of liquid crystal element: Each of 1 mg of the compound shown in Table 1 below (the dichroic pigment of the present invention and a conventional comparative compound) was mixed with 100 mg of the main liquid crystal shown in Table 1 below, at 80 ° C. Heat and stir. After cooling to room temperature, the cells A or B prepared in (1) were injected to produce a liquid crystal element. In addition, when the cell A is used, a liquid crystal with a negative dielectric anisotropy (Melco, Inc., "MLC-6608") is used, and when the cell B is used, a liquid crystal with a positive dielectric anisotropy ( "ZLI-508 1" by Merulco). (3) Measure the absorption spectrum when a voltage is applied to each of the produced liquid crystal elements, and irradiate polarized light parallel to the rubbing direction ', and make each absorption spectrum (A || (0V)) UV3100 (manufactured by Shimadzu, visible absorption spectrometer) ). Then, a rectangular AC voltage (10V, 60Hz) was applied to each of the produced liquid crystal elements, and polarized light was irradiated parallel to the rubbing direction, and the absorption spectra (A || (10 V)) were measured. The measurement of the absorption wavelength (A II (0V) and {A II (10V)}) can be obtained by the following formula: Dmax / Dmin. The results are shown in Table 2. For unit A: Dmax / Dmin = {A || ( l〇V)} / {A || (0V)} For unit B: Dmax / Dmin = {A || (0V)} / {A || (10V)} -43-1229766 V. Description of the invention (42 ) Table 1 Liquid crystal cell dichroic pigment main liquid crystal Example 1 Vertically aligned unit cell A Compound 1 of the present invention 1 -1 MLC-6608 (manufactured by Meruco) Example 2 Vertically aligned unit cell A Compound of the present invention 1-1 MLC-6609 (produced by Meruco) Example 3 Vertical alignment unit A The compound 1-1 of the present invention 1-1 MLC-6610 (produced by Meruco) Example 4 Vertical alignment To the unit cell A Compound 1-3 of the present invention MLC-6609 (manufactured by Meruco) Comparative Example 1 Vertical alignment unit A A MLC-6609 (manufactured by Meruco) Example 5 Vertically aligned unit cell A The present compound 2-1 MLC-6609 (manufactured by Merulco) Comparative Example 2 Vertically aligned unit A A conventional compound A-2 MLC-6609 (meruco (transliteration) (Company)) Example 6 Vertically aligned unit cell A Compound 3-3 MLC-6609 of the present invention (manufactured by Meruco) Comparative Example 3 Vertically aligned unit cell A Conventional compound A-3 MLC-6609 (ume (Company made by Luco) Example 7 Vertical alignment unit A Compound of the present invention 1-3 Compound of the present invention 2-1 Compound of the present invention 3-3 MLC-6609 (manufactured by Meruco) Comparative Example 4 Vertical alignment unit A Known compound A-1 Known compound A-2 Known compound A-3 MLC-6609 (Merco), Comparative Example 5 Horizontally aligned unit B Known compound A-1 ZLI-5081 (manufactured by Meruco) Example 8 Vertically aligned unit cell A The compound azo-3 MLC-6609 (Meru) Available (produced by the company) Comparative Example 6 Horizontal alignment unit A Known compound B-1 ZLI-5081 (produced by Meruco) -44- 1229766 V. Description of the invention (43) Table 2 Liquid crystal cell Measurement of absorption wavelength / nm Dmax / Dmi η Example 1 Vertically aligned cell A 455 12 Example 2 Vertically aligned cell A 455 14 Example 3 Vertically aligned cell A 455 13 Example 4 Vertically aligned cell A 455 14 Comparison Example 1 Vertically aligned cell A 455 9 Example 5 Vertically aligned cell A 550 12 Comparative example 2 Vertically aligned cell A 550 8 Example 6 Vertically aligned cell A 670 11 Comparative example 3 Vertically aligned cell A 650 6 Implementation Example 7 Vertically aligned cell A 455 13 550 12 670 11 Comparative example 4 Vertically aligned cell A 455 8 550 8 650 6 Comparative example 5 Horizontally aligned cell B 455 6 Example 8 Vertically aligned cell A 560 10 Comparative example 6 Vertical alignment unit cell A 560 5 -45-1229766 V. Description of the invention (44) Comparison: Jpn. J. Appl. Phys., Vol. 37, 3 4 2 2 (19 9 8).

(Cyanide Compound A-3) 巳 u—N = N (Compound B-1) Comparison: Liquid Crystal Handbook, vol. 2A, D. Demus, Wi ley-VCH, p262 (1 998).

-46- 1229766 V. Explanation of the invention (45) From the results shown in Table 2, it can be seen that the concentration ratio of the liquid crystal display element of the example to that of the liquid crystal display element of the comparative example using a conventional compound is compared to D ma X / D mi η. The time is higher, in other words, the display contrast is higher. In addition, in the liquid crystal display element of Example 1, except that the main liquid crystal is a positive liquid crystal with a dielectric anisotropy (manufactured by Meruco, "ZL1-5 80 1"), and the unit cell is replaced by a horizontally aligned unit cell B A liquid crystal display device was produced in the same manner as in Example 1. This liquid crystal display element was 9 when the concentration ratio Dmax / Dmin of 4 5 5 nm was measured in the same manner as described above. From this, it can be seen that the concentration ratio Dmax / Dm in of the liquid crystal display element of the present invention in the vertical alignment mode compared to the horizontal alignment mode is a tube. Effects of the Invention As described above, the present invention can provide a liquid crystal display element having a high display contrast and a method for manufacturing the same. -47- 1229766 ί ~ I, I sound $ Γ, XL ’, 'Γ-; --- 5. Description of the invention (2). However, the host-guest liquid crystal element using the horizontal alignment, when the voltage is applied, the main liquid crystal near the alignment film cannot be completely vertically aligned due to the interaction from the horizontal alignment film, so the dichroic pigments near the alignment film cannot be completely vertical. Alignment, which causes a reduction in display contrast. In addition, a high voltage must be used for completely vertical alignment, which increases the power consumption when the display contrast is increased. A host-guest display device using a vertical alignment method is disclosed in Japanese Patent Application Laid-Open No. 10-20346 and Japanese Patent Application Laid-Open No. 2000-2928 1 6. However, since the order parameters of dichroic pigments are low in these liquid crystal displays, Not enough display contrast. Problems to be Solved by the Invention In view of the various problems described above, the present invention provides a host-guest liquid crystal display element with high display contrast and a method for manufacturing the same. Means for solving the problem In order to solve the above-mentioned problem, the host-guest liquid crystal display element of the present invention is characterized by including a pair of substrates disposed opposite to each other, at least one of the substrates is a transparent electrode, and the host substrate is sandwiched between the pair of substrates. For the liquid crystal and the liquid crystal layer having a dichroic dye having a substituent represented by the following general formula (a), the main liquid crystal is at an angle of 60 with respect to the facing surface of at least one of the substrates. ~ 90. Aligned. -(Het) m-{(B1) p- (Q1) q- (B2) r} n-C1 general formula ⑻ wherein Het represents a sulfur atom or an oxygen atom, and B1 and B2 each represent a divalent aromatic group, a heterocyclic group Aryl or cyclic aliphatic hydrocarbon group, Q1 represents a divalent bonding group, C1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a fluorenyl group, an alkoxycarbonyl group or a fluorenyl group; m represents 0 or 1, p, q and r represent integers of 0 to 5, and η represents 1 to 3 1229766 —- Η ^-= — V. Any of the integers in the description of the invention (3)! '' 丨, (p + r) xn represents 3 to 10 , Ρ, 9 and r are each 2 or more inches, B1, Q1, and B2 may be different or different, n is 2 or more and 0 inches, and 2 or more {(B ^ p-iQ ^ q ^ B) r} can be the same or different. A preferred aspect of the present invention is to provide a host-guest liquid crystal display element having a vertical alignment film on opposite sides of at least one of the pair of substrates; the host liquid crystal display element having a negative dielectric anisotropy; The dichroic pigment is a host-guest type liquid crystal display element of the onion i pigment; the pretilt angle is 80. A host-guest liquid crystal display element of ~ 90 °; the host liquid crystal is a host-guest liquid crystal display element having one or more truncated atoms in one molecule. The dichroic pigment is a host-guest liquid crystal display element containing one or more yellow pigments, one or more magenta pigments, and one or more cyan pigments. A preferred aspect of the present invention is to provide a host-guest liquid crystal display device in which the above-mentioned dichroic pigment is a compound represented by the following general formula (1); a more preferable aspect is that the dichroic pigment is the following general formula (2) ~ (4) A host-guest liquid crystal display element represented by any one of the formulas.

.R8 〇 R1

FT 1229766

Amendment I. V. Description of the invention (4) where 'R1 is-^-((B ^ p-CQ ^ q ^ B2) ,. Un-C1 is not a substituent, S represents a sulfur atom, B1, B2, Q1 , P, q, r, and η are each synonymous with the above general formula U), and R2, R3, R4, R5, R6, R7, and R8 each represent an independent hydrogen atom or a substituent. [Chemical 3] 〇

R R3 〇 where 'R1 is-^-((BMp-iQ ^ q-iB2) ^)). -! ^ 1 is not a substituent, S represents a sulfur atom, B1, B2, Q1, p, q, r and η are each synonymous with the above general formula (1), and R9 represents an arylthio group or a heteroarylthio group . [Chemical 4]

R 12 〇

R

R 11 〇

R 10 wherein R 1 is a substituent shown, S represents a sulfur atom, and B 1, B 2, Q 1, p, q, r, and η are each the same as the above 1229766 y 'h! 5. Description of the invention (5 1) Chinese synonymous heteroarylthio. [Chem 5]

R R11 and R12 each independently represent an arylthio group or

u ^ 13 # where R1 is, Π1 9 '-(Β2) ^)) ^. The substituents shown, S represents a sulfur atom; gi, r2 b, Q, P, 'q, r, and η are each synonymous with the above general formula (1), and RU, 14 _ κ, and R 5, each For independent arylthio

, Heterosulfanyl group, substituted or substituted amine group, fluorenyl group or hydroxy group, at least one of R 13, R14 and R15 represents substituted or unsubstituted amine group, fluorenyl group or hydroxy group . In addition, in order to solve the above-mentioned problem, the present invention provides a host-guest type liquid crystal hiding inconvenient piece: the IA method, which is based on a pair of substrates with opposite arrangements, at least one of which is a transparent electrode, and The method for manufacturing a liquid crystal layer containing a main liquid crystal and a dichroic dye between substrates is characterized by including a pretilt angle of 60 on an opposing surface of at least one of the substrates. ~ 9 0. Step of using an alignment film and using a pigment having a substituent represented by the general formula (a) as a dichroic pigment. Embodiment 1229766 of the invention V. Description of the invention (37) Compounds such as substances, ultraviolet absorbers, antioxidants, etc. . Examples of such additives are TN and STN palmitizers described in "Liquid Crystal Device Handbook" (edited by the Japan Society for the Promotion of Science, Committee No. 42, Nippon Shimbun, 1989) on pages 199 to 202. The content of the main liquid crystal of the liquid crystal layer and the dichroic pigment of the present invention is not particularly limited, and the content of the dichroic pigment is preferably 0.1 to 15% by mass with respect to the content of the main liquid crystal. It is 0.5 to 6% by mass. In addition, it is preferable to determine the required optical density when determining the absorption spectrum of the liquid crystal layer. The liquid crystal display element of the present invention includes a pair of substrates. The substrate is preferably an electrode substrate in which a voltage is applied to the liquid crystal layer being held. The electrode plate is usually formed on a substrate made of glass or plastic to form an electrode layer. Examples of the plastic substrate include acrylic resin, polycarbonate resin, and epoxy resin. Substrates For example, those listed on pages 218 to 231 of the "Liquid Crystal Device Handbook" (edited by the Japan Society for the Promotion of Science, Committee No. 142, Yakuza Shimbun, 1989). At least one of the above pair of substrates is a transparent electrode substrate, and a structure in which a transparent electrode layer is preferably formed on a transparent substrate such as glass or plastic. The transparent electrode layer is formed of, for example, indium oxide, indium tin oxide (ITO), tin oxide, or the like. The above-mentioned transparent electrode layer is described in pages 232 to 239 of "Liquid Crystal Device Handbook" (edited by the Japan Society for the Promotion of Science, Committee No. 142, Nikkan Shimbun, 1989). The liquid crystal element of the present invention has, for example, a pair of substrates arranged opposite to each other at a distance of 1 to 50 μm via a distance-adjusting plate, and is produced by injecting a liquid crystal composition containing a main liquid crystal and a dichroic dye of the present invention into a space formed between the substrates. . The above-mentioned pitch adjustment-39-1229766 P / r: V. Description of the invention (38) For example, the "Liquid Crystal Device Handbook" (second edition of the Japan Society for the Promotion of Science No. 1 42 Committee, the Nikkan Shimbun, 1 989) can be used. 57-262 pages. The liquid crystal composition can be prepared by dissolving the dichroic dye of the present invention in a main liquid crystal. The dissolution system can be performed by mechanical stirring, heating, ultrasound, or a combination thereof. In the present invention, it is preferred that the main liquid crystal be subjected to an alignment of an angle of 60 ° to 90 ° (preferably 80 ° to 90 °) on the opposing surface of at least one of the pair of substrates. The method for determining the tilt angle of liquid crystal molecules for a substrate is described in "Liquid Crystal Fact Sheet" (Edited by the Liquid Crystal Filing Committee, Jiushan, 2000), pages 234 to 239. There are no particular restrictions on the alignment treatment, such as various methods such as rubbing treatment, light irradiation, and vapor deposition. Wherein, when an alignment film is formed on at least one of the opposite surfaces of the pair of substrates, and rubbing treatment, light irradiation, and the like are performed on the alignment film under various conditions, the liquid crystal molecules are made to the substrate at an angle in the above range. It is preferable that the liquid crystal is easily aligned. The above-mentioned alignment film may be of any material and can be used on pages 240 to 56 of the "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science and Technology, Nikkan Shimbun, 1989). The alignment film is preferably a film made of a polyfluorene-based material. Polyimide-based alignment films such as "Monthly Display" (2000, August issue, pages 13 ~ 18), "Liquid Crystal Fact Sheet" (edited by the Liquid Crystal Filing Committee, Jizen, 2000), pages 253 to 258 Page writer. In addition, the rubbing treatment is not particularly limited, and for example, a general method of rubbing the surface of the alignment film in a certain direction with a sponge to form fine grooves. A vertical alignment film with a pretilt angle of 60 to 90 ° formed by the alignment film is preferred, and more preferably -40-

Claims (1)

1229766 VI. Application for Patent Range No. 91 123020 "Host-Guest LCD Display Elements and Benefits VI. Application for Patent Range: A host-guest LCD display element is characterized by having a pair of substrates arranged opposite to each other. One sheet is a transparent electrode, and a liquid crystal layer containing a negative dielectric anisotropy main liquid crystal and a dichroic dye having a substituent represented by the following general formula (1) is sandwiched between the pair of substrates, with respect to the substrate. For at least one of the opposing surfaces, the main liquid crystal is aligned at an angle of 60 ° ~ 90 °, R8 O R1 R5. 〇R4 general formula (1), R3, S represents a sulfur atom, B1 and B2 each represents a divalent C2-C2 () aryl group, q-C20 heteroaryl or a cyclic aliphatic hydrocarbon group, and q 1 represents a divalent Bonding group, C1 represents CrCw alkyl, (VC3 () cycloalkyl, CVC2. Alkoxy, cvc20 fluorenyl, C2-C2. Fluorenyl or oxy, p, q and r each represent 0 ~ An integer of 5; n represents an integer of 1 to 3; (p + r) Xn represents 3 to 10 ′ When p, q, and r are each 2 or more, Bi, qi, and B2 of 2 or more may be the same or different, respectively, and ^ is When it is 2 or more, 以上 1),-(QMc ^ B2) J may be the same or different), and r2, R3, R4, R5, r6, r7, and R8 each independently represent a hydrogen atom or is selected from the following Substituent group v 1229766 6. Substituents in the scope of patent application, Substituent Group V: Halogen atom, mercapto group, cyano group, carboxyl group, phosphate group, sulfo group, C: _ClQ yringomethyl formamyl, amine sulfonyl, nitro, g g2. Y2OH ~ C6 C2 ° alkalyl, CrC2. fluorenyl, Cl-C2G fluorenyl, Ci_C2Q hydrazine, Cl-C2. sulfonyl, Ci_C2. sulfinyl, Ci_C2Q 〆2. Substituted or unsubstituted amine group, C0-C15 ammonium group, CV c15 hydrazine group, c ^ c15 urea group, Ci-Ci5 imino group, Ci_C2. Alkylthio group, C6_C8 ° square thio group , C1-C8. Heteroarylthio, C2-C2G alkoxycarbonyl, C6-C2Q aryloxycarbonyl, ci-Cl8 unsubstituted alkyl, Cl-cu substituted alkyl, C6-C2 () Substituted or unsubstituted aryl 'and Ci-C: 2. Substituted or unsubstituted heterocyclic group. 2. The host-guest type liquid crystal display element according to item 1 of the patent application scope, wherein the general formula (1 ), R2, R3, R4, R5, R6, R7, and R8 each independently represent a hydrogen atom or a substituent selected from the following substituent group V, and the substituent group Vi: an alkyl group, an aryl group, and an alkoxy group Group, aryloxy group, halogen atom, unsubstituted Group, substituted amine group, hydroxyl group, alkylthio group, and arylthio group. 3 · As in the host-guest type liquid crystal display element of the first patent application scope, in the general formula (1), p = 2, q = 0, r = l and nd 'B represents a square group' B represents 1,4-cyclohexanedifluorenyl group, and C1 represents an academy base. For the opposite side, the main LCD is at an angle of 80 ° ~ 90. 1229766 6. Scope of patent application. 5. The host-guest type liquid crystal display element according to any one of claims 1 to 4, wherein a facing surface of at least one of the pair of substrates has a vertical alignment film. 6. The host-guest type liquid crystal display element according to any one of claims 1 to 4, wherein the host liquid crystal has one or more fluorine atoms in the molecule. 7. The host-guest liquid crystal display element according to any one of claims 1 to 4, wherein the dichroic pigment contains one or more yellow pigments, one or more magenta pigments, and one or more cyan pigments. 8. A method for manufacturing a host-guest liquid crystal display element, which is based on a pair of substrates arranged oppositely, at least one of which is a transparent electrode, and a host liquid crystal and the following general formula are sandwiched between the pair of substrates. The method for producing a liquid crystal layer having a dichroic dye having a substituent as shown in (a), which comprises forming a pretilt angle of 60 on an opposite surface of at least one of the substrates. Step of aligning film to 90 °, and using a pigment having a substituent represented by the following general formula (a) as a dichroic pigment,-(Het) m- {(B1) · ^ (Q1) ^ (B2) ,} ,,-^ 1 General formula (a) wherein He t represents a sulfur atom or an oxygen atom, and B1 and B2 each represent a divalent aromatic group, a heteroaryl group or a cyclic aliphatic hydrocarbon group, and a divalent bonding group C1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a fluorenyl group, an alkoxycarbonyl group, or a fluorenyl group, m represents 0 or 1, p, q, and r represent an integer of 0 to 5, and η represents an integer of 1 to 3. Integer, (p + r) xn represents 3 to 10. When p, q & r are 2 or more, B1, Q1, and B2 of 2 or more may be the same or different. When n is 1229766 and the scope of patent application is 2 or more, 2 The above can be the same or different