TWI482769B - Compound, optical film and method for making an optical film - Google Patents

Description

Compound, optical film and optical film manufacturing method

The present invention relates to a method for producing a compound, an optical film, and an optical film.

A flat panel display device (FPD) includes a member using an optical film such as a polarizing plate or a phase difference plate. The optical film sheet is, for example, an optical film obtained by applying a solution obtained by dissolving a polymerizable compound in a solvent to a support substrate and then polymerizing the solution. Such a polymerizable compound is disclosed in SID Symposium Digest of Technical Papers, 2006, Vol. 37, p. 1673, which is a compound represented by the following formula (LC242).

The present invention provides the following.

[1] A compound having a divalent group represented by formula (1-1) or formula (1-2):

(wherein Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl sulfinyl group having 1 to 6 carbon atoms, and carbon. 1 to 6 alkylsulfonyl, 1 to 6 fluoroalkyl, 1 to 6 alkoxy, 1 to 6 sulfanyl, carbon number 1 to 6 N-alkylamino group, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dioxane having 2 to 12 carbon atoms Aminylsulfonyl or -COOH; Q ¹ and Q ² each independently represent -CR ¹ R ² -, -S-, -NR ² -, -CO- or O-, and R ¹ and R ² each independently represent a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms; Y ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group; and D ¹ and D ² each independently represent a single bond Or a divalent linking group; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a fluoroalkyl group having 1 to 4 carbon atoms. An alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the -CH ₂ - of the alicyclic hydrocarbon group may also be substituted by -O-, -S- or -NH-).

[2] The compound according to [1], which has a divalent group represented by formula (2-1) or formula (2-2):

(wherein, Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² respectively represent the same meanings as defined in [1]; E ¹ and E ² respectively Independently represents a single bond or a divalent linking group; B ¹ and B ² each independently represent a single bond or a divalent linking group; and A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic ring The hydrocarbon group and the aromatic hydrocarbon group may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a fluorocarbon having 1 to 4 carbon atoms. An oxy group, a cyano group or a nitro group; k and l each independently represent an integer of 0 to 3).

[3] The compound of [1], which is represented by formula (3-1) or formula (3-2): (wherein Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k And l respectively represent the same meanings as defined in the items [1] and [2]; F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms; and the alkanediyl group may also have a carbon number of 1 to An alkyl group of 5, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and -CH ₂ - of the alkanediyl group may be substituted by -O- or -CO-; and P ¹ and P ² each independently represent a hydrogen atom or Polymerizable group).

[4] The compound according to any one of [1] to [3] wherein Y ¹ is a group represented by the formula (Y ¹ -1) or the formula (Y ¹ -4):

(wherein Z ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. a sulfinyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an N,N-dialkylamine having 2 to 8 carbon atoms Base, N-alkylamino group having 1 to 4 carbon atoms, amine sulfonyl group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dialkylamine sulfonate having 2 to 12 carbon atoms Mercapto or -COOH; V ¹ represents -CO-, -S-, -NR ³ -, -O-, -Se- or -SO ₂ -; W ¹ , W ² , W ³ , W ⁴ and W ⁵ respectively Independently represents -CR ³ = or -N=, and R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; however, among V ¹ , W ¹ , W ² , W ³ , W ⁴ and W ⁵ At least one of the lines contains S, N, O or Se; a each independently represents an integer from 0 to 3.

[5] The compound according to [4], wherein the group represented by the formula (Y ¹ -1) is a group represented by the formula (Y ³ -1), and is represented by the formula (Y ¹ -4) The base is the base shown by the formula (Y ³ -3):

(wherein, Z ³ , a, V ¹ and W ² respectively have the same meanings as defined in the item [4]).

[6] The compound of [4] or [5], wherein V ¹ is -S-, -NR ³ -, or -O-.

[7] The compound according to any one of [1] to [6] wherein G ¹ and G ² are trans-1,4-cyclohexanediyl.

[8] The compound according to any one of [2] to [7] wherein A ¹ and A ² are each independently represented by a 1,4-phenylene group or a 1,4-cyclohexanediyl group. The 4-phenylene group and the 1,4-cyclohexanediyl group may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a cyano group or a nitro group.

[9] of [3] to a compound of any one of [8], wherein, only in conjunction with the A ¹ and B ¹ A B ² binds only to the ² each independently represent -CH ₂ -CH ₂ -, - CO-O -, - O- CO -, - CO-NH -, - NH-CO -, - O-CH 2 -, - CH 2 -O- or a single bond, F B binding to the binding ¹¹ and to B ^{2 of} F ² independently represents -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or a single bond.

[10] The compound according to any one of [3] to [9], wherein P ¹ and P ² each independently represent a hydrogen atom, an acryloxy group or a methacryloxy group, and P ¹ and P ^{2 is} not a hydrogen atom at the same time.

[11] A composition comprising the compound of any one of [1] to [10] and a liquid crystal compound (except that is different from the aforementioned compound).

[12] The composition of [11], wherein the liquid crystal compound is a liquid crystal compound represented by formula (20):

(In the formula, A ¹¹ each independently represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group, and the heterocyclic group may have a halogen atom, An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, and a nitro group , cyano or thio; B ¹¹ and B ¹² each independently represent -CR ¹⁴ R ¹⁵ -, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S) -O-, -OC(=S)-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O) -, -OCH ₂ -, -OCF ₂ -, -NR ¹⁶ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-, -OC(=O)- CH=CH- or a single bond, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, or R ¹⁴ and R ^{15 are} bonded together to represent a carbon number of 4 to 7 alkane. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms; and the alkanediyl group may have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to a halogen atom or an alkoxy group of 6; P ¹¹ represents a polymerizable group; G represents a hydrogen atom a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, and a carbon number of 2 to 26 An N,N-dialkylamino group, a cyano group or a nitro group, or an alkyl group having 1 to 18 carbon atoms having a polymerizable group, and the alkyl group may have an alkoxy group having 1 to 6 carbon atoms or a halogen atom; t represents an integer from 1 to 5.

[13] The composition of [11] or [12], which further comprises a polymerization initiator.

[14] The composition according to [13], wherein the polymerization initiator contains an acetophenone-based compound.

[15] An optical film obtained by polymerizing a compound according to any one of [1] to [10].

[16] An optical film obtained by polymerizing the composition of any one of [11] to [14].

[17] The optical film of [15] or [16], which is a λ/4 plate having a phase difference (Re(550)) at a wavelength of 550 nm of 113 to 163 nm.

[18] The optical film of [15] or [16], which is a λ/2 plate having a phase difference (Re(550)) at a wavelength of 550 nm of 250 to 300 nm.

[19] A polarizing plate comprising the optical film of any one of [15] to [18] and a polarizing film.

[20] A color filter which is formed on an alignment film coated on a color filter substrate to form an optical film according to any one of [15] to [18].

[21] A liquid crystal display device comprising the color filter of [20].

[22] A flat panel display device comprising a liquid crystal panel comprising the polarizing plate of [19].

[23] An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate of [19].

[24] A method for producing an unpolymerized film, which comprises applying a solution comprising the compound of any one of [1] to [10] on a support substrate or on an oriented film formed on a support substrate. Dry again.

[25] A method of producing an optical film, comprising: curing an unpolymerized film obtained by the method of [24].

The compound of the present invention contains a divalent group represented by the following formula (1-1) or formula (1-2).

In the formulae (1-1) and (1-2), Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a carbon number of 1 to 6. Alkylsulfinyl group, alkylsulfonyl group having 1 to 6 carbon atoms, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, carbon An N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylamine sulfonyl group having 1 to 6 carbon atoms, and a carbon number of 2 to 12 , N-dialkylamine sulfonyl or -COOH.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom, a chlorine atom or a bromine atom.

The alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group or a hexyl group, and is preferably a carbon number. The alkyl group of 1 to 4 is more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

The alkylsulfinyl group having 1 to 6 carbon atoms may, for example, be a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group or a butylsulfinylene group. Base, isobutylsulfinyl, t-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl and hexylsulfinyl, preferably a carbon number of 1 to 4 The sulfinyl group is more preferably an alkylsulfinyl group having 1 to 2 carbon atoms, particularly preferably a methylsulfinyl group.

The alkylsulfonyl group having 1 to 6 carbon atoms may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl or isobutylsulfonate. An anthracenyl group, a second butyl sulfonyl group, a tert-butylsulfonyl group, a pentylsulfonyl group and a hexylsulfonyl group, preferably an alkylsulfonyl group having 1 to 4 carbon atoms, more preferably a carbon number of 1 The alkylsulfonyl group to 2 is particularly preferably a methylsulfonyl group.

The fluoroalkyl group having 1 to 6 carbon atoms may, for example, be a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group or a nonafluorobutyl group, and preferably a fluorine having a carbon number of 1 to 4. The alkyl group is more preferably a fluoroalkyl group having 1 to 2 carbon atoms, particularly preferably a trifluoromethyl group.

The alkoxy group having 1 to 6 carbon atoms may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group or a third butoxy group. The pentyloxy group and the hexyloxy group are preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, and particularly preferably a methoxy group.

The alkylthio group having 1 to 6 carbon atoms may, for example, be a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a second butylthio group or a third butylthio group. The pentylthio group and the hexylthio group are preferably an alkylthio group having 1 to 4 carbon atoms, more preferably an alkylthio group having 1 to 2 carbon atoms, and particularly preferably a methylthio group.

Examples of the N-alkylamine group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, and N-butylamine. Base, N-isobutylamino group, N-second butylamino group, N-tert-butylamino group, N-pentylamino group and N-hexylamino group, preferably having a carbon number of 1 to 4 The alkylamino group is more preferably an N-alkylamino group having 1 to 2 carbon atoms, particularly preferably an N-methylamino group.

Examples of the N,N-dialkylamino group having 2 to 12 carbon atoms include N,N-dimethylamino group, N-methyl-N-ethylamino group, and N,N-diethylamino group. , N,N-dipropylamino, N,N-diisopropylamino, N,N-dibutylamino, N,N-diisobutylamino, N,N-dipentyl An amine group, N,N-dihexylamino group, preferably an N,N-dialkylamino group having 2 to 8 carbon atoms, more preferably an N,N-dialkylamino group having 2 to 4 carbon atoms, especially It is preferably an N,N-dimethylamino group.

Examples of the N-alkylamine sulfonyl group having 1 to 6 carbon atoms include N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, and N-isopropyl group. Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl and N-hexylamine sulfonyl, preferably an N-alkylamine sulfonyl group having 1 to 4 carbon atoms, more preferably an N-alkylamine sulfonyl group having 1 to 2 carbon atoms, particularly preferably It is an N-methylamine sulfonyl group.

The N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms may, for example, be N,N-dimethylaminesulfonyl, N-methyl-N-ethylaminesulfonyl, N,N. -diethylamine sulfonyl, N,N-dipropylamine sulfonyl, N,N-diisopropylamine sulfonyl, N,N-dibutylamine sulfonyl, N,N- Diisobutylamine sulfonyl, N,N-dipentylamine sulfonyl and N,N-dihexylamine sulfonyl, preferably N,N-dialkylamine sulfonate having 2 to 8 carbon atoms The group is more preferably an N,N-dialkylamine sulfonyl group having 2 to 4 carbon atoms, particularly preferably N,N-dimethylamine sulfonyl group.

Z ¹ and Z ² should independently represent a hydrogen atom, a halogen atom, a methyl group, a cyano group, a nitro group, a methylsulfonyl group, a trifluoromethyl group, a methoxy group, a methylthio group or an N-methylamino group. , N,N'-dimethylamino, N-methylaminesulfonyl, N,N'-dimethylaminesulfonyl or -COOH.

In the formulae (1-1) and (1-2), Q ¹ and Q ² each independently represent -CR ¹ R ² -, -S-, -NR ² -, -CO- or O-, R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms in R ¹ and R ² may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group, and preferably has a carbon number of 1 to 2 alkyl, more preferably methyl.

Q ¹ and Q ² should independently represent -S-, -CO-, -NH-, -N(CH ₃ )-, more preferably -S- or -CO-.

The group represented by the formula (1-1-A) in the divalent group represented by the formula (1-1) may, for example, be represented by the following formula (1-1-1) to formula (1-1-18). The base shown.

The group represented by the formula (1-2-A) in the divalent group represented by the formula (1-2) is, for example, the following formula (1-2-1) to the formula (1-2-5). ) The base shown.

In the formula (1-1) and the formula (1-2), Y ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group. The "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and examples thereof include a condensed aromatic hydrocarbon group formed by condensation of two or more aromatic rings and an aromatic bond formed by combining two or more aromatic rings. A hydrocarbon group. The "polycyclic aromatic heterocyclic group" means an aromatic heterocyclic group having at least one heterocyclic aromatic ring and having at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring, and is exemplified. An aromatic heterocyclic group formed by condensing one or more aromatic heterocyclic rings with one or more selected from the group consisting of an aromatic ring and a heteroaromatic ring, and at least one heteroaromatic ring An aromatic heterocyclic group formed by bonding at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring.

The polycyclic aromatic hydrocarbon group and the polycyclic aromatic heterocyclic group may be unsubstituted or may have a substituent. The substituent group may, for example, be a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, or an alkylsulfonyl group having 1 to 6 carbon atoms. Mercapto group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, carbon number 2 to An N,N-dialkylamino group, an amine sulfonyl group, an N-alkylamine sulfonyl group having 1 to 6 carbon atoms, an N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms or -COOH.

Y ^{1 is} preferably a group represented by the formula (Y ¹ -1) to the formula (Y ¹ -7), and more preferably a group represented by the formula (Y ¹ -1) to the formula (Y ¹ -4).

(wherein Z ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. a sulfinyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an N,N-dialkylamine having 2 to 8 carbon atoms Base, N-alkylamino group having 1 to 4 carbon atoms, amine sulfonyl group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dialkylamine sulfonate having 2 to 12 carbon atoms Mercapto or -COOH; V ¹ and V ² independently represent -CO-, -S-, -NR ² -, -O-, -Se- or -SO ₂ -; W ¹ , W ² , W ³ , W ⁴ and W ⁵ each independently represent -CR ³ = or -N=, and R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; however, V ¹ , V ² , W ¹ , W ² , W ³ , At least one of W ⁴ and W ⁵ contains S, N, O or Se; a each independently represents an integer of 0 to 3, and b each independently represents an integer of 0 to 2).

To the formula (Y ² -6) the group shown in the groups is suitably shown in the formula (Y ¹ -1) In formula (Y ² -1) according to any one.

The base represented by the formula (Y ¹ -2) is a group represented by the formula (Y ² -7) or the formula (Y ² -9), and the formula represented by the formula (Y ¹ -3) is preferably A group represented by the formula (Y ² -8) or the formula (Y ² -10).

The group represented by the formula (Y ¹ -4) is any one of the groups represented by the formula (Y ² -11) to the formula (Y ² -13).

The group represented by the formula (Y ¹ -5) is any one of the groups represented by the formula (Y ² -14) to the formula (Y ² -16).

More preferably, it is any one of the groups represented by the formula (Y ³ -1) to the formula (Y ³ -6).

(wherein, Z ³ , V ¹ , V ² , W ¹ , W ² , W ³ , W ⁴ , W ⁵ , a and b represent the same meaning as described above) a halogen atom in Z ³ , a carbon number of 1 to 6 Alkyl group, alkylsulfonyl group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, carbon Alkanethio group having 1 to 6 alkyl groups, N,N-dialkylamino group having 2 to 8 carbon atoms, N-alkylamino group having 1 to 4 carbon atoms, and N-alkylamine sulfonyl having 1 to 6 carbon atoms Examples of the fluorenyl group and the N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms are the same as those described above.

Wherein Z ^{3 is} preferably a halogen atom, a methyl group, an ethyl group, an isopropyl group, a second butyl group, a pentyl group, a hexyl group, a cyano group, a nitro group, a methylsulfonyl group, a nitroso group, a trifluoromethyl group, Methoxy, methylsulfonyl, N,N-dimethylamino, N-methylamino or -COOH, more preferably a halogen atom, a methyl group, an ethyl group, an isopropyl group, a second butyl group , pentyl, hexyl, cyano, nitro, trifluoromethyl, especially preferably methyl, ethyl, isopropyl, t-butyl, pentyl or hexyl.

V ¹ and V ² should each independently be -S-, -NR ³ - or -O-.

W ¹ to W ⁵ should be independently -CR ³ = or -N=.

At least one of V ¹ , V ² and W ¹ to W ⁵ preferably contains S, N or O.

a should be 0 or 1, and b should be 0.

Specific examples of Y ¹ include, for example, a group represented by the formula (ar-1) to the formula (ar-840). Further, in the following groups, Me represents a methyl group, Et represents an ethyl group, and * represents a binding site.

In the formulae (1-1) and (1-2), D ¹ and D ² each independently represent a single bond or a divalent linking group. The divalent linking group may, for example, be -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -CR ⁴ R ⁵ -, -CR ⁴ R ⁵ - CR ⁶ R ⁷ -, -O-CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -O-, -CR ⁴ R ⁵ -O-CR ⁶ R ⁷ -, -CR ⁴ R ⁵ -O-CO-, - ^{O-CO-CR 4 R 5} -, - CR 4 R 5 -O-CO-CR 6 R 7 -, - CR 4 R 5 -CO-O-CR 6 R 7 -, - NR 8 -CR 4 R 5 ^{-, - CR 4 R 5 -NR} 8 -, - CO-NR 8 -, - NR 8 -CO -, - O -, - S -, - NR 8 -, and -CR ⁴ = CR ⁵ -. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.).

D ¹ and D ^{2 are} preferably *-O-CO-, *-OC(=S)-, *-O-CR ⁴ R ⁵ -, *-NR ⁸ -CR ⁴ R ⁵ - or *-NR ⁸ -CO More preferably, it is *-O-CO-, *-OC(=S)- or *-NR ⁸ -CO. Here, * represents a binding site of a group represented by the formula (1-1-A) or a group represented by the formula (1-2-A). R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group. R ^{8 is} preferably a hydrogen atom, a methyl group or an ethyl group.

In the formulae (1-1) and (1-2), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom of the alicyclic hydrocarbon group may also pass through a halogen atom and have a carbon number of 1 to 4. An alkyl group, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the -CH _{2 of} the alicyclic hydrocarbon group may also be subjected to -O-, -S- Or -NH- substituted.

The number of carbon atoms and hetero atoms constituting the ring of the divalent alicyclic hydrocarbon group may, for example, be a divalent alicyclic hydrocarbon group of 3 to 10 and 0 to 2, and preferably a formula (g-1) to a formula (g-). 10) The base shown is preferably a 5-member ring or a 6-member ring.

The hydrogen atom of the group represented by the above formula (g-1) to the formula (g-10) may be an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a t-butyl group; Alkoxy group having 1 to 4 carbon atoms such as an oxy group or an ethoxy group; fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. G ¹ and G ^{2 are} preferably a group represented by the formula (g-1), more preferably a 1,4-cyclohexanediyl group, and particularly preferably a trans-1,4-cyclohexanediyl group.

The compound of the present invention is preferably a compound containing a divalent group represented by formula (2-1) or formula (2-2):

(wherein, Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² respectively have the same meanings as described above; and E ¹ and E ² each independently represent a single bond or 2 a valent linking group; B ¹ and B ² each independently represent a single bond or a divalent linking group; and A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic group The hydrocarbon group may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, or a cyano group or Nitro; k and 1 each independently represent an integer from 0 to 3).

The divalent linking group in E ¹ and E ² may, for example, be -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, - O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, - O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S-, -NR ¹¹ -, and -CR ⁹ =CR ¹⁰ -. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E ¹ and E ² should be independently -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -CH ₂ -O-, -CH ₂ -S- or a single bond, more preferably -CO-O-.

The divalent linking group in B ¹ and B ² may, for example, be -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, - O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, - O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S-, -NR ¹¹ -, and -CR ⁹ =CR ¹⁰ -. For easy manufacture of the compounds of the present invention, it should only bind to B A ^{1 1} and only binds to A ² B ² each independently represent the _{-CH 2 -CH 2 - O-CO-} -, - CO-O -, -CO-NH-, -NH-CO-, -O-CH ₂ -, -CH ₂ -O- or a single bond, in the case where the compound of the present invention exhibits high liquid crystallinity, it is preferably -CO-O- Or -O-CO-.

Insofar as it is easier to manufacture the compounds of the invention, it is preferred that B ¹ and B ² are the same. The divalent alicyclic hydrocarbon group or the divalent aromatic hydrocarbon group in A ¹ and A ² may, for example, be a group represented by the above formula (g-1) to formula (g-10), and have the following formula (a-1) a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (a-8).

The hydrogen atom having a group represented by the above formula (a-1) to formula (a-8) may also be an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; Alkoxy group having 1 to 4 carbon atoms such as an oxy group or an ethoxy group; fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

Wherein, A ¹ and A ² are each independently a 1,4-phenylene group or a 1,4-cyclohexanediyl group, and it is more preferable to produce a compound of the present invention, more preferably a 1,4-phenylene group. .

Insofar as it is easier to manufacture the compounds of the invention, it is preferred that A ¹ and A ² are the same. From the viewpoint of the liquid crystallinity of the compound of the present invention, k and 1 are from 0 to 2. The sum of k and 1 is preferably 5 or less, more preferably 4 or less.

The compound of the present invention is more preferably a compound represented by formula (3-1) or formula (3-2):

(wherein Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k And 1 respectively have the same meanings as described above; F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms; the alkanediyl group may also have an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5 the alkoxy group or a halogen atom, the alkyl group of the two -CH ₂ - may by -O -, - CO- substituted; P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group).

The alkanediyl group having 1 to 12 carbon atoms in F ¹ and F ² is preferably -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₉ -, -(CH ₂ ) ₁₀ -, -(CF ₂ ) ₄ -, -(CF ₂ ) ₆ -, and - (CF ₂ ) ₈ -, more preferably -(CH ₂ ) ₄ -, and -(CH ₂ ) ₆ -.

B ^{1 which is} preferably bound to F ¹ and B ² which is bound to F ² are independently -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, - NH-CO- or single bond.

At least one of P ¹ and P ² is preferably a polymerizable group, and in view of the fact that the optical film obtained from the compound of the present invention has excellent film hardness, P ¹ and P ² are more preferably a polymerizable group.

The polymerizable group may be a group which can participate in the polymerization reaction of the compound of the present invention, and specific examples thereof include a vinyl group, a vinyloxy group, a styryl group, a p-(2-phenylvinyl)phenyl group, and an acrylonitrile group. a group, a methacryl oxime group, a propylene oxime group, a methacryloxy group, a carboxyl group, an ethyl fluorenyl group, a hydroxyl group, an aminomethyl fluorenyl group, an N-alkylamino group having 1 to 4 carbon atoms, an amine group, An epoxy group, an oxetanyl group, a decyl group, an isocyanate group, and an isothiocyanate group. Among them, a point suitable for photopolymerization, preferably a radical polymerizable group or a cationic polymerizable group, is easy to handle and the compound of the present invention is also easy to manufacture, and is more preferably an acryloxy group or a methacryl group. The decyloxy group is particularly preferably an acryloxy group.

The polymerizable group may be directly bonded to F ¹ and F ² , but it is preferably bonded via one or more divalent linking groups (for example, a divalent linking group in the above B ¹ and B ² ).

-D ¹ -G ¹ -E ¹ -(A ¹ -B ¹ ) _k -F ¹ -P ¹ and -D ² -G ² -E ² -(A ² -B ² ) ₁ -F ² -P ² Specific examples thereof include a group represented by the formula (R-1) to the formula (R-134). Further, in the following formula, * represents a binding site to a group represented by the formula (1-1-A) or the formula (1-2-A), and n represents an integer of 2 to 12.

The compound of the present invention may, for example, be a compound represented by the formula (A1-1) to the formula (A73-8). Further, in the following formula, * represents a binding site, and for example, the compound represented by the formula (A1-1) is a compound described below.

Next, a method for producing the compound of the present invention will be described.

The compound of the present invention is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, etc. (for example, condensation reaction, esterification reaction, William Son reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, taro reaction, Suzuki-Miyaura reaction, root bank reaction, bear field reaction, Laoshan reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol The reaction or the like is produced by appropriately combining the structures according to the structure.

For example, a compound represented by the formula (3-1) or the formula (3-2) in which D ¹ and D ² are *-O-CO- can be obtained by using a compound represented by the formula (11-1) The compound represented by the formula (11-2) is reacted to obtain a compound represented by the formula (11-3), and the compound represented by the formula (11-3) is obtained by using the compound represented by the formula (11-3) The compound shown is reacted to produce: HO-Ar-OH (11-1) (wherein Ar represents a divalent group represented by the above formula (1-1) or the above formula (1-2))

(wherein, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above)

(wherein Ar, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above)

(wherein, G ² , E ² , A ² , B ² , F ² , P ² and 1 represent the same meanings as described above).

Further, when G ¹ and G ² , E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , F ¹ and F, P ¹ and P ^{2 ,} and k and l are all the same, respectively, The compound of the formula (11-1) is reacted with 2 equivalents or more of the compound of the formula (11-2) to produce a compound of interest in one stage.

Reaction of a compound represented by the formula (11-1) with a compound represented by the formula (11-2), and a compound represented by the formula (11-3) and a compound represented by the formula (11-4) The reaction is preferably carried out in the presence of a condensing agent.

The condensing agent may, for example, be 1-cyclohexyl-3-(2-morpholinoethyl)carbonyldiazide imine p-toluenesulfonate, dicyclohexylcarbonyldiimide, 1-ethyl-3-(3) -Dimethylaminopropyl)carbonyldiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride, bis(2,6-diiso) a carbonyldiamine compound such as propylphenyl)carbonyldiamine, bis(trimethyldecyl)carbonyldiimide, N,N'-diisopropylcarbonyldiimide, or the like; -6-nitrobenzoic anhydride, 2,2'-carbonyl bis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenyl azide phosphate, 1 (4-nitrophenylsulfonyl) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxy hexafluorophosphate Tris(dimethylamino)phosphonium salt, N,N,N',N'-tetramethyl-O-(N-ammonium imino)urea salt, N-(1, 2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazole) -1-yl)-N,N,N',N'-tetramethyluronium salt, O-(6-chlorobenzotriazol-1-yl)-N,N,N hexafluorophosphate ',N'-tetramethyluronium salt, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolium chloride, hexafluorophosphate 2- Chloro-1,3-dimethylimidazolinium salt, 2-chloro-1-methylpyridinium iodide salt, 2-chloro-1-methylpyridinium salt of p-toluenesulfonate, 2-p-toluenesulfonic acid Fluoro-1-methylpyridinium salt, pentachlorophenyl trichloroacetate, and the like. From the viewpoints of many reactivity, cost, and selectivity of the solvent that can be used, it is preferably dicyclohexylcarbonyldiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiazine. Amine, 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride, bis(2,6-diisopropylphenyl)carbonyldiimide, double Trimethyldecyl)carbonyldiimide, N,N'-diisopropylcarbonyldiimide, and 2,2'-carbonylbis-1H-imidazole.

Next, the composition relating to the present invention will be explained. The composition of the present invention comprises a compound of the present invention and a liquid crystal compound different from the compound of the present invention.

Specific examples of the liquid crystal compound are, for example, "Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Compilation Committee, Maruzen Co., Ltd., issued on October 30, 2004), Chapter 3 Molecular Structure and Liquid Crystallinity, 3.2 Non-Planar Rod Liquid Crystals A compound having a polymerizable group among the molecules described in "3.3 palmar rod-like liquid crystal molecules".

One type of liquid crystal compound can be used, and two or more types of liquid crystal compounds can also be used.

By using the composition containing the compound of the present invention and a liquid crystal compound, optical characteristics such as a wavelength dispersion value or a phase difference value of the optical film obtained by polymerizing the composition can be adjusted to a desired value.

The liquid crystal compound may, for example, be a liquid crystal compound represented by the formula (20) (hereinafter sometimes referred to as a compound (20)) or the like:

(In the formula, A ¹¹ each independently represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group, and the heterocyclic group may have a halogen atom, An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, and a nitro group , cyano or thio; B ¹¹ and B ¹² each independently represent -CR ¹⁴ R ¹⁵ -, -C≡ C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S) -O-, -OC(=S)-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O) -, -OCH ₂ -, -OCF ₂ -, -NR ¹⁶ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-, -OC(=O)- CH=CH- or a single bond, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, or R ¹⁴ and R ^{15 are} bonded together to represent a carbon number of 4 to 7 alkane. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms; and the alkanediyl group may have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 Alkoxy or halogen atom to 6; P ¹¹ represents a polymerizable group; G represents a hydrogen atom a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, and a carbon number of 2 to An N,N-dialkylamino group, a cyano group or a nitro group having 26 or a carbon number of 1 to 18 having a polymerizable group, and the alkyl group may have an alkoxy group having 1 to 6 carbon atoms or a halogen atom; t represents an integer from 1 to 5.

In particular, the polymerizable group in P ¹¹ and G may be a group which can be polymerized with the compound of the present invention, and examples thereof include a vinyl group, a vinyloxy group, a styryl group, and a p-(2-phenylvinyl group). Phenyl, propylene fluorenyl, propylene decyloxy, methacryl fluorenyl, methacryloxy group, carboxyl group, ethyl hydrazino group, hydroxyl group, aminomethyl fluorenyl group, amine group, N to carbon number 1 to 4 Alkylamino group, epoxy group, oxetanyl group, formamyl group, -N=C=O or -N=C=S, and the like. In particular, in view of high reactivity of photopolymerization, a radical polymerizable group or a cationic polymerizable group is preferred, and in terms of ease of handling, the production of a liquid crystal compound is also easy, and it is preferably an acryloxy group or a methyl group. Acryloxy or vinyloxy.

Further, the carbon number of the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group of A ¹¹ is preferably from 3 to 18, more preferably from 5 to 12, particularly preferably 5 or 6.

The compound (20) may, for example, be a compound represented by the formula (20-1) and the formula (20-2): P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t1 - B ¹² -E ¹² -P ¹² ( 20-1) P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t2 -B ¹² -F ¹¹ (20-2) (wherein P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² represent the above The same meaning; F ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, and N having a carbon number of 1 to 13. An alkylamino group, a N,N-dialkylamino group having 2 to 26 carbon atoms, a cyano group or a nitro group; E ¹² represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group may have a carbon number of 1 An alkyl group of 6, an alkoxy group having 1 to 6 carbon atoms or a halogen atom; P ¹² represents a polymerizable group; and t ¹ and t ² represent an integer of 1 to 5).

The compounds represented by the formulae (20-1) and (20-2) may, for example, be a compound represented by the formula (I), the formula (II), the formula (III), the formula (IV) and the formula (V). :P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -A ¹⁵ -B ¹⁶ -E ¹² -P ¹² (I)P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -E ¹² -P ¹² (II)P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -E ¹² -P ¹² (III)P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -F ¹¹ (IV)P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -F ¹¹ (V) (wherein A ¹² to A ¹⁵ represent the same meaning as A ¹¹ , B ¹³ to B ^{16 have the} same meaning as B ¹¹ ).

P ¹¹ and E ¹¹ are preferred among the compounds represented by formula (20-1), (20-2), formula (I), formula (II), formula (III), formula (IV) and formula (V). The bond is an ether bond or an ester bond, and it is preferred that the bond between P ¹² and E ¹² is an ether bond or an ester bond.

Specific examples of the liquid crystal compound include, for example, the formula (I-1) to the formula (I-5), the formula (B1-1) to the formula (B20-8), and the formula (C1-1) to the formula (C4-8). a compound represented by the formula (I), a compound represented by the formula (II-1) to the formula (II-6), and the like, a compound represented by the formula (II); a compound represented by the formula (III-19), such as a compound represented by the formula (III); a compound represented by the formula (IV-1) to the formula (IV-14), etc., represented by the formula (IV) A compound represented by the formula (V), a compound represented by the formula (V-1) to the formula (V-5), or the like. Further, in the following formula, k represents an integer of 1 to 11, and * represents a binding site. These liquid crystal compounds are preferred liquid crystal compounds because they are easily synthesized or commercially available and are easily available.

When a composition containing a liquid crystal compound is used for the purpose of controlling the thermal properties of the obtained optical film, it is preferable to use the formula (I-1) to formula (I) in terms of excellent reliability of the obtained optical film. -5), formula (B1-1) to formula (B20-8), (C1-1) to formula (C4-8), formula (II-1) to formula (II-6) and formula (III-1) The liquid crystal compound represented by the formula (III-19) is preferably of the formula (I-1) to the formula (I-5) or the formula (B1-1) in terms of excellent compatibility with the compound of the present invention. The liquid crystal compounds of the formula (B20-8), (C1-1) to (C4-8) and the formula (III-1) to the formula (III-19). In the case of an optical film exhibiting reverse wavelength dispersion, a liquid crystal compound represented by the formula (B1-1) to the formula (B20-8) and (C1-1) to the formula (C4-8) is preferable.

The amount of the liquid crystal compound used is generally 90 parts by weight or less based on 100 parts by weight of the total of the liquid crystal compound and the compound of the present invention. The composition of the present invention preferably further comprises a polymerization initiator. The polymerization initiator preferably contains a photopolymerization initiator, and the photopolymerization initiator is preferably a photopolymerization initiator which generates a radical by irradiation with light.

The photopolymerization initiator may, for example, be a benzoin compound, a benzophenone compound, an acetophenone compound, a mercaptophosphine oxide compound, or the like. Compounds, iodonium salts and sulfonium salts.

The benzoin compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether.

The benzophenone compound may, for example, be benzophenone, methyl orthobenzoyl benzoate, 4-phenylbenzophenone or 4-benzylidene-4'-methyldiphenyl sulfide. 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

The acetophenone compound may, for example, be α,α-diethoxyethyl benzene, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-benzene. Methyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1, 2-diphenyl-2,2-dimethoxy-1-ethanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one An oligomer of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide.

three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri .

For the photopolymerization initiator, Irgacure 907 (manufactured by Ciba Japan Co., Ltd.), Irgacure 184 (manufactured by Ciba Japan Co., Ltd.), Irgacure 651 (manufactured by Ciba Japan Co., Ltd.), and Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can be used. , Irgacure 250 (manufactured by Ciba Japan Co., Ltd.), Irgacure 369 (manufactured by Ciba Japan Co., Ltd.), SEIKUOL BZ (made by Seiko Chemical Co., Ltd.), SEIKUOLZ (made by Seiko Chemical Co., Ltd.), SEIKUOL BEE (Seiko Chemicals Co., Ltd.) Co., Ltd.), KAYACURE BP100 (manufactured by Nippon Chemical Co., Ltd.), KAYACURE UVI-6992 (manufactured by DOW Co., Ltd.), ADEKA OPTOMER SP-152 (manufactured by ADEKA Co., Ltd.), ADEKA OPTOMER SP-170 (manufactured by ADEKA Co., Ltd.) ), TAZ-A (manufactured by Siber Hegner, Japan), TAZ-PP (manufactured by Siber Hegner, Japan), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

In view of the tendency of the obtained optical film to have high heat resistance and moist heat resistance, the photopolymerization initiator is preferably acetophenone, more preferably 2-benzyl-2-dimethylamino group- 1-(4-morpholinylphenyl)-1-butanone. The content of the polymerization initiator in the composition of the present invention is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound of the present invention. If it is in the above range, the compound of the present invention can be polymerized without disturbing the orientation of the liquid crystal compound.

The composition of the present invention may also contain a photosensitizer. The photosensitizer may, for example, be an xanthone compound such as xanthone or thioxanthone (for example, 2,4-diethylthiazinone or 2-isopropylthioxanthene). a ketone or the like, a ruthenium compound, a ruthenium compound having a substituent such as an alkoxy group (for example, dibutoxy fluorene, etc.), and thiophene (phenothiazine) and rubrene.

By using a photosensitizing agent, the polymerization reaction of the compound of the present invention can be carried out with high sensitivity, and the temporal stability of the obtained optical film can be improved. The content of the photosensitizer is usually from 0.1 to 30 parts by weight, preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total of the liquid crystal compound and the compound of the present invention. When it is in the above range, the compound of the present invention can be polymerized without disturbing the orientation of the liquid crystal compound.

The composition of the present invention may also comprise a polymerization inhibitor. Examples of the polymerization inhibitor include a hydroquinone compound having a substituent such as a hydroquinone or an alkoxy group, a catechol compound having a substituent such as an alkyl group such as a butyl catechol, a pyrogallol compound, and 2, 2, and 6. a radical scavenger such as a 6-tetramethyl-1-piperidinyloxy radical, a thiophenol compound, a β-naphthylamine compound, or a β-naphthol compound.

By using a polymerization inhibitor, the polymerization reaction of the liquid crystal compound or the compound of the present invention can be easily controlled, and the stability of the obtained optical film can be improved. The content of the polymerization inhibitor is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by total of the total of the liquid crystal compound and the compound of the present invention. Within the above range, the compound of the present invention can be polymerized without disturbing the orientation of the liquid crystal compound.

The composition of the present invention may also contain a leveling agent. The coating agent may, for example, be an additive for a radiation hardening coating (BYK Japan, BYK-352, BYK-353, BYK-361N), a coating additive (manufactured by Toray Dow Corning Co., Ltd.: SH28PA, DC11PA, ST80PA), and a coating additive. (Shin-Etsu Chemical Co., Ltd.: KP321, KP323, X22-161A, KF6001), fluorine-based additives (made by DIC Corporation: F-445, F-470, F-479).

By using a leveling agent, a smoother optical film can be obtained. Further, in the production process of the optical film, the fluidity of the composition of the present invention or the crosslinking density in the obtained optical film can be controlled. The content of the leveling agent is usually from 0.01 to 30 parts by weight, preferably from 0.05 to 10 parts by weight, per 100 parts by weight of the total of the liquid crystal compound and the compound of the present invention. Within the above range, the compound of the present invention can be polymerized without disturbing the orientation of the liquid crystal compound.

The composition of the present invention preferably contains an organic solvent in terms of its fluidity. The organic solvent is not particularly limited as long as it is an organic solvent which dissolves the compound of the present invention, a liquid crystal compound or the like and is inert to the polymerization reaction, and specific examples thereof include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, and B. Alcohol solvents such as glycol methyl ether and ethylene glycol butyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, lactic acid Ester solvent such as ethyl ester; ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; non-chlorine such as pentane, hexane or heptane Aliphatic hydrocarbon solvent; non-chlorinated aromatic hydrocarbon solvent such as toluene, xylene, phenol; nitrile solvent such as acetonitrile; ether solvent such as propylene glycol monomethyl ether, tetrahydrofuran or dimethoxyethane; chloroform, chlorobenzene Isochlorinated hydrocarbon solvent; phenol and the like. These organic solvents may be used singly or in combination of two or more kinds. In particular, the compound of the present invention and the composition of the present invention are excellent in compatibility, and are soluble in an alcohol solvent, an ester solvent, a ketone solvent, a non-chlorinated aliphatic hydrocarbon solvent, and a non-chlorinated aromatic hydrocarbon solvent. Film formation without using a chlorinated hydrocarbon solvent such as chloroform.

The content of the organic solvent is usually 10 to 10,000 parts by weight, preferably 100 to 5,000 parts by weight, based on 100 parts by weight of the compound of the present invention.

When the composition of the present invention contains an organic solvent, the viscosity thereof tends to be less likely to cause uneven film thickness of the optical film, and is usually 0.1 to 10 Pa‧s, preferably 0.1 to 7 Pa‧s.

The concentration of the solid component in the composition of the present invention is generally from 2 to 50% by weight, preferably from 5 to 50% by weight. When the concentration of the solid content is 2% by weight or more, the optical film is not too thin, and there is a tendency that an optical film having a birefringence required for optical compensation of the liquid crystal panel can be easily obtained. Further, when the concentration of the solid content is 50% by weight or less, the viscosity of the composition is not too small, and the film thickness unevenness of the optical film tends to be less likely to occur. Here, the "solid content" means a component remaining after removing an organic solvent from the composition of the present invention.

Next, an optical film relating to the present invention will be described.

In the present invention, the term "optical film" means a film which can penetrate light through a film and has an optical function. Optical function means refraction, birefringence, and the like. A retardation film of one type of optical film is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or vice versa to convert circularly polarized light or elliptically polarized light into linearly polarized light.

The optical film of the present invention has a structural unit derived from the compound of the present invention, but the wavelength dispersion characteristics of the optical film can be adjusted by adjusting the content of the structural unit. When the content of the structural unit derived from the compound of the present invention in the optical film is increased, it exhibits flatter wavelength dispersion characteristics and further inverse wavelength dispersion characteristics.

Specifically, the composition of the present invention containing an optical film having a content of a structural unit derived from the compound of the present invention, which is determined by the operations shown in the following (a) to (e), is prepared and The composition may be polymerized: (a) preparing a composition of the present invention in which the content of the compound of the present invention is different from about 2 to 5; (b) producing the same film thickness for each of the prepared compositions and derived from An optical film having a different structural unit content of the compound of the present invention; (c) determining a phase difference value of the optical film obtained in (b); (d) a phase difference value obtained according to (c), And determining the correlation between the content of the structural unit derived from the compound of the present invention and the phase difference of the optical film; (e) determining the correlation between the (d) and the optical film imparting the film thickness The desired phase difference value is required to be derived from the content of the building blocks of the compounds of the invention.

Generally, the phase difference value Re(λ) in a certain wavelength λ is divided by the value of the phase difference value Re (550) in 550 nm (Re(λ)/Re(550)) is close to 1 in a wide band region, or is displayed. In the wide-band region of [Re(450)/Re(550)]<1 and [Re(650)/Re(550)]>1 with inverse wavelength dispersion, the same polarization conversion can be performed.

The optical film of the present invention can be obtained by polymerizing the compound of the present invention. It is also possible to polymerize one type of the compound of the invention or to polymerize two types of the compounds of the invention. Further, the optical film of the present invention can be produced by polymerizing the compound of the present invention.

In the case of easy film formation, a solution in which the compound of the present invention is dissolved in an organic solvent is preferably used, and the solution is applied onto a support substrate, dried, polymerized, and an optical film is obtained. The solid content concentration in such a solution is generally from 2 to 50% by weight, preferably from 5 to 50% by weight.

The unpolymerized film sheet can be obtained by coating a solution of the compound of the present invention on a support substrate and drying. When the unpolymerized film shows a nematically equal liquid crystal phase, the resulting optical film system exhibits birefringence produced by monodomain orientation.

The film thickness of the optical film can be adjusted by appropriately adjusting the content of the compound of the present invention in the compound solution of the present invention or the coating amount of the solution on the support substrate. When the amount of the compound of the present invention is constant, the phase difference (retardation value, Re(λ)) of the obtained optical film is determined according to the formula (7), so that the desired Re is obtained ( λ), just adjust the film thickness d and Δn(λ).

Re(λ)=d×Δn(λ) (7)

(wherein, Re(λ) represents a phase difference value in a wavelength λ nm, d represents a film thickness, and Δn (λ) represents a birefringence in a wavelength λ nm).

The coating method of the solution of the compound of the present invention on the support substrate may, for example, be an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, or a die coating method. For example, a method of coating using an applicator such as a dip coater, a bar coater, or a spin coater may be employed.

Examples of the support substrate include glass, a plastic sheet, a plastic film, and a light-transmitting film. The translucent film may, for example, be a polyolefin film such as polyethylene, polypropylene or a norbornene-based polymer; a polyvinyl alcohol film; a polyethylene terephthalate film; a polymethacrylate film; Polyacrylate film; cellulose ester film; polyethylene naphthalate film; polycarbonate film; polysulfone film; polyether film; polyether ketone film; Phenylene sulfide film; polyphenylene oxide film and the like.

In the step of requiring the strength of the optical film, such as the bonding step, the transporting step, and the storage step of the optical film, it is possible to easily handle the optical film without damage or the like by using the supporting substrate.

After forming an oriented film on the support substrate, a solution of the compound of the present invention is applied to the oriented film. The oriented film system preferably has a solvent resistance which is insoluble in the solution when the solution of the compound of the present invention is applied. Further, the orientation film preferably has heat resistance in a heat treatment for removing a solvent or aligning liquid crystal molecules. Further, it is preferable that an oriented film such as peeling due to friction or the like does not occur during rubbing. Such an oriented film is preferably composed of a directional polymer or a composition containing a directional polymer.

The above-mentioned directional polymer may, for example, be a polyamine or a gelatin compound having a guanamine bond in the molecule, a polyamidimide having a ruthenium bond in the molecule, and a polyglycolic acid or polyvinyl alcohol having a hydrolyzate thereof. Alkyl modified polyvinyl alcohol, polypropylene decylamine, poly Polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylate. These oriented polymers may be used singly or in combination of two or more kinds. Copolymers of oriented polymers can also be used for this purpose. These oriented polymers can be easily obtained by chain polymerization such as polycondensation such as dehydration polycondensation or deamination polycondensation, radical polymerization, anionic polymerization, cationic polymerization or the like, coordination polymerization, ring-opening polymerization or the like.

These oriented polymers are generally dissolved in a solvent and used as a solution. Solvents are not limited. Specifically, for example, water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, and ethylene glycol butyl ether; ethyl acetate, butyl acetate, and ethylene glycol; An ester solvent such as methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, a ketone solvent such as methyl isobutyl ketone; a non-chlorinated aliphatic hydrocarbon solvent such as pentane, hexane or heptane; a non-chlorinated aromatic hydrocarbon solvent such as toluene or xylene; a nitrile solvent such as acetonitrile; An ether solvent such as an ether, tetrahydrofuran or dimethoxyethane; a chlorinated hydrocarbon solvent such as chloroform or chlorobenzene. These organic solvents may be used singly or in combination of two or more.

The oriented film can also be formed directly using a commercially available oriented film material. The commercially available oriented film material may, for example, be Sunever (registered trademark; manufactured by Nissan Chemical Industries, Ltd.), Optmer (registered trademark; manufactured by JSR Co., Ltd.), or the like.

If such an alignment film is used, since the refractive index control by extension is not required, the in-plane unevenness of the birefringence can be provided, and the support substrate can also be enlarged corresponding to the flat panel display device (FPD). Large optical film.

The method of forming the alignment film on the support substrate may be, for example, a method in which a commercially available alignment film material or a compound which is a material of the alignment film is formed into a solution and coated, and then annealed.

The thickness of the oriented film is generally from 10 to 10,000 nm, preferably from 10 to 1,000 nm. If it is in the above range, the compound of the present invention can be made to be oriented at the desired angle on the oriented film. The alignment film may be rubbed as needed, or may be subjected to polarized UV irradiation on the alignment film, by which the compound of the present invention or the like may be oriented in a desired direction. That is, the shape or inclination of the refractive index ellipsoid showing the birefringence state of the manufactured optical film can be adjusted.

The method of rubbing the oriented film may be, for example, a method of winding a rubbing cloth to bring the rubbing roller in rotation into contact with the oriented film carried on the stage.

The method of laminating an unpolymerized film on an oriented film laminated on such a supporting substrate can reduce the production cost as compared with the method of producing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell, and Film production diaphragm.

The removal of the solvent may be carried out in parallel with the polymerization reaction, but in terms of film formability, it is preferred to remove almost all of the solvent before the polymerization reaction.

The method of removing the solvent may, for example, be a method such as natural drying, air drying, or reduced pressure drying. The temperature at which the solvent is removed by heating is usually from 0 to 250 ° C, preferably from 50 to 220 ° C, more preferably from 80 to 170 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. When the heating temperature and the heating time are within the above range, a supporting substrate which is not sufficiently heat-resistant can be used as the supporting substrate.

By polymerizing the obtained unpolymerized film to be cured, a film having a direct orientation of the compound of the present invention, that is, a polymer film can be obtained. A diaphragm that is less susceptible to the effects of heat on birefringence can be obtained.

The method of polymerizing the unpolymerized film may be appropriately determined depending on the type of the liquid crystal compound and the compound of the present invention. When the polymerizable group in the compound of the present invention and the liquid crystal compound is a photopolymerizable group, a photopolymerization method can be used, and when the polymerizable group is a thermally polymerizable group, a thermal polymerization method can be used. When the photopolymerization method is used, the unpolymerized film can be polymerized at a low temperature to increase the range of heat resistance of the support substrate, and industrially easy to manufacture, and photopolymerizable polymerizability is preferably used. A compound of the invention and a liquid crystal compound. Further, from the viewpoint of film formability, photopolymerization is also preferred. The photopolymerization reaction can be carried out by irradiating the unpolymerized film with visible light, ultraviolet light or laser light. In terms of handling, it is particularly suitable for ultraviolet light. Light irradiation can also be carried out by taking the temperature of the liquid crystal phase of the compound of the present invention. At this time, the polymerized film may be patterned by masking or the like.

The birefringence Δn(λ) can be modulated by appropriately adjusting the exposure amount during the polymerization, the heating temperature, and the heating time to impart a desired phase difference.

The optical film of the present invention has a thinner film thickness than the stretched film which imparts a phase difference by stretching the polymer.

By peeling off the support substrate, a film in which the alignment film and the optical film are laminated can be obtained. Further, the oriented film can be peeled off to obtain an optical film.

The optical film thus obtained is excellent in transparency and can be used as a film for various displays. The thickness of the optical film is as described above, and varies depending on the phase difference of the optical film, but the thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.5 to 3 μm in terms of reduction in photoelasticity.

The retardation of the optical film exhibiting birefringence is generally from 50 to 500 nm, preferably from 100 to 300 nm.

Such an optical film which can perform the same polarization conversion in a wider wide-band region can be used as an optical compensation film in all liquid crystal panels or FPDs such as organic EL.

The optical film of the present invention can be used as a wide-band λ/4 plate or a λ/2 plate. When it is used as a wide-band λ/4 plate or a λ/2 plate, the content of the structural unit derived from the compound of the present invention and the film thickness of the optical film in the optical film may be appropriately selected. When the λ/4 plate is used, the film thickness may be adjusted such that the Re (550) of the obtained optical film is generally 113 to 163 nm, preferably 135 to 140 nm, and particularly preferably about 137.5 nm. When the λ/2 plate is used, it is preferable to adjust the film thickness so that Re (550) of the obtained optical film is generally 250 to 300 nm, preferably 273 to 277 nm, and particularly preferably about 275 nm.

The optical film of the present invention can also be used as an optical film for a VA (Vertical Alignment) mode. When it is used as the optical film for VA mode, the content of the structural unit derived from the compound of the present invention in the optical film may be appropriately selected. The film thickness may be adjusted so that the Re (550) of the obtained optical film is generally 40 to 100 nm, preferably 60 to 80 nm.

Using only a small amount of the compound of the present invention, the wavelength dispersion characteristic of the optical film can be shifted toward a value close to 1, and the desired wavelength dispersion characteristics can be modulated in a simple manner.

The optical film of the present invention can also be used for an anti-reflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, or an optical compensation film for viewing angle compensation of a transmissive liquid crystal display. Wait.

The optical film of the present invention can exhibit excellent optical characteristics even in one sheet, and can be used by laminating a plurality of sheets. Further, it can also be used in combination with other films. Specific examples of the combination with other films include, for example, an elliptically polarizing plate in which a polarizing film is bonded to the optical film of the present invention, and the optical film of the present invention is further bonded to the ellipsic polarizing plate as a wide-band λ/4 plate. Wide-band circular polarizers, etc.

The optical film of the present invention can be formed by being applied to a support substrate or an alignment film and polymerizing it. Therefore, as shown in Fig. 1, a wide band is formed on the color filter more simply than in the past. Domains, such as optical films of λ/4, λ/2.

Fig. 1 is a schematic view showing a color filter 1 of the present invention.

The color filter 1 sequentially laminates the color filter layer 4, the alignment film 3, and the optical film 2 of the present invention.

An example of a method of manufacturing such a color filter 1 will be described below. First, a directional polymer is laminated on the color filter layer 4, and rubbing treatment is performed to form the alignment film 3. The oriented polymer can also be laminated using an inkjet method.

Then, on the obtained oriented film 3, a solution of the compound of the present invention in which the content of the compound of the present invention is adjusted is prepared in such a manner that the obtained optical film has a desired wavelength dispersion property, and the solution is applied. The optical film 2 is formed by the thickness of the desired phase difference.

By using such a color filter 1, a thinner liquid crystal display device can be manufactured. As an example, a schematic view of the liquid crystal display device 5 of the present invention is shown in Fig. 2 .

The liquid crystal display device 5 shown in FIG. 2 is a substrate 7 on which a glass substrate or the like faces the backlight, such as a glass substrate, is fixed to the polarizing plate 6 via an adhesive. The optical film 2' is formed on the color filter layer 4' formed on the substrate 7 via the alignment film 3'. Further, a counter electrode 8 is formed on the optical film 2', and a liquid crystal phase 9 is formed on the counter electrode 8. On the backlight side, the polarizing plate 10 is fixed to the substrate 11 such as a glass substrate via an adhesive. Further, a thin film transistor (TFT) and an insulating layer 12 for actively driving the liquid crystal layer are formed on the substrate 11. Further, a transparent electrode 13 and/or a reflective electrode 13' made of Ag, Al or ITO (Indium Tin Oxide) is formed on the TFT. The liquid crystal display device 5 shown in Fig. 2 has a configuration in which the number of optical films is smaller than that of the conventional liquid crystal display device, and a thinner liquid crystal display device can be manufactured.

An example of a method of manufacturing the liquid crystal display device 5 on the liquid crystal layer side of the substrate on which the color filter 1' is formed will be described below. On the substrate on the backlight side, a gate electrode, a gate insulating film, and an amorphous germanium composed of Mo or MoW may be deposited and patterned on the borosilicate glass, and then the amorphous germanium is excimer. The laser is annealed to form a crystallized semiconductor film, and thereafter, P, B, and the like are doped in regions on both sides of the gate electrode to form n-channel and p-channel TFTs. Further, by forming the insulating layer 12 composed of SiO ₂ , a substrate on the backlight side can be obtained. Further, ITO is sputtered on the backlight side substrate 11, and the transparent electrode 13 for the full-transmission type display device is laminated on the backlight side substrate. Further, in the same manner, instead of ITO, Ag, Al, or the like is used to obtain a reflective electrode 13' for a total reflection type display device. Further, by appropriately combining the reflective electrode and the transparent electrode, an electrode on the backlight side for a transflective liquid crystal display device can be obtained.

Further, a color filter layer 4' is formed on the opposite substrate 7. A full-color liquid crystal display device can also be obtained by using R, G, and B color filters in combination. Next, a directional polymer is applied onto the color filter layer 4', and rubbing is performed to form an alignment film 3'. A solution of the compound of the present invention is applied to the alignment film 3' and heated to a temperature range in which the liquid crystal phase is taken, and simultaneously polymerized by ultraviolet irradiation to form an optical film 2'. After the optical film is formed, the counter electrode 8 can be formed by sputtering ITO. Further, an alignment film is formed on the counter electrode to form a liquid crystal phase 9. Finally, the liquid crystal display device 5 can be fabricated by being assembled and assembled with the substrate on the backlight side.

Further, the optical film of the present invention can be used for a phase difference plate of a reflective liquid crystal display or an organic EL display, and an FPD including the phase difference plate or the optical film. The FPD is not particularly limited, and examples thereof include a liquid crystal display (LCD) or an organic EL.

Next, a polarizing plate and an FPD having a polarizing plate according to the present invention will be described.

The polarizing plate of the present invention comprises the optical film of the present invention and a film (polarizing film) having a polarizing function. Generally, it can be obtained by laminating the optical film of the present invention and a polarizing film. Specifically, it is obtained by laminating the optical film of the present invention directly on one side or both sides of the polarizing film or using an adhesive. In the present specification, "adhesive" means both an adhesive and an adhesive. Hereinafter, a polarizing plate according to the present invention will be described using Figs. 3 to 5.

3(a) to 3(e) are schematic views showing a polarizing plate of the present invention.

The polarizing plate 30a shown in Fig. 3(a) directly bonds the laminate 14 and the polarizing film 15, and the laminated body 14 is composed of the supporting substrate 16, the alignment film 17, and the optical film 18. The polarizing plate 30a is laminated with a supporting base material 16, an orientation film 17, an optical film 18, and a polarizing film 15 in this order.

The polarizing plate 30b shown in Fig. 3(b) is bonded to the polarizing film 15 via the adhesive layer 19.

The polarizing plate 30c shown in Fig. 3(c) directly bonds the laminate 14 and the laminate 14', and further laminates the laminate 14' and the polarizing film 15 directly.

The polarizing plate 30d shown in Fig. 3(d) is bonded to the polarizing film 14' via the adhesive layer 19, and the laminate 14' and the polarizing film 15 are directly bonded together.

The polarizing plate 30e shown in Fig. 3(e) has the laminate 14 laminated on the polarizing film 14' via the adhesive layer 19, and further, the laminate 14' and the polarized film are interposed via the adhesive layer 19'. The film 15 is laminated.

An optical film 18 from which the support substrate 16 and the alignment film 17 are peeled off from the laminate 14 or a film composed of the alignment film 17 and the optical film 18 from which the support substrate 16 is peeled off from the laminate 14 may be used. Sheet to replace laminate 14. An optical film 18' from which the support substrate 16' and the alignment film 17' are peeled off from the laminate 14' may be used, or the alignment film 17' and the optical film may be peeled off from the laminate 14'. A diaphragm composed of a diaphragm 18' is substituted for the laminate 14'.

The polarizing plate of the present invention may also laminate a plurality of laminates, and the plurality of laminates may all be the same or different.

The polarizing film 15 may be a film having a polarizing function, and specifically, for example, a film in which a polyvinyl alcohol film is formed by adsorbing iodine or a dichroic dye, and a polyvinyl alcohol film is stretched. A membrane or the like which adsorbs iodine or a dichroic dye.

The adhesive used for the adhesive layer 19 and the adhesive layer 19' is preferably an adhesive having high transparency and excellent heat resistance. Examples of such an adhesive include an acrylic adhesive, an epoxy adhesive, and a urethane adhesive.

The flat panel display device of the present invention includes the optical film of the present invention, and specifically includes, for example, a liquid crystal display device having a laminate in which a polarizing plate of the present invention and a liquid crystal panel are bonded, or a method in which the present invention is bonded An organic EL display device of an organic EL panel of a polarizing plate and a light-emitting layer.

The liquid crystal display device and the organic EL display device are taken as an example, and an embodiment of the flat panel display device of the present invention will be described below.

Fig. 4 is a schematic view showing a bonding product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device of the present invention. The laminate 21 is obtained by bonding the polarizing plate 30 of the present invention and the liquid crystal panel 20 via the adhesive layer 22. A voltage is applied to the liquid crystal panel 20 by using an electrode (not shown), and the liquid crystal molecules can be driven to display black and white.

Fig. 5 is a schematic view showing an organic EL panel 23 of an organic EL display device of the organic EL display device of the present invention. The organic EL panel 23 is formed by bonding the polarizing film 30 of the present invention and the light-emitting layer 24 via the adhesive layer 25.

In the above organic EL panel, the polarizing film 30 functions as a wide-band circular polarizing plate. Further, the light-emitting layer 24 is a layer of at least one layer composed of a conductive organic compound.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.

(Example 1) <Synthesis Example of Compound (A1-1)>

(1) Synthesis example of compound (1-a)

21.5 g of 2,5-dimethoxyaniline, 25.0 g of benzothiophene-2-carboxylic acid, and 125.3 g of dehydrated chloroform were mixed and reacted. To the resulting mixture, 1.71 g of N,N-dimethylaminopyridine was added. The obtained mixture was cooled in an ice bath, and 31.8 g of N,N'-dicyclohexylcarbodiimide was added and allowed to react for 1 hour. Thereafter, the mixture was returned to room temperature, and the resulting mixture was filtered through a silica gel to remove a precipitate, which was concentrated under reduced pressure. A 1/2 (v/v) solution of ethyl acetate-heptane was added to the residue to cause crystallization. The crystals thus precipitated were filtered and dried in vacuo to give 33.4 g of compound (1-a) as a pale yellow powder. The yield was 76% based on 2,5-dimethoxyaniline.

(2) Synthesis example of compound (1-b)

Mixed compound (1-a) 33.35g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) 22.4g and 200g of toluene, heated to 80 ° C to obtain The mixture reacted. After cooling, it was concentrated to obtain a red viscous solid having a compound (1-b) and a decomposition product of Lawesson's reagent as a main component.

(3) Synthesis example of compound (1-c)

A mixture containing the compound (1-b) obtained in the above item, 25.5 g of sodium hydroxide and 580 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, an aqueous solution containing 95.6 g of potassium ferricyanide was added to the mixture under ice cooling, and reacted at room temperature for 12 hours. The precipitated yellow precipitate was collected by filtration. The precipitate thus obtained was washed with water and then washed with hexane, washed with ethanol, and dried in vacuo to give 19.5 g of pale yellow solid compound (1-c) as a main component. The yield was 56% based on the compound (1-a).

(4) Synthesis example of compound (1-d)

19.5 g of the compound (1-c) and 97.5 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was collected by filtration, washed with water and then hexane to obtain 18 g of a solid compound (1-d) as a main component. The yield was 95% based on the compound (1-c).

(5) Synthesis example of compound (Al-1)

5.00 g of compound (1-d), 14.68 g of compound (A), 0.20 g of dimethylaminopyridine and 60 ml of chloroform were mixed. To the resulting mixture, 7.68 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride was added under ice cooling. The obtained reaction solution was stirred, filtered with hydrazine, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added, and the resulting white precipitate was collected by filtration and dried in vacuo to give 10.9 g of Compound (A1-1) as a white powder. The yield was 59% based on the compound (1-d). ¹ H-NMR (CDCl ₃ ) of the compound (A1-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.35 to 2.83 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79~5.84 (dd, 2H), 6.07~6.17(m, 2H), 6.37~6.44(m, 2H), 6.87~7.02(m, 8H), 7.22(s, 2H), 7.40 ~7.46(m,2H), 7.83~7.89(m,3H)

The phase transition temperature of the obtained compound (A1-1) was confirmed by pattern observation with a polarizing microscope. The compound (A1-1) exhibits a smectic phase from 147 ° C to 155 ° C at a temperature rise, a nematic phase from 155 ° C to 180 ° C or more, and a nematic phase at 93 ° C at a temperature drop to carry out crystallization. .

(Example 2) <Synthesis Example of Compound (A5-1))

(1) Synthesis example of compound (5-a)

18.9 g of 2,5-dimethoxyaniline, 20.0 g of benzofuran-2-carboxylic acid, and 125.0 g of dehydrated chloroform were mixed and reacted. To the resulting mixture was added 1.51 g of N,N-dimethylaminopyridine. The obtained mixture was cooled in an ice bath, and 28.0 g of N,N'-dicyclohexylcarbodiimide was added and allowed to react for 1 hour. Thereafter, it was returned to room temperature and reacted overnight. The obtained mixture was filtered through a silica gel to remove a white precipitate and a brown component, and then concentrated under reduced pressure. The residue was added to an ethyl acetate/heptane solution (v/v = 1/2) to crystallize. The precipitated crystals were filtered and dried under vacuum to give a pale yellow powder compound (5-a) 14.4 g. The yield was 39% based on 2,5-dimethoxyaniline.

(2) Synthesis example of compound (5-b)

Mixed compound (5-a) 13.0 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) 9.2 g and 100 g of toluene were heated to 80 ° C and the resulting mixture was reacted for 5 hours. After cooling, it was concentrated to obtain a red viscous solid having a compound (5-b) and a decomposition product of Lawesson's reagent as a main component.

(3) Synthesis example of compound (5-c)

A mixture containing the compound (5-b) obtained in the above item, 10.5 g of sodium hydroxide and 250 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, an aqueous solution containing 39.3 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was allowed to proceed for 12 hours at room temperature, and the precipitated yellow precipitate was filtered. The precipitate which was collected by filtration was washed with water, washed with hexane, washed with ethanol, and dried in vacuo to give a pale yellow solid (0.3g) of Compound (5-c) as a main component. The yield was 69% based on the compound (5-a).

(4) Synthesis example of compound (5-d)

7.0 g of the compound (5-c) and 35.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was collected by filtration, washed with water and then hexane to give 6.5 g of a solid compound (5-d) as a main component. The yield was 100% based on the compound (5-c).

(5) Synthesis example of compound (A5-1)

1.60 g of compound (5-d), 4.96 g of compound (A), 0.07 g of dimethylaminopyridine, and 30 ml of chloroform were mixed. To the resulting mixture, 1.71 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added thereto, and the resulting white precipitate was collected by filtration, washed with ethanol, and dried in vacuo to yield 4.73 g of Compound (A5-1) as a white powder. The yield was 77% based on the compound (5-d). ¹ H-NMR (CDCl ₃ ) of the compound (A5-1): δ (ppm) 1.45 to 1.91 (m, 24H), 2.35 to 2.83 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.01 (m, 8H), 7.25 (s, 2H), 7.31 ~7.34(t,1H), 7.40~7.42(t,1H), 7.55~7.60(m,2H), 7.68~7.71(d,1H)

The phase transition temperature of the obtained compound (A5-1) was confirmed by pattern observation with a polarizing microscope. The compound (A5-1) exhibits a nematic phase from 139 ° C to 180 ° C or higher at the time of temperature rise, and exhibits a nematic phase at 93 ° C when it is cooled, and is crystallized.

(Example 3) <Synthesis Example of Compound (A6-1)>

(1) Synthesis example of 5-methylbenzofuran-2carboxylic acid 50 g of 5-methyl salicylaldehyde, 101.51 g of potassium carbonate, 11.84 g of tetrabutylammonium bromide, 30.48 g of potassium iodide and toluene, and heated to 80 ° C. To the obtained dispersion, 114.1 g of diethyl bromomalonate was added dropwise, and the mixture was reacted at 110 ° C (returning at the boiling point of toluene) for 24 hours. To the obtained brown solution, 3 ml of 3 g of potassium hydroxide was added and further reacted for 24 hours. After the obtained reaction liquid was cooled to room temperature, it was concentrated under reduced pressure with an evaporator. 40 g of potassium hydroxide and 400 ml of ethanol were added to the residue, and the mixture was stirred at 80 ° C for 1 hour. After cooling to room temperature, the ethanol was distilled off in a distiller. The residue was dissolved in 500 ml of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The precipitated yellow precipitate was collected by filtration, washed with 1000 ml of purified water, and dried in vacuo to give 43.7 g of 5-methylbenzofuran-2carboxylic acid as a pale yellow powder. The yield was 68% based on 4-methyl salicylaldehyde.

(2) Synthesis Example of Compound (6-a): 30.4 g of 2,5-dimethoxyaniline, 35.0 g of 5-methylbenzofuran-2-carboxylic acid, 20.1 g of triethylamine, N, N' 4.85 g of dimethylaminopyridine and 175.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 92.28 g of 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (hereinafter referred to as BOP reagent) was added and The reaction was carried out at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol), and dried in vacuo to give a pale yellow powder compound (6-a) 23.8 g. The yield was 39% based on 2,5-dimethoxyaniline.

(3) Synthesis Example of Compound (6-b) Mixed Compound (6-a) 23.8 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 16.1 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 80 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 8 hours. After cooling, it was concentrated to obtain a red viscous solid having a compound (6-b) and a decomposition product of Lawesson's reagent as a main component.

(4) Synthesis Example of Compound (6-c) A mixture containing the compound (6-b) obtained in the above item, 18.4 g of sodium hydroxide and 400 g of water were mixed, and the obtained mixture was stirred under ice cooling. Then, an aqueous solution containing 68.7 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was allowed to proceed at room temperature for 24 hours, and the precipitated yellow precipitate was filtered. The precipitate thus obtained was washed with water and then washed with hexane, washed with ethanol, and dried in vacuo to give 14.8 g of pale yellow solid compound (6-c) as a main component. The yield was 59% based on the compound (6-a).

(5) Synthesis Example of Compound (6-d) 14.8 g of the compound (6-c) and 74.0 g (5 times by mass) of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was filtered, washed with water and then hexane to obtain 10.4 g of a solid compound (6-d) as a main component. The yield was 77% based on the compound (6-c).

(6) Synthesis Example of Compound (A6-1) 1.70 g of a compound (6-d), 5.02 g of a compound (A), 0.07 g of dimethylaminopyridine, and 30 ml of chloroform were mixed. To the resulting mixture, 1.73 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give Compound (A6-1) 4.72 g. The yield was 75% based on the compound (6-d). ¹ H-NMR (CDCl ₃ ) of the compound (A6-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.34 to 2.83 (m, 12H), 2.84 (s, 3H), 3.92 to 3.97 (t) , 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.01 (m, 8H), 7.22 (m, 3H), 7.44 to 7.47 (m, 3H)

The phase transition temperature of the obtained compound (A6-1) was confirmed by pattern observation with a polarizing microscope. The compound (A6-1) exhibits a nematic phase from 146 ° C to 190 ° C or higher at the time of temperature rise, and exhibits a nematic phase at 100 ° C when it is cooled, and is crystallized.

(Example 4) <Synthesis Example of Compound (A10-1)>

(1) Synthesis Example of 5-Isobutylbenzofuran 40 g of 4-isobutylphenol was dissolved in 240.0 g of N,N'-dimethylacetamide. After the solution was cooled by an ice bath, 10.9 g of sodium hydroxide was added in 10 portions to be added. After stirring at room temperature for 1 hour, after the completion of hydrogen generation, 33.17 g of chloroacetaldehyde dimethyl acetal was added dropwise. After stirring at 80 ° C for 5 hours, it was confirmed that the reaction mixture was completed, and the reaction liquid was added to 1000 ml of water and 400 ml of methyl isobutyl ketone to carry out liquid separation. The organic layer was recovered, and further, the organic layer was washed twice with 800 ml of pure water. After the organic layer was recovered, it was dried over anhydrous sodium sulfate and concentrated under reduced pressure on an evaporator to give a red viscous liquid. Further, 400 g of toluene and 2.61 g of orthophosphoric acid were mixed and heated to 110 °C. A solution of a red viscous liquid dissolved in 100 ml of toluene was added dropwise to the solution. After stirring at 110 ° C for 3 hours, it was cooled to room temperature. The reaction solution was washed twice with a 1N aqueous sodium hydrogencarbonate solution, and finally washed with 500 ml of purified water. The organic layer was collected, dried over anhydrous sodium sulfate, evaporated, evaporated, evaporated, evaporated. The yield was 90% based on 4-isopropylphenol.

(2) Synthesis example of 2-mercapto-5-isobutylbenzofuran 25.77 g of 5-isobutylbenzofuran was dissolved in 28.4 g of N,N'-dimethylformamide. After the solution was cooled in a water bath, 25 g of phosphonium chloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then stirred at 100 ° C for 10 hours. The reaction solution was allowed to cool to room temperature, and 100 ml of pure water was added and stirred for 1 hour, and then neutralized with 1N sodium hydrogencarbonate. After adjusting the pH to 8, the liquid was separated from the toluene. The organic layer was recovered, and 2.6 g of activated carbon was added thereto, followed by filtration. The mixture was concentrated under reduced pressure with an evaporator, and the residue was dissolved in chloroform, and the mixture was applied to a column chromatography apparatus (solvent: chloroform / heptane = 1 / 1 (v / v) → chloroform 100 vol%). The original ingredients were taken out, concentrated on an evaporator, and dried in vacuo to give a pale red viscous liquid of 2-carbamido-5-isobutylbenzofuran 8.5 g. The yield was 28% on the basis of 5-isobutylbenzofuran.

(3) Synthesis example of 5-isobutylbenzofuran-2-carboxylic acid 16.40 g of 2-mercapto-5-isobutylbenzofuran and 9.43 g of aminesulfonic acid were mixed with 60 ml of pure water. After cooling in an ice bath, a solution of 8.78 g of sodium chlorite in water (50 ml) was added dropwise. The reaction was carried out in a water bath for 36 hours. 100 ml of toluene and 5 g of potassium hydroxide were added dropwise to the reaction solution to adjust the pH to 12. After liquid separation, the aqueous layer was recovered, and the aqueous layer was further washed with 300 ml of toluene. The aqueous layer was recovered, and the pH was made 2 with 2N-hydrochloric acid, and then 300 ml of toluene was added to carry out liquid separation. The organic layer was collected, dried over anhydrous sodium sulfate, evaporated, evaporated, evaporated. The yield was 38% based on 2-carbamido-5-isobutylbenzofuran.

(4) Synthesis Example of Compound (10-a): 4.71 g of 2,5-dimethoxyaniline, 8.71 g of 5-isobutylbenzofuran-2-carboxylic acid, 3.11 g of triethylamine, N, N 0.75 g of '-dimethylaminopyridine and 35.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 14.28 g of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol), and dried in vacuo to give 5.7 g of compound (10-a) as a pale yellow powder. The yield was 53% based on 2,5-dimethoxyaniline.

(5) Synthesis Example of Compound (10-b) Mixed Compound (10-a) 4.7 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 9.2 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 100 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 5 hours. After cooling, it was concentrated to obtain a red viscous solid having a compound (10-b) and a decomposition product of Lawesson ^, s as a main component.

(6) Synthesis Example of Compound (10-c) A mixture containing the compound (10-b) obtained in the above item, 3.1 g of sodium hydroxide and 50 g of water were mixed, and the obtained mixture was stirred under ice cooling. Then, an aqueous solution containing 11.94 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was allowed to proceed at room temperature for 24 hours, and the precipitated yellow precipitate was filtered. The precipitate thus obtained was washed with water, then with hexane, and washed with methanol. The yellow powder was added to a solvent of 1:1 (volume ratio) of heptane-ethyl acetate, and the mixture was stirred at room temperature for 1 hour, and then allowed to stand overnight in an ice bath. The pale yellow powder obtained was collected by filtration, and dried in vacuo to give 2.5 g of pale-yellow solid as compound as compound (10-c). The yield was 51% based on the compound (10-a).

(7) Synthesis Example of Compound (10-d) 2.5 g of the compound (10-c) and 12.5 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After cooling the obtained mixture, water was added thereto, and the obtained precipitate was collected by filtration, washed with water, toluene and then hexane to obtain 1.8 g of a solid compound (10-d) as a main component. The yield was 77% based on the compound (10-c).

(8) Synthesis Example of Compound (A10-1) 1.80 g of a compound (10-d), 4.92 g of a compound (A), 0.07 g of dimethylaminopyridine, and 30 ml of chloroform were mixed. To the resulting mixture, 1.70 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added, and the resulting white precipitate was collected by filtration, washed with ethanol, and the first component eluted with chloroform 80 vol%-acetone 20 vol% was recovered by a gel column chromatography to reduce the evaporator. After concentration by pressure, it was crystallized with cold methanol. The resulting pale yellow powder was collected by filtration and dried in vacuo to give Compound (A10-1) 4.60 g. The yield was 72% based on the compound (10-d).

1H-NMR (CDCl ₃ ) of the compound (A10-1): δ (ppm) 0.81 to 0.87 (t, 3H), 1.29 to 1.31 (d, 3H), 1.48 to 1.79 (m, 26H), 2.35 to 2.47 ( m, 8H), 2.63 to 2.83 (m, 5H), 3.93 to 3.97 (m, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.23 (m, 3H), 7.48 to 7.50 (m, 3H)

The phase transition temperature of the obtained compound (A10-1) was confirmed by pattern observation with a polarizing microscope. The compound (A10-1) showed a highly viscous phase from 144 ° C at a temperature rise, and showed a clear point at 169 ° C. At the time of cooling, a nematic phase was obtained from 167 ° C, and a nematic phase was exhibited at 105 ° C to carry out crystallization.

(Example 5) <Synthesis Example of Compound (A11-1)>

(1) Synthesis Example of 4,6-Dimethylbenzofuran 25 g of 3,5-dimethylphenol was dissolved in 150.0 g of N,N'-dimethylacetamide. After the solution was cooled in an ice bath, 9.82 g of sodium hydroxide was added. After stirring at room temperature for 1 hour, 25.49 g of chloroacetaldehyde dimethyl acetal was added dropwise. After stirring at 100 ° C for 15 hours, the reaction mixture was added to 1000 ml of water and 400 ml of methyl isobutyl ketone to carry out liquid separation. The organic layer was collected, and the organic layer was washed twice with 500 ml of 1N aqueous sodium hydroxide solution, and the organic layer was further washed twice with 800 ml of pure water. After the organic layer was recovered, it was dried over anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator to give a pale red viscous liquid. Further, 400 g of toluene and orthophosphoric acid (3.01 g) were mixed and heated to 110 °C. A solution of a pale red viscous liquid dissolved in 100 ml of toluene was added dropwise to the solution. After stirring at 110 ° C for 3 hours, it was cooled to room temperature. The reaction solution was washed twice with a 1N aqueous sodium hydrogencarbonate solution, and finally washed with 500 ml of purified water. The organic layer was taken up, dried over anhydrous sodium sulfate, evaporated, evaporated, evaporated, evaporated. The yield is 55% based on 3,5-dimethylphenol.

(2) Synthesis example of 2-methionyl-4,6-dimethylbenzofuran 21.62 g of 4,6-dimethylbenzofuran was dissolved in N,N'-dimethylformamide 28.4 g . After the solution was cooled in a water bath, 25 g of phosphonium chloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then stirred at 100 ° C for 10 hours. The reaction solution was allowed to cool to room temperature, and 100 ml of pure water was added and stirred for 1 hour, and then neutralized with 1N sodium hydrogencarbonate. After adjusting the pH to 8, the liquid was separated from the toluene. The organic layer was recovered, and 2.6 g of activated carbon was added thereto, followed by filtration. The mixture was concentrated under reduced pressure with an evaporator, and the residue was dissolved in chloroform and crystallised from heptane. The crystals were collected by filtration and dried in vacuo to give a pale-yellow powder of &lt;RTIgt;&lt;/RTI&gt; The yield was 76% on the basis of 4,6-dimethylbenzofuran.

(3) Synthesis example of 4,6-dimethylbenzofuran-2-carboxylic acid 19.50 g of 2-mercapto-4,6-dimethylbenzofuran, 13.04 g of aminesulfonic acid and 100 ml of pure Water mixed. After cooling in an ice bath, a solution of 12.15 g of sodium chlorite in water (100 ml) was added dropwise. The reaction was carried out in a water bath for 36 hours. To the reaction solution, 100 ml of toluene and 25 g of potassium hydroxide were added to adjust the pH to 12. After liquid separation, the aqueous layer was recovered, and the aqueous layer was further washed with 200 ml of toluene. The aqueous layer was recovered, and the pH was made 2 with 2N-hydrochloric acid, and then 400 ml of toluene was added to carry out liquid separation. The organic layer was collected, dried over anhydrous sodium sulfate, and evaporated. The yield was 67% based on 2-mercapto-4,6-dimethylbenzofuran.

(4) Synthesis of 4,6-dimethylbenzofuran-2-carboxylic acid

150 g of 3,5-dimethylphenol, 230.1 g of paraformaldehyde, and 175.4 g of anhydrous magnesium chloride were dispersed in 900 ml of acetonitrile. After stirring for 30 minutes in an ice bath, 474 g of triethylamine was added dropwise over two hours. The mixture was allowed to react in a water bath for 8 hours and at room temperature for 14 hours. After adding 1500 ml of cold 5N-hydrochloric acid to the reaction mixture to adjust the acidity, the mixture was separated into 400 ml of ethyl acetate to collect an organic layer. The aqueous layer was further partitioned with 400 ml of ethyl acetate. The organic layer was taken up, mixed with the previous organic layer, dried over anhydrous sodium sulfate, and evaporated. The residue was dissolved in 400 ml of toluene, and 3 g of activated carbon and 20 g of silica gel were added thereto, and the mixture was stirred at room temperature for 30 minutes, and filtered. The filtrate was recovered, concentrated under reduced pressure on an evaporator, and dried in vacuo to give &lt;RTIgt;&lt;/RTI&gt; The yield was 92% based on 3,5-dimethylphenol.

45.0 g of 4,6-dimethyl salicylaldehyde and 101.0 g of potassium carbonate were dispersed in 360 ml of N,N'-dimethylacetamide. After warming to 80 ° C, 50.0 g of ethyl bromoacetate was added dropwise over 1 hour. The mixture was allowed to react at 80 ° C for 4 hours. After cooling the reaction mixture to room temperature, 400 ml of methyl isobutyl ketone was added, and the mixture was adjusted to be acidic with 1000 ml of cold 1N-hydrochloric acid, and then liquid-separated. The organic layer was washed three times with 1000 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off in a distiller. 40 g of potassium hydroxide and 400 ml of ethanol were added to the residue, and the mixture was stirred at 80 ° C for 1 hour. After cooling to room temperature, the solvent was distilled off in a distiller, and 1000 ml of pure water was added. After confirming that the pH was 12 or more, the aqueous layer was washed twice with toluene and washed once with heptane. The aqueous layer was recovered, neutralized with 4N-sulfuric acid, and the pH was adjusted to 3. The precipitated yellow precipitate was filtered, washed with purified water and dried in vacuo to give 4,6 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 83% based on 4,6-dimethyl salicylaldehyde.

(5) Synthesis Example of Compound (11-a): 11.49 g of 2,5-dimethoxyaniline, 14.27 g of 4,6-dimethylbenzofuran-2-carboxylic acid, 7.59 g of triethylamine, N 1,8 g of N'-dimethylaminopyridine and 100.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 34.85 g of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (3 parts by volume of water, 2 parts by volume of methanol), and dried in vacuo to give 16.2 g of compound (11-a) as a pale yellow powder. The yield was 66% based on 2,5-dimethoxyaniline.

(6) Synthesis Example of Compound (11-b) 16.0 g of Compound (11-a), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 9.2 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 100 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 12 hours. After cooling, it was concentrated to obtain a red viscous solid which had a compound (11-b) and a decomposition product of Lawesson's reagent as a main component.

(7) Synthesis Example of Compound (11-c) A mixture containing the compound (11-b) obtained in the above item, 11.8 g of sodium hydroxide and 250 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, an aqueous solution containing 44.17 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was carried out at 60 ° C for 12 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate thus obtained was washed with water and then with hexane, and crystallized from toluene. The obtained yellow color was dried under vacuum to give a pale yellow solid (4.1 g) which had compound (11-c) as a main component. The yield was 25% based on the compound (11-a).

(8) Synthesis Example of Compound (11-d): 4.0 g of the compound (11-c) and 40.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, it was washed with toluene, and dried under vacuum to obtain 3.4 g of a loess-colored solid containing compound (11-d) as a main component. The yield was 93% based on the compound (11-c).

(9) Synthesis Example of Compound (A11-1) 3.00 g of Compound (11-d), 8.47 g of Compound (A), 0.12 g of dimethylaminopyridine, and 40 ml of chloroform were mixed. To the resulting mixture, 2.92 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution, the filtrate was concentrated to 1/3 under reduced pressure in an evaporator, and then methanol was added to the mixture, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give a white powder (A11-1). 7.60g. The yield was 71% based on the compound (11-d). ¹ H-NMR (CDCl ₃ ) of the compound (A11-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.36 to 2.87 (m, 18H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.45 (m, 2H), 6.87 to 7.01 (m, 9H), 7.20 (s, 1H), 7.23 (s, 2H), 7.53 (s, 1H)

The phase transition temperature of the obtained compound (A11-1) was confirmed by pattern observation with a polarizing microscope. The compound (A11-1) showed a highly viscous intermediate phase from 105 ° C to 137 ° C at elevated temperature. The discrimination of the liquid crystal phase is difficult, but a clear nematic phase is exhibited above 137 °C. When the nematic liquid crystal phase is at 180 ° C or higher, the crystal phase is formed at 61 ° C when the temperature is lowered.

(Example 6) (Synthesis Example of Compound (A15-1)>

(1) Synthesis Example of 5-Fluorobenzofuran-2carboxylic Acid 25 g of 5-fluorosalicylaldehyde, 49.32 g of potassium carbonate, and 200 g of 2-butanone were mixed, and the mixture was heated to 80 °C. 55.5 g of diethyl bromomalonate was added dropwise to the obtained dispersion, and the mixture was reacted at 100 ° C for 24 hours. The obtained red-brown solution was allowed to cool to room temperature, and then washed with pure water and 1 mol/L aqueous potassium carbonate solution. The organic layer was taken, dried over anhydrous sodium sulfate and evaporated. 25 g of potassium hydroxide and 250 ml of ethanol were added to the residue, and the mixture was stirred at 80 ° C for 2 hours. After cooling to room temperature, the ethanol was distilled off in a distiller. The residue was dissolved in 500 ml of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The precipitated lavender precipitate was collected by filtration, washed with 1000 ml of pure water, and dried in vacuo to give 23.4 g of 5-fluorobenzofuran-2carboxylic acid as a pale yellow powder. The yield was 73% based on the 4-fluorosalicylaldehyde standard.

(2) Synthesis Example of Compound (15-a): 17.01 g of 2,5-dimethoxyaniline, 20.0 g of 5-fluorobenzofuran-2carboxylic acid, 11.24 g of triethylamine, and N,N'-di 2.71 g of methylaminopyridine and 100.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 51.57 g of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol), and dried in vacuo to give 32.1 g of the compound (15-a) as a pale yellow powder. The yield was 92% based on 2,5-dimethoxyaniline.

(3) Synthesis Example of Compound (15-b) Mixed Compound (15-a) 32.0 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 24.6 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 320 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 24 hours. After cooling, it was concentrated to obtain a yellow solid which had a compound (15-b) and a decomposition product of Lawesson's reagent as a main component.

(4) Synthesis Example of Compound (15-c) A mixture containing the compound (15-b) obtained in the above item, 21.7 g of sodium hydroxide and 500 g of water were mixed, and the obtained mixture was stirred under ice cooling. Then, 81.3 g of potassium ferricyanide was added to cause a reaction. The reaction was carried out for 2 hours at room temperature. The precipitated yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then hexane, washed with toluene, and dried in vacuo to give 27.1 g of a pale yellow solid compound (15-c). The yield was 91% based on the compound (15-a).

(5) Synthesis Example of Compound (15-d) 10.0 g of the compound (15-c) and 50.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was collected by filtration, washed with water, hexane, and toluene to obtain 6.0 g of a solid as a compound (15-d). The yield was 66% based on the compound (15-c).

(6) Synthesis Example of Compound (A15-1) 3.00 g of Compound (15-d), 8.75 g of Compound (A), 0.12 g of dimethylaminopyridine, and 50 ml of chloroform were mixed. To the resulting mixture, 3.02 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. 0.3 g of activated carbon was added and stirred for 1 hour, followed by filtration. After the filtrate was concentrated by an evaporator, methanol was added while stirring, and the resulting white precipitate was collected by filtration. The mixture was washed with heptane and dried in vacuo to give 8.20 g of Compound (A15-1) as a white powder. The yield was 75% based on the compound (15-d). ¹ H-NMR (CDCl ₃ ) of the compound (A15-1): δ (ppm) 1.46 to 1.90 (m, 24H), 2.36 to 2.84 (m, 12H), 3.93 to 3.98 (t, 4H), 4.15 to 4 , 20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.14 to 7.19 (dt, 1H), 7.28 (s, 2H), 7.33 to 7.37 (dd, 1H), 7.50 to 7.55 (m, 2H)

The phase transition temperature of the obtained compound (A15-1) was confirmed by pattern observation with a polarizing microscope. The compound (A15-1) exhibits a highly viscous phase from 143 ° C to 178 ° C at a temperature rise, and the discrimination of the liquid crystal phase is difficult. However, a clear nematic phase is exhibited above 178 ° C, and a nematic phase is exhibited above 200 ° C. At the time of cooling, a nematic phase is exhibited at 110 ° C to carry out crystallization.

(Example 7) <Synthesis Example of Compound (A57-1)>

(1) Synthesis example of 5-propylbenzofuran-2carboxylic acid: 27.8 g of 4-propyl salicylaldehyde, 46.81 g of potassium carbonate, 11.84 g of tetrabutylammonium bromide, 30.48 g of potassium iodide and toluene, heating To 80 ° C. 52.6 g of diethyl bromomalonate and 2.8 g of 18-crown-6 (2.8 g) were added dropwise to the obtained dispersion, and the mixture was reacted at 110 ° C (returning at the boiling point of toluene) for 24 hours. The obtained reddish brown reaction liquid was cooled to room temperature, and then concentrated under reduced pressure with an evaporator. 27.8 g of potassium hydroxide and 278 ml of ethanol were added to the residue, and the mixture was stirred at 80 ° C for 1 hour. After cooling to room temperature, the ethanol was distilled off in a distiller. The residue was dissolved in 500 ml of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The precipitated yellow precipitate was collected by filtration, washed with 1000 ml of purified water, and dried in vacuo to give 5.8 g of 5-propylbenzofuran-2carboxylic acid as a pale yellow powder. The yield was 17% based on 4-propyl salicylaldehyde.

(2) Synthesis Example of Compound (57-a): 4.3 g of 2,5-dimethoxyaniline, 5.7 g of 5-propylbenzofuran-2-carboxylic acid, 2.82 g of triethylamine, N, N' 0.68 g of dimethylaminopyridine and 30.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 12.96 g of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol), and dried in vacuo to give a pale yellow powder compound (57-a) 6.33 g. The 2,5-dimethoxyaniline standard was 67%.

(3) Synthesis Example of Compound (57-b) Mixed Compound (57-a) 6.0 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 9.2 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 100 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 5 hours. After cooling, it was concentrated to obtain a red viscous solid having a compound (57-b) and a decomposition product of Lawesson's reagent as a main component.

(4) Synthesis Example of Compound (57-c) A mixture containing the compound (57-b) obtained in the above item, 4.5 g of sodium hydroxide and 50 g of water were mixed, and the obtained mixture was stirred under ice cooling. Then, 16.8 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was carried out for 48 hours at room temperature, and the precipitated yellow precipitate was filtered. The precipitate thus obtained was washed with water and then washed with hexane, washed with ethanol, and dried in vacuo to give 2.8 g of pale yellow solid compound (57-c). The yield was 42% based on the compound (57-a).

(5) Synthesis Example of Compound (57-d): 2.7 g of the compound (57-c) and 13.5 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 2 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was collected by filtration and washed with water and hexane to obtain 2.4 g of a solid of compound (57-d) as a main component. The yield was 97% based on the compound (57-c).

(6) Synthesis Example of Compound (A57-1) 1.85 g of a compound (57-d), 5.00 g of a compound (A), 0.07 g of dimethylaminopyridine, and 20 ml of chloroform were mixed. To the obtained mixture, 1.72 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added thereto, and the resulting white precipitate was collected by filtration, washed with hexane, and dried in vacuo to give 3.85 g of Compound (A57-1) as a white powder. The yield was 77% based on the compound (57-d).

¹ H-NMR (CDCl ₃ ) of the compound (A57-1): δ (ppm): 0.94 to 0.99 (t, 3H), 1.45 to 1.86 (m, 26H), 2.35 to 2.47 (m, 8H), 2.67 to 2.83 (m, 6H), 3.92 to 3.97 (m, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H) , 6.87 to 7.01 (m, 8H), 7.25 (s, 2H), 7.46 to 7.49 (m, 4H)

The phase transition temperature of the obtained compound (A57-1) was confirmed by pattern observation with a polarizing microscope. The compound (A57-1) showed a highly viscous phase from 131 ° C to 143 ° C at a temperature rise, and a clear nematic phase was obtained from 143 ° C, and a further phase (A57-1) to 180 ° C or more exhibited a nematic phase. At the time of cooling, a nematic phase is exhibited at 100 ° C to carry out crystallization.

(Example 8) <Synthesis Example of Compound (A25-1)>

(1) Synthesis Example of Compound (25-a): 15.8 g of 2,5-dimethoxyaniline, 19.0 g of thieno[3,2-b]thiophene-2-carboxylic acid, and 10.4 g of triethylamine, N 4,5 g of N'-dimethylaminopyridine and 95.0 g of dehydrated N,N'-dimethylacetamide. After the obtained solution was cooled in an ice bath, 47.9 g of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol), and dried in vacuo to give 21.0 g of compound (25-a) as a yellow powder. The yield was 64% based on 2,5-dimethoxyaniline.

(2) Synthesis Example of Compound (25-b) 27.0 g of Compound (25-a), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 17.8 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 122 g of toluene were heated to 80 ° C, and the resulting mixture was reacted for 5 hours. The precipitate which precipitated after cooling was collected by filtration to obtain a brown solid having a compound (25-b) and a decomposition product of Lawesson's reagent as a main component.

(3) Synthesis Example of Compound (25-c) A mixture 26.4 containing the compound (25-b) obtained in the above paragraph, 18.9 g of sodium hydroxide and 450 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, an aqueous solution containing 70.7 g of potassium ferricyanide was added under ice cooling to cause a reaction. The reaction was allowed to proceed for 12 hours at room temperature, and the precipitated yellow precipitate was filtered. The precipitate which was collected by filtration was washed with water and then washed with hexane, and washed with ethanol and dried in vacuo to give 15 g of a yellow solid compound (25-c) as a main component. The yield was 58% based on the compound (25-a).

(4) Synthesis Example of Compound (25-d) 15.0 g of the compound (25-c) and 75.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. After the obtained mixture was cooled, water was added thereto, and the obtained precipitate was filtered, washed with water, hot toluene and hexane to obtain 6.6 g of a solid compound (25-d) as a main component. The yield was 45% based on the compound (25-c). (5) Synthesis Example of Compound (A25-1) 2.0 g of the compound (25-d), 5.76 g of the compound (A), 0.08 g of dimethylaminopyridine, and 30 ml of chloroform were mixed. To the resulting mixture, 1.98 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, 0.8 g of activated carbon was added, and after standing overnight, it was filtered with a silica gel and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration and redissolved in chloroform. While stirring the obtained solution, methanol was added, and the resulting brown precipitate was collected by filtration, washed with ethanol, and dried in vacuo to give 4.30 g of Compound (A25-1) as a pale brown powder. The yield was 60% based on the compound (25-d). ¹ H-NMR (CDCl ₃ ) of the compound (A25-1): δ (ppm) 1.26 to 1.87 (m, 24H), 2.33 to 2.81 (m, 12H), 3.92 to 3.96 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79~5.84 (dd, 2H), 6.07~6.17 (m, 2H), 6.37~6.44 (m, 2H), 6.87~7.01 (m, 8H), 7.18 (s, 2H), 7.23 ~7.31(d, 1H), 7.52~7.54(d, 1H), 7.82(s, 1H)

The phase transition temperature of the obtained compound (A25-1) was confirmed by grain observation with a polarizing microscope. The compound (A25-1) exhibited a nematic phase from 175 ° C to 180 ° C at a temperature rise, a nematic phase from 180 ° C to 238 ° C or more, and a clear point at 238 ° C. At the time of cooling, a nematic phase is exhibited at 168 ° C to carry out crystallization.

(Example 9) <Synthesis Example of Compound (A41-1)>

(1) Synthesis Example of Compound (41-a) In a container, 35.4 g of 2,5-dimethoxyaniline, 46.7 g of triethylamine, and 400 g of dehydrated chloroform were mixed, and 4-phenylbenzhydrazine was added while reacting. Base chlorine 50.0g. The mixed solution was heated to 60 ° C, matured for 3 hours, cooled to room temperature, and poured into water. The separated organic layer was taken out. Wash with water and then with hydrochloric acid. The obtained organic layer was concentrated to give 76.6 g of Compound (41-a). The yield was 98% on the basis of 2.5-dimethoxyaniline.

(2) Synthesis Example of Compound (41-b) A solid having a compound (41-b) and a decomposition product of Lawesson's reagent as a main component was obtained in the same manner as in the synthesis of the compound (1-b).

(3) Synthesis Example of Compound (41-c) A solid having the compound (41-c) as a main component was obtained in the same manner as in the synthesis of the compound (1-c).

(4) Synthesis Example of Compound (41-d) A solid having the compound (41-d) as a main component was obtained in the same manner as in the synthesis of the compound (1-d).

(5) Synthesis Example of Compound (A41-1) The compound (A41-1) was obtained in the same manner as in the synthesis of the compound (A1-1). The yield was 68% based on the compound (41-d). ¹ H-NMR (CDCl ₃ ) of the compound (A41-1): δ (ppm) 1.44 to 1.82 (m, 24H), 2.32 to 2.64 (m, 12H), 3.91 to 3.97 (t, 4H), 4.14 to 4.20 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36 to 6.44 (m, 2H), 6.85 to 7.01 (m, 8H), 7.37 to 7.90 (m, 9H) 8.13 to 8.17 (m, 2H)

The phase transition temperature of the obtained compound (A41-1) was confirmed by pattern observation with a polarizing microscope. If the temperature is raised, it is transferred to the smectic phase near 214 °C. If the temperature is further raised, it changes to the nematic phase at around 234 °C. If the temperature is further raised, it changes to an isotropic phase at around 275 °C. When the temperature is lowered from this, it becomes a nematic phase in the vicinity of 269 ° C, becomes a smectic phase in the vicinity of 227 ° C, and returns to the crystal at around 204 ° C. That is, the compound (A41-1) exhibits a smectic phase from 214 ° C to 234 ° C at a temperature rise, and a nematic phase from 234 ° C to 275 ° C. Further, at the time of temperature lowering, a nematic phase is exhibited from 269 ° C to 227 ° C, and a smectic phase is exhibited from 227 ° C to 204 ° C.

(Example 10) <Synthesis Example of Compound (A43-1)>

(1) Synthesis example of compound (43-d)

In the synthesis example of the compound (41-d), the same is carried out except that 4-(4-n-propylphenyl)benzhydryl chloride is substituted for the 4-phenylbenzhydryl chloride of the starting material. In the same manner, the compound (43-d) is synthesized in accordance with the above reaction mechanism.

(2) Synthesis Example of Compound (A43-1) In the synthesis example of the compound (1-1), the same method is used except that the compound (1-d) of the starting material is changed to the compound (43-d). The compound (A43-1) was obtained. The yield was 65% based on the compound (43-d).

¹ H-NMR (CDCl ₃ ) of the compound (A43-1): δ (ppm) 0.95 to 1.01 (t, 3H) 1.44 to 1.87 (m, 26H), 2.34 to 2.83 (m, 14H), 3.92 to 3.98 ( t, 4H), 4.14 to 4.21 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.20 to 7.31 (m, 4H), 7.56 to 7.60 (d, 2H), 7.69 to 7.73 (d, 2H), 8.07 to 8.11 (d, 2H)

The phase transition temperature of the crystal of the obtained compound (A43-1) was confirmed by pattern observation with a polarizing microscope. If the temperature is raised, it changes to a uniform phase at around 143 °C. When the temperature is lowered from this, it returns to crystallization at around 118 °C. It is also known that the compound (A43-1) does not exhibit a liquid crystal phase.

(Example 11) <Synthesis Example of Compound (A66-1)

(1) Synthesis Example of Compound (66-a) 10.0 g of 2,3-dicyanohydroquinone, 35.0 g of potassium hydroxide and 70.0 g of water were mixed, and the mixture was heated at 100 ° C while stirring the mixture. The obtained mixture was cooled to room temperature, and 40.0 g of sulfuric acid was added thereto, followed by further stirring. Ethyl acetate was added to the obtained mixture and stirred, and the organic layer was taken. The obtained organic layer was concentrated under reduced pressure, and the solvent was evaporated, and then dried in vacuo to give 8.5 g of compound (66-a). The yield was 68% based on the 2,3-dicyanohydroquinone.

(2) Synthesis Example of Compound (66-b) 10.0 g of compound (66-a), 19.1 g of 2-amino-6-methoxybenzothiophene and 200.0 g of tetrahydrofuran were mixed while heating at 70 ° C while stirring the mixture. . The obtained mixture was cooled to room temperature, and 12.5 g of N,N'-dicyclohexylcarbodiimide was dissolved in 37.5 g of tetrahydrofuran, and after dropwise addition at room temperature, the mixture was stirred and heated at 80 ° C for 36 hours while stirring. The obtained mixture was allowed to cool to room temperature, and the white precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure to remove solvent, and the residue was crystallized with chloroform. The resulting pale green powder was filtered and washed with chloroform. The obtained pale green powder was dissolved again in tetrahydrofuran, and methanol was added thereto to cause crystallization. After the resulting green precipitate was filtered, it was dried in vacuo to give 2.8 g of Compound (66-b). The yield was 16% based on the compound (66-a).

(3) Synthesis Example of Compound (A66-1) 2.1 g of the compound (66-b), 0.18 g of 4-dimethylaminopyridine, 6.16 g of the compound (A), and 123 g of chloroform were mixed. Then, a solution obtained by dissolving 4.56 g of N,N'-dicyclohexylcarbonyldiimine in 10.7 g of chloroform was added dropwise to the obtained mixture at room temperature, followed by stirring. After filtering the obtained mixture, 62 g of 2N hydrochloric acid was placed and stirred to separate the liquid, and the organic layer was taken out. After repeating the above liquid separation operation twice, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off with an evaporator, and methanol was added and stirred. The precipitate formed was filtered, and dried under vacuum to give Compound (A66-1) 4.1 g. The yield was 59% based on the compound (66-b).

¹ H-NMR (CDCl ₃ ) of the compound (A66-1): δ (ppm) 1.45 to 1.85 (m, 12H), 2.29 to 2.56 (m, 8H), 2.56 to 2.75 (2tt, 4H), 3.89 (s) 3H), 3.92 to 3.97 (t, 4H), 4.16 to 4.19 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 ~7.01 (m, 8H), 7.08 to 7.13 (dd, 1H), 7.32 (d, 1H), 7.50 to 7.52 (m, 2H), 8.00 (d, 1H)

The phase transition temperature of the obtained compound (A66-1) was confirmed by pattern observation with a polarizing microscope. When the compound (A66-1) was elevated in temperature, it exhibited a highly viscous phase from 140 ° C from 140 ° C, and the liquid crystal phase was difficult to discriminate. However, a clear liquid crystal phase is shown above 140 °C.

(Examples 12 to 24 and Comparative Example 1)

<Example of Manufacturing Optical Film>

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and after drying, a film having a thickness of 89 nm was formed. Then, the surface of the obtained film was rubbed, and the composition of the composition of Table 1 was applied by spin coating on the surface on which the rubbing treatment was carried out, and dried at the drying temperature shown in Table 2 for 1 minute. Then, while heating to the temperature at the time of light irradiation shown in Table 2, the ultraviolet ray of the integrated light amount shown in Table 2 was irradiated to form an optical film of the film thickness shown in Table 3.

LC242: Liquid crystal compound of the following formula sold by BASF Corporation

Polymerization initiator: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.: fluorenylphosphine oxide compound) Coating agent: BYK361N (manufactured by BYK Japan) Solvent: cyclopentanone

<Measurement of optical characteristics>

The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Further, since the glass substrate used for the substrate has no birefringence, the film of the glass substrate is measured by a measuring machine, and the front surface difference value of the optical film produced on the glass substrate can be obtained. The obtained optical measurement front-end retardation values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re(447.3)/Re(546.9)] (as α) and [Re(627.8)/Re were calculated. (546.9)] (as β). Further, the film thickness d (μm) of the optical film was measured using a laser microscope (LEXT, manufactured by 01ympus Co., Ltd.). The results are shown in Table 3. Δn is calculated by dividing the value of Re (546.9) by the film thickness (Δn = Re (546.9) / d).

(Example 25) <Synthesis Example-2 of Compound (A11-1)>

(1) Synthesis example of 4,6-dimethylbenzofuran-2-carboxylic acid 146.6 g of 4,6-dimethyl salicylaldehyde and 330.7 g of potassium carbonate are dispersed in N,N'-dimethyl B Indoleamine 700ml. After heating to 80 ° C, 190.5 g of tributyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C for 2 hours. After cooling the reaction mixture to room temperature, 600 ml of methyl isobutyl ketone was added, and the mixture was separated into 1200 ml of pure water. Further, the organic layer was washed twice with 1000 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 240 g of acetic acid, and 72 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, and then dried in vacuo to give 81.7 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 44% based on 4,6-dimethyl salicylaldehyde.

(2) Synthesis Example of Compound (11-a): 96.6 g of 2,5-dimethoxyaniline, 80.0 g of 4,6-dimethylbenzofuran-2-carboxylic acid, and 400.0 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 88.7 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 300 g of chloroform was added over 4 hours. The reaction was carried out for 48 hours at room temperature. The obtained mixture was concentrated, and a mixed solution of 1N-hydrochloric acid and methanol (2 parts by volume of water and 1 part by volume of methanol) was added thereto to cause crystallization. The obtained precipitate was collected by filtration, and a mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added. The pale yellow precipitate which precipitated was collected by filtration, washed with a water-methanol mixture (2 parts by volume of water, 1 part by volume of methanol), and dried in vacuo to give a pale yellow powder compound (11-a) 124.2 g. The yield was 91% based on 4,6-dimethylbenzofuran-2-carboxylic acid.

(3) Synthesis Example of Compound (11-b) 123.0 g of Compound (11-a), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 9.2 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 1200 g of toluene were heated to 110 ° C, and the resulting mixture was reacted for 8 hours. After cooling to room temperature, it was separated from a 1N-aqueous sodium hydroxide solution. The organic layer was recovered and 800 ml of heptane was added. The precipitated yellow precipitate was filtered, washed with heptane, and dried in vacuo to give 109.2 g of pale yellow powder of compound (11-b) as a main component. The yield was 85% based on the compound (11-a).

(4) Synthesis Example of Compound (11-c) Compound (11-b) 60.0, sodium hydroxide 53.8 g, and water 1000 g were mixed, and the obtained mixture was stirred under ice cooling. Then, 133.0 g of potassium ferricyanide and 51 g of methanol were added to cause a reaction. The reaction was carried out for 36 hours at room temperature, and the precipitated yellow precipitate was collected by filtration. The precipitate obtained by filtration was washed with a mixed solution of heptane and toluene (3 parts by volume of heptane and 1 part by volume of toluene), and the obtained yellow powder was dried in vacuo to give a yellow compound (11-c) as a main component. Solid 51.3 g. The yield was 86% based on the compound (11-b).

(5) Synthesis Example of Compound (11-d) 40.0 g of the compound (11-c) and 400.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, the mixture was washed with toluene and dried in vacuo to give 36.6 g of a yellow solid compound (11-d). The yield was 99% based on the compound (11-c).

(6) Synthesis Example of Compound (A11-1) 35.0 g of the compound (11-d), 98.8 g of the compound (A), 1.37 g of dimethylaminopyridine and 700 ml of toluene were mixed. To the obtained mixture, 55.6 g of N,N'-dicyclohexylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 2.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added to the mixture, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give a white powder (A11-1 ) 74.5g. The yield was 60% based on the compound (11-d).

(Example 26) <Synthesis Example-3 of Compound (A11-1)>

Compound (A-11) was synthesized in the same manner as in Synthesis Example-2 of Compound (A11-1), except that ethyl chloroacetate was used instead of butyl bromoacetate.

(Example 27) <Synthesis Example of Compound (A61-1)>

(1) Synthesis Example of 3,6-Dimethyl Salicylaldehyde 50 g of 2,5-dimethylphenol, 30.7 g of polyacetal, and 58.4 g of anhydrous magnesium chloride were dispersed in 500 ml of tetrahydrofuran. After stirring for 30 minutes in an ice bath, 82.83 g of triethylamine was added dropwise over two hours. The mixture was allowed to react in a water bath for 8 hours and at room temperature for 120 hours. After adding 1500 ml of cold 5N-hydrochloric acid to the reaction mixture to adjust the acidity, the mixture was extracted twice with 400 ml of ethyl acetate, and the organic layer was collected. After the organic layer was dried over anhydrous sodium sulfate, it was filtered over Celite, and the filtrate was concentrated under reduced pressure at 40 ° C under an evaporator. The residue was dissolved in 100 ml of toluene, and 600 ml of heptane was added to the solution. 30 g of tannin was added to the solution and stirred for 1 hour, followed by filtration. The filtrate was concentrated under reduced pressure, and heptane was further added to the residue to extract, and then, the heptane was evaporated to give a yellow liquid, 10.5 g of 3,6-dimethyl salicylaldehyde. The yield was 17% based on 2,5-dimethylphenol.

(2) Synthesis example of 4,7-dimethylbenzofuran-2-carboxylic acid 10.48 g of 3,6-dimethyl salicylaldehyde and 23.63 g of potassium carbonate are dispersed in N,N'-dimethyl B Indoleamine 70ml. After heating to 80 ° C, 13.61 g of tributyl bromoacetate was added dropwise over 10 minutes. The mixture was reacted at 130 ° C for 3 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. Further, the organic layer was washed twice with 300 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 40 g of acetic acid, and 8 g of an aqueous hydrobromic acid solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 10 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid water, and then washed with heptane, and dried in vacuo to give 7.31 g of 4,7-dimethylbenzofuran-2-carboxylic acid as a white powder. The yield was 55% based on 3,6-dimethyl salicylaldehyde.

(3) Synthesis Example of Compound (61-a): 8.82 g of 2,5-dimethoxyaniline, 7.30 g of 4,7-dimethylbenzofuran-2-carboxylic acid, and 38 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 8.09 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 50 g of chloroform was added over 4 hours. The reaction was carried out at room temperature for 24 hours. Further, 1.18 g of 2,5-dimethoxyaniline was added to the reaction solution and allowed to react for 48 hours. The obtained mixture was concentrated, and 400 g of a mixed solution of 1 N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue, and 150 g of heptane was added thereto to cause crystallization. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The precipitated pale yellow-green precipitate was collected by filtration, and further washed with a water-methanol mixture solution (2 parts by volume of water and 1 part by volume of methanol). The obtained pale yellow-green precipitate was washed with a mixed solution of 1N-KOH aqueous solution-methanol (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol), and then washed with 150 g of water and then filtered. The compound (61-a) (8.82 g) was obtained as a pale yellow powder. The yield was 71% based on 4,7-dimethylbenzofuran-2-carboxylic acid.

(4) Synthesis Example of Compound (61-b) Compound (61-a) 8.82 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 6.58 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 88 g of toluene were heated to 110 ° C, and the resulting mixture was reacted for 12 hours. After cooling, the precipitated orange solid was removed by filtration, and heptane was added to the filtrate to crystallize. The precipitated yellow precipitate was collected by filtration, and dried (yield) to afford 4.7 g of compound (61-b) as bright yellow powder. The yield was 51% based on the compound (61-a).

(5) Synthesis Example of Compound (61-c) Compound (61-b) 4.27, 3.83 g of potassium hydroxide and 73 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, 11.23 g of potassium ferricyanide was added under ice cooling, and then 15 g of methanol was added to cause a reaction. The reaction was allowed to proceed for 12 hours at room temperature, and the precipitated yellow precipitate was filtered. The precipitate thus obtained was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The obtained yellow powder was dried under vacuum to give 3.08 g of a pale yellow solid compound (61-c). The yield was 73% based on the compound (61-a).

(6) Synthesis Example of Compound (61-d): 3.08 g of compound (61-c) and 15.4 g of pyridinium chloride were mixed, and the mixture was heated to 190 ° C to carry out a reaction for 7 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, it was washed with toluene and dried under vacuum to give 2.41 g of yellow solid as compound as compound (61-d). The yield was 85% based on the compound (61-c).

(7) Synthesis Example of Compound (A61-1) 2.41 g of compound (61-d), 6.80 g of compound (A), 0.09 g of dimethylaminopyridine, and 38 ml of chloroform were mixed. To the resulting mixture, 2.34 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added with vigorous stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried in vacuo to give a white powder (A61- 1) 4.52g. The yield was 53% based on the compound (61-d). ¹ H-NMR (CDCl ₃ ) of the compound (A61-1): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.85 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.02 to 7.13 (m, 2H) , 7.24 (s, 2H), 7.57 (s, 1H)

The phase transition temperature of the obtained compound (A61-1) was confirmed by pattern observation with a polarizing microscope. The compound (A61-1) showed a highly viscous phase from 136 ° C to 138 ° C at a temperature rise, and a clear nematic phase was obtained from 138 ° C. Further compound (A61-1) exhibits a nematic phase above 150 °C. At the time of cooling, a nematic phase is exhibited at 90 ° C to carry out crystallization.

(Example 28) <Synthesis Example of Compound (A69-1)>

(1) Synthesis Example of 3-Cyclohexyl-6-methylsalicylaldehyde 100 g of 2-cyclohexyl-5-methylphenol, 39.5 g of polyacetal, and 75.0 g of anhydrous magnesium chloride were dispersed in 900 ml of tetrahydrofuran. After stirring for 30 minutes in an ice bath, 106.4 g of triethylamine was added dropwise over two hours. The mixture was allowed to react in a water bath for 8 hours and at room temperature for 96 hours. After adding 1500 ml of cold 5N-hydrochloric acid to the reaction mixture to adjust the acidity, the mixture was extracted twice with 400 ml of ethyl acetate, and the organic layer was collected. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure at 40 ° C or less. The residue was dissolved in 100 ml of toluene, and 600 ml of heptane was added to the solution. After 38 g of tannin was added to the solution, the solvent was removed by an evaporator. After heptane was added to the residue for extraction, heptane was distilled off, and 35.2 g of 4,6-dimethyl salicylaldehyde which was slowly crystallized as a yellow crystal was obtained. The yield was 31% based on 2-cyclohexyl-5-methylphenol.

(2) Synthesis example of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid 35.0 g of 3-cyclohexyl-6-methylsalicylaldehyde and 72.2 g of potassium carbonate are dispersed in N,N'- In dimethyl acetamide 300 ml. After warming to 80 ° C, 41.6 g of butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C for 3 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. The organic layer was further washed twice with 500 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 240 g of acetic acid, and 72 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, and then washed with heptane, and dried in vacuo to give 2,5 g of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid as a white powder. The yield was 59% based on 3-cyclohexyl-6-methyl salicylaldehyde.

(3) Synthesis Example of Compound (69-a): 22.2 g of 2,5-dimethoxyaniline, 25.00 g of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid, and 9.79 g of triethylamine. Dispersed in 125 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 20.4 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 100 g of chloroform was added over 4 hours. The reaction was carried out at room temperature for 72 hours. The obtained mixture was concentrated, and 400 g of a mixed solution of 1 N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue, and 150 g of heptane was added thereto to cause crystallization. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The precipitated pale yellow-green precipitate was collected by filtration, and further washed with a water-methanol mixture solution (2 parts by volume of water and 1 part by volume of methanol). The obtained pale yellow-green precipitate was washed with a mixed solution of 1N-KOH aqueous solution-methanol (1 part by volume of aqueous potassium hydroxide solution, 2 parts by volume of methanol), and then washed with 150 g of methanol and then filtered. The compound (69-a) (12.3 g) was obtained as a pale yellow powder. The yield was 32% based on 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid.

(4) Synthesis Example of Compound (69-b) 12.3 g of Compound (69-a), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 7.6 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 120 g of toluene were heated to 110 ° C, and the resulting mixture was reacted for 6 hours. After cooling, the toluene solution was washed three times with 500 ml of a 2N-aqueous sodium hydroxide solution, and then the organic layer was collected, and then concentrated, and heptane was added thereto, and the solvent was further distilled off with an evaporator. 50 g of methanol was added to the residue to cause crystallization. The obtained fresh yellow crystals were collected by filtration and dried (yield) to give a pale yellow powder of compound (69-b) 11.5 g. The yield was 90% based on the compound (69-a).

(5) Synthesis Example of Compound (69-c) 11.5 g of the compound (69-b) obtained in the above item, 9.58 g of potassium hydroxide and 182 g of water were mixed, and the obtained mixture was reacted under ice cooling. Then, 28.09 g of potassium ferricyanide was added to prepare a dispersion containing the compound (69-b). 40 g of methanol was added to the dispersion and reacted at 40 ° C for 2 hours, and reacted at room temperature for 24 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then with hexane. Further, it was dispersed in 400 ml of a mixed solution of toluene-heptane (1 part by volume of toluene and 2 parts by volume of heptane) to recover a pale yellow insoluble component. The obtained pale yellow color was obtained by vacuum drying, and 4.5 g of pale yellow solid which had compound (69-c) as a main component. The yield was 36% based on the compound (69-a).

(6) Synthesis Example of Compound (69-d) 4.54 g of compound (69-c) and 45.4 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, the mixture was washed with toluene and dried in vacuo to give 3.4 g (yel. The yield was 80% based on the compound (69-c).

(7) Synthesis Example of Compound (A69-1) 3.40 g of Compound (69-d), 7.87 g of Compound (A), 0.11 g of dimethylaminopyridine, and 40 ml of chloroform were mixed. To the obtained mixture, 2.71 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added to the mixture, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give a white powder (A69-1). ) 4.84g. The yield was 45% based on the compound (69-d). ¹ H-NMR (CDCl ₃ ) of the compound (A69-1): δ (ppm) 1.45 to 1.87 (m, 34H), 2.34 to 2.54 (m, 11H), 2.65 to 2.85 (m, 4H), 3.10 to 3.14 (tt, 1H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H) , 6.86 to 7.14 (m, 10H), 7.25 (s, 2H), 7.56 (s, 1H)

The phase transition temperature of the obtained compound (A69-1) was confirmed by pattern observation with a polarizing microscope. The compound (A69-1) showed a highly viscous phase from 207 ° C at a temperature rise, and was thermally polymerized at 220 ° C.

(Example 29) <Synthesis Example of Compound (A70-1)>

(1) Synthesis Example of 3-propyl Salicylaldehyde 75 g of 2-propylphenol, 41.3 g of polyacetal, and 78.7 g of anhydrous magnesium chloride were dispersed in 900 ml of tetrahydrofuran. After stirring for 30 minutes in an ice bath, 111.5 g of triethylamine was added dropwise over two hours. The mixture was allowed to react in a water bath for 8 hours and at room temperature for 96 hours. After adding 1500 ml of cold 5N-hydrochloric acid to the reaction mixture to adjust the acidity, the mixture was extracted twice with 400 ml of ethyl acetate, and the organic layer was collected. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure at 40 ° C or less. The residue was dissolved in 100 ml of toluene, and 600 ml of heptane was added to the solution. After 90 g of tannin was added to the solution, the solvent was removed by an evaporator. After heptane was added to the residue for extraction, heptane was distilled off to obtain 28.8 g of 3-propyl salicylaldehyde as a yellow liquid. The yield was 32% based on 2-propylphenol.

(2) Synthesis example of 7-propylbenzofuran-2-carboxylic acid 28.8 g of 3-propyl salicylaldehyde and 59.3 g of potassium carbonate were dispersed in 200 ml of N,N'-dimethylacetamide. After heating to 80 ° C, 34.2 g of tributyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C for 2 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. The organic layer was further washed twice with 500 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, and 45 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid water, washed with heptane, and dried in vacuo to give a white powder of y-propyl benzofuran-2-carboxylic acid 28.1 g. The yield was 78% based on 3-propyl salicylaldehyde.

(3) Synthesis Example of Compound (70-a) 20.25 g of 2,5-dimethoxyaniline, 18.0 g of 7-propylbenzofuran-2-carboxylic acid, and 8.92 g of triethylamine were dispersed in 90 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 18.6 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 100 g of chloroform was added over 4 hours. The reaction was carried out at room temperature for 72 hours. The obtained mixture was concentrated, and a mixed solution of 1 N-hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) and 400 g of heptane and 150 g of heptane were added to the residue to be crystallized. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The pale yellow-green precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixture (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol), and then filtered. The compound (70-a) was obtained as a pale yellow powder (19.8 g). The yield was 66% based on 7-propylbenzofuran-2-carboxylic acid.

(4) Synthesis Example of Compound (70-b) Mixed Compound (70-a) 19.8 g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di 14.2 g of phosphotidine-2,4-disulfide (Lawesson's reagent) and 198 g of toluene were heated to 110 ° C, and the resulting mixture was reacted for 6 hours. After cooling, the toluene solution was washed three times with 500 ml of a 2N-aqueous sodium hydroxide solution, and then the organic layer was collected and concentrated, and then heptane was added and crystallized. The obtained fresh yellow crystals were collected by filtration, and dried in vacuo to give a pale yellow powder compound (70-b) 18.6 g. The yield was 90% based on the compound (70-a).

(5) Synthesis Example of Compound (70-c) 18.6 g of Compound (70-b), 17.86 g of potassium hydroxide and 320 g of water were mixed, and the obtained mixture was reacted under ice cooling. Then, 52.41 g of potassium ferricyanide was added to prepare a dispersion containing the compound (70-b). 70 g of methanol was added to the dispersion and reacted at 40 ° C for 2 hours, and reacted at room temperature for 24 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then with methanol. The yellow powder was further washed with hot ethanol and filtered. The obtained yellow powder was dried under vacuum to give 15.8 g of pale yellow solid compound (70-c). The yield was 76% based on the compound (70-a).

(6) Synthesis Example of Compound (70-d) 15.8 g of a compound (70-c) and 158 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The obtained mixture was added to ice, and the obtained precipitate was collected by filtration, washed with water, washed with toluene, and dried in vacuo to give 13.6 g of a solid yellow solid compound (70-d). The yield was 94% based on the compound (70-c).

(7) Synthesis Example of Compound (A70-1) 5.00 g of compound (70-d), 13.5 g of compound (A), 0.19 g of dimethylaminopyridine, and 60 ml of chloroform were mixed. To the resulting mixture, 4.65 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over silica gel, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added to the mixture, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give a white powder (A70-1). ) 8.38g. The yield was 48% based on the compound (70-d).

¹ H-NMR (CDCl ₃ ) of the compound (A70-1): δ (ppm) 1.01 to 1.06 (t, 3H), 1.45 to 1.84 (m, 26H), 2.34 to 2.48 (m, 8H), 2.63 to 2.71 (m, 4H), 2.94 to 3.00 (t, 2H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H) 6.36 to 6.44 (m, 2H), 6.87 to 6.98 (m, 8H), 7.22 to 7.24 (m, 4H), 7.52 to 7.53 (m, 2H)

The phase transition temperature of the obtained compound (A70-1) was confirmed by pattern observation with a polarizing microscope. The compound (A70-1) showed a highly viscous phase from 137 ° C to 142 ° C at a temperature rise, and a clear nematic phase was obtained from 142 ° C. Further, the compound (A70-1) exhibited a nematic phase at 220 ° C or higher, and when it was cooled, it exhibited a nematic phase at 125 ° C and was crystallized.

(Examples 30 to 33 and Comparative Example 1)

<Example of Manufacturing Optical Film>

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and after drying, a film having a thickness of 89 nm was formed. Then, the surface of the obtained film was rubbed, and the composition of the composition of Table 4 was applied by spin coating on the surface subjected to the rubbing treatment, and dried at the drying temperature shown in Table 5 for 1 minute. Then, while heating to the temperature at the time of light irradiation described in Table 5, the ultraviolet ray of the integrated light amount shown in Table 5 was irradiated to form an optical film of the film thickness shown in Table 6.

B1-1: a liquid crystal compound represented by formula (B1-1)

LC242: The same polymerization initiator as above: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.: fluorenylphosphine oxide compound) Coating agent: BYK361N (manufactured by BYK Japan) Solvent: cyclopentanone

<Measurement of optical characteristics>

The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Further, since the glass substrate used for the substrate has no birefringence, the film of the glass substrate is measured by a measuring machine, and the front surface difference value of the optical film produced on the glass substrate can be obtained. The obtained optical measurement front-end retardation values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re(447.3)/Re(546.9)] (as α) and [Re(627.8)/Re were calculated. (546.9)] (as β). Further, the film thickness d (μm) of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.). The results are shown in Table 6. The value of Δn system Re (546.9) was calculated by dividing the film thickness (Δn = Re (546.9) / d).

(Examples 34 to 39 and Comparative Examples 2 to 7) <Thermal physical properties of the composition>

<modulation of composition>

The composition of the composition of Table 7 was prepared.

Polymerization initiator: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.: fluorenylphosphine oxide compound) Coating agent: BYK361N (manufactured by BYK Japan) Solvent: cyclopentanone

<Thermal observation]

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and dried by heating to form a film having a thickness of 89 nm. A rubbing treatment is performed on the surface of the diaphragm to form an oriented film. The composition of the composition of Table 8 was applied by spin coating on the surface on which the rubbing treatment was carried out. The coated substrate was subjected to a polarizing microscope (heating station: LTS 350, manufactured by Linkam Co., Ltd., polarizing microscope: BX-51, manufactured by Olympus Co., Ltd.), and heated at a temperature increase rate of 30 ° C /min. The behavior of the composition. Observe the behavior with natural cooling when cooling. The results are shown in Table 8.

T _a : the temperature at which the single phase structure begins to form from the crystalline phase to the nematic phase;

T _b : maintaining the temperature of the nematic phase at a high temperature;

T _c : temperature of crystallization

<Production Example of Diaphragm>

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and dried by heating to form a film having a thickness of 89 nm. A rubbing treatment is performed on the surface of the diaphragm to form an oriented film. The composition described in Table 7 was applied by spin coating on the surface on which the rubbing treatment was carried out, and dried at the temperature (T _d ) shown in Table 9 for 1 minute. After leaving at the temperature (T _e ) shown in Table 9, the film was irradiated with ultraviolet rays having a cumulative light amount of 2400 mJ/cm ^{2 to} form a film. Here, T _e is a temperature required to produce a uniform film in a single domain reproducibility without crystallizing the liquid crystal, and the lower the T _e , the more the optical film can be produced at a lower temperature.

(Example 40) <Synthesis Example of Compound (A71-1)>

(1) Synthesis of 5-chloro-4,6-dimethyl salicylaldehyde

100 g of 4-chloro-3,5-dimethylphenol, 47.94 g of polyacetal, and 91.19 g of anhydrous magnesium chloride were dispersed in 800 ml of acetonitrile. After stirring for 30 minutes in an ice bath, 129.23 g of triethylamine was added dropwise over two hours. The mixture was allowed to react in a water bath for 3 hours and at 50 ° C for 18 hours. After adding cold 5N-hydrochloric acid to the reaction mixture to make it acidic, it was extracted twice with 600 ml of ethyl acetate, and the organic layer was collected. After the organic layer was dehydrated with anhydrous sodium sulfate, 3 g of activated carbon was added and stirred, and the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure at 40 ° C or less. After adding 1000 ml of heptane to the residue, the insoluble matter was removed by filtration. The filtrate was recovered and recrystallized to give a pale yellow powder of 2,5 g of 5-chloro-4,6-dimethyl salicylaldehyde. The yield was 17% based on 4-chloro-3,5-dimethylphenol.

(2) Synthesis of 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid

20.00 g of 5-chloro-4,6-dimethyl salicylaldehyde and 36.68 g of potassium carbonate were dispersed in 150 ml of N,N'-dimethylacetamide. After heating to 80 ° C, 21.13 g of tributyl bromoacetate was added dropwise over 10 minutes. The mixture was reacted at 130 ° C for 3 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. Further, the organic layer was washed twice with 300 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 60 g of acetic acid, and 20 g of trifluoroacetic acid was added thereto, followed by stirring at 60 ° C for 1 hour. After cooling to room temperature, 10 g of 1N-hydrochloric acid water was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid water, then washed with heptane and dried in vacuo to give 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid as a white powder. 19.37g. The yield was 80% based on 5-chloro-4,6-dimethyl salicylaldehyde.

(3) Synthesis example of compound (71-a)

19.43 g of 2,5-dimethoxyaniline and 19.00 g of 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid were dispersed in 200 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 17.64 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 80 g of chloroform was added over 6 hours. The reaction was carried out at room temperature for 24 hours. Further, 0.2 g of 2,5-dimethoxyaniline was added to the reaction solution and allowed to react for 48 hours. The obtained mixture was concentrated, and 400 g of a mixed solution of 1 N-hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue to be crystallized. The obtained pale yellow powder was washed with methanol, washed with toluene, and then filtered. The compound (71-a) (13.63 g) was obtained as a pale yellow powder. The yield was 45% based on the 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid standard.

(4) Synthesis example of compound (71-b)

Mixed compound (71-a) 13.63g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide The material (Lawesson's reagent) was 9.19 g and 150 g of toluene, and the mixture was heated to 110 ° C to react the resulting mixture for 6 hours. After cooling, a 1N-aqueous sodium hydroxide solution was added. The organic layer was recovered, and 100 ml of heptane was added to crystallize it. The red crystals were collected by filtration and dried to give the compound (71-b) 14.24 g of an orange powder. Although impurities from Lawesson's reagents are mixed in, they are still used directly in the next stage.

(5) Synthesis example of compound (71-c)

The compound (71-b) 14.24, potassium hydroxide 11.60 g and water 220 g were mixed, and the obtained mixture was allowed to react under ice cooling. Then, 34.03 g of potassium ferricyanide was added under ice cooling, and then 44 g of methanol was added to cause a reaction. The reaction was carried out at room temperature for 12 hours and at 80 ° C for 8 hours. The precipitated pale yellow precipitate was collected by filtration. The precipitate thus obtained was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The pale yellow powder obtained was dried under vacuum to give 10.3 g of pale yellow solid compound (71-c) as a main component. The yield was 73% based on the compound (71-a) and the second stage.

(6) Synthesis example of compound (71-d)

10.00 g of the compound (71-c) and 100 g of pyridinium chloride were mixed, and the mixture was heated to 190 ° C to carry out a reaction for 2 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After washing with water, the mixture was washed with toluene and chloroform, and dried in vacuo to give 7.20 g of a yellow solid compound (71-d) as a main component. The yield was 78% based on the compound (71-c).

(7) Synthesis example of compound (A71-1)

1.00 g of the compound (71-d), 2.54 g of the compound (A), 0.04 g of dimethylaminopyridine, and 40 ml of chloroform were mixed. To the resulting mixture, 0.88 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over Celite, and concentrated under reduced pressure. Ethanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added, and the resulting white precipitate was filtered, washed with heptane, and dried in vacuo to give a white powder (A71-1). ) 2.58g. The yield was 78% based on the compound (71-d).

¹ H-NMR (CDCl ₃ ) of the compound (A71-1): δ (ppm) 1.45 to 1.83 (m, 24H), 2.35 to 2.85 (m, 18H), 3.93 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.01 (m, 8H), 7.25 (s, 1H), 7.32 (s, 1H), 7.52 (d, 1H)

The phase transition temperature of the obtained compound (A71-1) was confirmed by pattern observation with a polarizing microscope. The compound (A71-1) showed a highly viscous phase from 148 ° C to 154 ° C at a temperature rise, and a clear nematic phase was obtained from 154 ° C. Further, the compound (A71-1) exhibited a nematic phase at 160 ° C or higher, and when it was cooled, it exhibited a nematic phase at 127 ° C and was crystallized.

(Example 41) <Synthesis Example of Compound (A21-1)>

(1) Synthesis example of compound (21-a)

12.82 g of 2,5-dimethoxyaniline and 10.00 g of benzothiazole-2-carboxylic acid were dispersed in 100 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 11.77 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 70 g of chloroform was added over 4 hours. The reaction was carried out at room temperature for 24 hours. Further, 0.5 g of 2,5-dimethoxyaniline was added to the reaction solution and allowed to react for 48 hours. The obtained mixture was concentrated, and 400 g of a mixed solution of 1 N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue, and 150 g of heptane was added thereto to cause crystallization. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The precipitated fresh yellow precipitate was collected by filtration, and further washed with a water-methanol mixture solution (2 parts by volume of water and 1 part by volume of methanol). The obtained fresh yellow precipitate was washed with a mixed solution of 1 N-KOH aqueous solution/methanol (1 part by volume of a potassium hydroxide aqueous solution and 2 parts by volume of methanol), and then washed with 150 g of water and then filtered. The compound (21-a) (8.47 g) was obtained as a yellow powder. The yield was 48% based on the benzothiazole-2-carboxylic acid standard.

(2) Synthesis example of compound (21-b)

Mixed compound (21-a) 8.47g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide The material (Lawesson's reagent) was 6.54 g and 85 g of toluene, and the mixture was heated to 110 ° C to react the resulting mixture for 6 hours. After cooling, a 1N-aqueous sodium hydroxide solution was added. The organic layer was recovered, and 100 ml of heptane was added to crystallize it. The orange crystals were collected by filtration and dried under vacuum to give a compound (21-b) as a pale yellow powder. Although impurities from Lawesson's reagents are mixed in, they are still used directly in the next stage.

(3) Synthesis example of compound (21-c)

8.90 g of the compound (21-b), 8.25 g of potassium hydroxide and 156 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, 24.19 g of potassium ferricyanide was added under ice cooling, and then 30 g of methanol was added to cause a reaction. The reaction was carried out for 12 hours at room temperature, and reacted at 50 ° C for 12 hours, and the precipitated pale yellow precipitate was collected by filtration. The precipitate thus obtained was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The pale yellow powder obtained was dried under vacuum to give 7.40 g of pale yellow solid compound (21-c). The yield was 84% based on the compound (21-a).

(4) Synthesis example of compound (21-d)

7.00 g of the compound (21-c) and 105 g of pyridinium chloride were mixed, and the mixture was heated to 190 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, it was washed with toluene and dried under vacuum to give 6.00 g of a yellow solid compound (21-d) as a main component. The yield was 94% based on the compound (21-c).

(5) Synthesis example of compound (A21-1)

1.00 g of the compound (21-d), 2.93 g of the compound (A), 0.04 g of dimethylaminopyridine, and 50 ml of chloroform were mixed. To the resulting mixture, 1.01 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The obtained reaction solution was allowed to react at room temperature overnight, filtered over Celite, and concentrated under reduced pressure. Methanol was added to the residue to cause crystallization. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, and the mixture was stirred at room temperature for 1 hour. After filtering the solution and concentrating the filtrate to 1/3 under reduced pressure in an evaporator, methanol was added thereto with vigorous stirring, and the resulting white precipitate was filtered, washed with heptane and dried in vacuo to give a white powder (A21-1). 2.70g. The yield was 74% based on the compound (21-d).

¹ H-NMR (CDCl ₃ ) of the compound (A21-1): δ (ppm) 1.45 to 1.83 (m, 24H), 2.32 to 2.50 (m, 8H), 2.62 to 2.84 (m, 4H), 3.93 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.03 (m, 8H) , 7.25 to 7.32 (2d, 2H), 7.50 to 7.59 (m, 2H), 7.97 to 8.00 (dd, 1H), 8.14 to 8.17 (dd, 1H)

The phase transition temperature of the obtained compound (A21-1) was confirmed by pattern observation with a polarizing microscope. The compound (A21-1) showed a highly viscous phase from 137 ° C to 155 ° C at a temperature rise, and a clear nematic phase was obtained from 155 ° C. Further, the compound (A21-1) exhibited a nematic phase at 170 ° C or higher, and when it was cooled, it exhibited a nematic phase at 121 ° C and was crystallized.

(Examples 42 to 43, Comparative Example 1)

<Example of Manufacturing Optical Film>

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and after drying, a film having a thickness of 89 nm was formed. Then, the surface of the obtained film was rubbed, and the composition of the composition of Table 10 was applied by spin coating on the surface on which the rubbing treatment was carried out, and dried at the drying temperature shown in Table 11 for 1 minute. Then, while heating to the temperature at the time of light irradiation described in Table 11, the ultraviolet ray of the integrated light amount shown in Table 11 was irradiated to form an optical film of the film thickness shown in Table 12.

LC242: same as above

Polymerization initiator: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.:

Mercapto phosphine oxide compound)

Coating agent: BYK361N (made by BYK Japan)

Solvent: cyclopentanone

<Measurement of optical characteristics>

The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Further, since the glass substrate used for the substrate has no birefringence, the film of the glass substrate is measured by a measuring machine, and the front surface difference value of the optical film produced on the glass substrate can be obtained. The obtained optical measurement front-end retardation values were measured at wavelengths of 450.9 nm, 549.4 nm, and 627.8 nm, respectively, and [Re(450.9)/Re(549.4)] (as α) and [Re(627.8)/Re were calculated. (549.4)] (as β). Further, the film thickness d (μm) of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.). The results are shown in Table 12. The value of Δn system Re (549.4) was calculated by dividing the film thickness (Δn = Re (549.4) / d).

The optical film systems [Re (447.3) / Re (546.9)] (α in the table) of Examples 12 to 24, Examples 30 to 33, and Examples 42 to 43 have a value of 1 or less. Further, the value of [Re(627.8)/Re(546.9)] (β in the table) is 1 or more. That is, the wavelength dependence of the refractive index indicates the so-called inverse wavelength dispersion property, so that the same polarization conversion can be performed in a wide wide-band region.

When the film of the embodiment is used for a liquid crystal panel, it has characteristics excellent in optical compensation. Further, from Examples 20 to 24 and Examples 32 to 33, it is understood that only the compound of the present invention is mixed with the liquid crystal compound, and the wavelength dispersion property can be freely controlled from the positive wavelength dispersion to the reverse wavelength dispersion.

Further, when Comparative Examples 34 to 39 and Comparative Examples 2 to 7 were compared, it was found that by mixing the compound of the present invention with a liquid crystal compound, the temperature of the single domain structure was shifted to the low temperature side, and the optical film was produced at a lower temperature.

(Examples 44 to 45)

<Example of Manufacturing Optical Film>

In the same manner as in the examples 42 to 43 and the comparative example 1, the composition of the composition shown in Table 13 was applied by spin coating, and after drying at 140 ° C for 1 minute, the integrated light amount was 2400 mJ/cm ² while being heated at 80 ° C. The ultraviolet rays form an optical film. The results are shown in Table 14.

Polymerization initiator: Irgacure 369 (manufactured by Ciba Japan Co., Ltd.: acetonitrile compound)

Irgacure 819 (manufactured by Ciba Japan Co., Ltd.: fluorenylphosphine oxide compound)

Coating agent: BYK361N (made by BYK Japan)

Solvent: cyclopentanone

<The heat resistance test of optical film>

The optical film obtained in Example 44 and Example 45 was kept in an oven at a temperature of 85 ° C and a humidity of 0% for 1,000 hours to carry out a heat resistance test. The optical characteristics before and after the test were measured, and the value of the α value after the test minus the α value of the initial value was used as the amount of change Δα. When Δα is -0.2 or more and +0.2 or less, it can be judged that the change in optical characteristics is small. The results are shown in Table 15.

<The heat and humidity resistance test of optical film>

The optical film obtained in Example 44 and Example 45 was kept in an oven at a temperature of 60 ° C and a humidity of 90% for 1,000 hours, and subjected to a moist heat resistance test. The optical characteristics before and after the test were measured, and the value of the α value after the test minus the α value of the initial value was used as the amount of change Δα. When Δα is -0.2 or more and +0.2 or less, it can be judged that the change in optical characteristics is small. The results are shown in Table 16.

As shown in Tables 15 and 16, it is found that the optical film of the present invention exhibits excellent heat resistance and moist heat resistance in the heat resistance test and the heat and humidity resistance test in which Δα is -0.2 or more and +0.2 or less. . Further, as shown in Table 16, it was found that the optical film of Example 44 showed a smaller Δα in the heat and humidity resistance. Therefore, when an acetophenone compound was used as a polymerization initiator, it was further shown to have good moist heat resistance. , that is, good durability.

(Example 46) <Synthesis Example of Compound (A72-1)>

(1) Synthesis of 4,5,6-trimethyl salicylaldehyde

10.00 g of 3,4,5-trimethylphenol, 5.51 g of polyacetal, and 10.49 g of anhydrous magnesium chloride were dispersed in 60 ml of acetonitrile. After stirring for 30 minutes in an ice bath, 14.86 g of triethylamine was added dropwise over two hours. The mixture was reacted at 50 ° C for 8 hours and at room temperature for 24 hours. After 400 ml of ethyl acetate and 100 ml of pure water were added to the reaction mixture, the mixture was adjusted to be acidic by adding 1N-hydrochloric acid, and then the organic layer was collected. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure at 40 ° C or less. The residue was purified by column chromatography using ethyl acetate and heptane (1:3 by volume) as a solvent to obtain a yellow powder of 4.10 g of 4,5,6-trimethyl salicylaldehyde. The yield was 67% based on 3,4,5-trimethylphenol.

(2) Synthesis of 4,5,6-trimethylbenzofuran-2-carboxylic acid

8.10 g of 4,5,6-trimethyl salicylaldehyde and 16.36 g of potassium carbonate were dispersed in 50 ml of N,N'-dimethylacetamide. After heating to 80 ° C, 9.62 g of tributyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 135 ° C for 2 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, followed by filtration. The filtrate was recovered and separated from 1000 ml of pure water. The organic layer was further washed twice with 500 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, and 45 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid water was added, and the precipitated pale red powder was collected by filtration. The obtained pale red powder was further washed with 1N-hydrochloric acid water, then washed with toluene, and dried in vacuo to give a pale red powder of 4,5,6-trimethylbenzofuran-2-carboxylic acid 6.34. g. The yield was 63% based on 4,5,6-trimethyl salicylaldehyde.

(3) Synthesis example of compound (72-a)

6.13 g of 2,5-dimethoxyaniline and 6.34 g of 4,5,6-trimethylbenzofuran-2-carboxylic acid were dispersed in 30 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 6.55 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 100 g of chloroform was added over 4 hours. The reaction was carried out for 48 hours at room temperature. The obtained mixture was concentrated under reduced pressure, and a mixture of 1N-hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue to crystallize it. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The pale orange precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixture (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol), and then filtered. The compound (72-a) 9.39 g was obtained as a pale yellow powder. The yield was 89% based on 4,5,6-trimethylbenzofuran-2-carboxylic acid.

(4) Synthesis example of compound (72-b)

Mixed compound (72-a) 9.39g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide The material (Lawesson's reagent) was 6.71 g and 95 g of toluene, and the mixture was heated to 110 ° C to react the resulting mixture for 4 hours. After cooling, 500 ml of a 2N-aqueous sodium hydroxide solution and 100 g of heptane were added to the toluene solution, and the precipitated yellow crystals were collected by filtration. The obtained precipitate was further washed with a heptane or a 2N-sodium hydroxide aqueous solution, and dried in vacuo to give a pale yellow powder compound (72-b) 9.83 g. Although the compound (72-b) contained a decomposition product of 3% Lawesson's reagent, it was used directly in the next stage.

(5) Synthesis example of compound (72-c)

9.83 g of compound (72-b), 8.47 g of potassium hydroxide and 400 g of water were mixed, and the obtained mixture was allowed to react under ice cooling. Then, 24.84 g of potassium ferricyanide was added under ice cooling to prepare a dispersion containing the compound (72-b). 70 g of methanol was added to the dispersion, and the mixture was reacted at 60 ° C for 48 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then washed with methanol.

The yellow powder was further recrystallized from hot toluene. The pale yellow crystals formed were collected by filtration and dried in vacuo to give 4.60 g of pale yellow solid compound (72-c). The yield was 47% based on the compound (72-a).

(6) Synthesis example of compound (72-d)

4.60 g of compound (72-c) and 64.4 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After rinsing with water, it was washed with toluene, and dried under vacuum to give 4.10 g of a yellow-green solid compound (72-d) as a main component. The yield was 97% based on the compound (72-c).

(7) Synthesis example of compound (A72-1)

1.10 g of compound (72-d), 2.97 g of compound (A), 0.04 g of dimethylaminopyridine, 20 ml of chloroform, and 20 ml of toluene were mixed. To the resulting mixture, 1.02 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The resulting reaction solution was allowed to react at room temperature overnight. 4 g of tannin extract and 200 mg of activated carbon were added to the reaction liquid, and the mixture was stirred at room temperature for 1 hour, and then filtered over Celite, and the filtrate was concentrated under reduced pressure. After removing chloroform, methanol was added to the solution to cause crystallization. The off-white powder was collected by filtration, washed with ethanol twice, then washed with heptane, and dried in vacuo to give the compound (A72-1) 2.95 g. The yield was 78% based on the compound (72-d).

¹ H-NMR (cDCl ₃ ) of the compound (A72-1): δ (ppm) 1.45 to 1.84 (m, 24H), 2.27 to 2.50 (m, 17H), 2.62 to 2.84 (m, 4H), 3.93 to 3.97 (t, 4H), 4.16 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.45 (m, 2H), 6.87 to 7.02 (m, 8H) , 7.22 to 7.23 (2s, 3H), 7.54 (s, 1H)

The phase transition temperature of the obtained compound (A72-1) was confirmed by pattern observation with a polarizing microscope. The compound (A72-1) showed a highly viscous phase from 136 ° C to 148 ° C at a temperature rise, and a clear nematic phase was obtained from 148 ° C. Further, the compound (A72-1) exhibited a nematic phase at 170 ° C or higher, and when it was cooled, it exhibited a nematic phase at 120 ° C and was crystallized.

(Example 47) <Synthesis Example of Compound (A73-1)>

(1) Synthesis example of 6-methylbenzofuran-2-carboxylic acid

20.0 g of 4-methylsalicylaldehyde and 48.73 g of potassium carbonate were dispersed in 100 ml of N,N'-dimethylacetamide. After warming to 70 ° C, 28.65 g of tributyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 135 ° C for 2 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. The organic layer was further washed twice with 500 ml of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, and 45 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, and then washed with heptane and toluene, and then dried in vacuo to give a white powder (yield: 20.58 g of 6-methylbenzofuran-2-carboxylic acid). The yield was 80% based on 4-methyl salicylaldehyde.

(2) Synthesis example of compound (73-a)

26.09 g of 2,5-dimethoxyaniline, 20.00 g of 6-methylbenzofuran-2-carboxylic acid, and 100 g of chloroform were mixed. After cooling the obtained suspension in an ice bath, a mixture of 23.94 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 120 g of chloroform was added over 4 hours. The reaction was carried out for 48 hours at room temperature. The obtained mixture was concentrated, and 400 g of a mixed solution of 1 N-hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue to be crystallized. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The pale yellow-green precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixture (2 parts by volume of potassium hydroxide aqueous solution, 1 part by volume of methanol) and filtered. The compound (73-a) (31.26 g) was obtained as a pale yellow powder. The yield was 89% based on the 6-methylbenzofuran-2-carboxylic acid standard.

(3) Synthesis example of compound (73-b)

Mixed compound (73-a) 31.26g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide The material (Lawesson's reagent) was 24.73 g and 300 g of toluene, and the mixture was heated to 110 ° C to react the resulting mixture for 6 hours. After cooling, the toluene solution was washed three times with 500 ml of a 2N-aqueous sodium hydroxide solution, and then the organic layer was collected, and n-heptane was added thereto to be crystallized. The obtained fresh yellow crystals were collected by filtration, and dried in vacuo to give a pale yellow powder compound (73-b). The total amount of the obtained compound (73-b) was directly used in the following stages.

(4) Synthesis example of compound (73-c)

The compound (73-b) 35.69, 33.37 g of potassium hydroxide and 630 g of water were mixed. Then, 97.91 g of potassium ferricyanide was added to prepare a dispersion containing the compound (73-b). 126 g of methanol was added to the dispersion, and the mixture was reacted at 40 ° C for 2 hours, and reacted at room temperature for 24 hours, and the precipitated pale yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then washed with methanol. The yellow powder was further washed with hot methanol and filtered. The pale yellow color obtained was dried under vacuum to give 23.31 g of pale yellow solid compound (73-c). The yield was 66% based on the compound (73-a).

(5) Synthesis example of compound (73-d)

23.31 g of the compound (73-c) and 233.1 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After washing with water, it was washed with toluene, and then dispersed in a saturated aqueous solution of sodium dithionite and chloroform, and stirred at room temperature for 2 hours. The dispersion was filtered, and the precipitate was washed with pure water, and then dried in vacuo to give 21.2 g of a yellow solid compound (73-d) as a main component. The yield was 100% based on the compound (73-c).

(6) Synthesis example of compound (A73-1)

1.00 g of the compound (73-d), 2.96 g of the compound (A), 0.04 g of dimethylaminopyridine, 20 ml of chloroform, and 20 ml of toluene were mixed. To the resulting mixture, 1.02 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The resulting reaction solution was allowed to react at room temperature overnight. 4 g of tannin extract and 200 mg of activated carbon were added to the reaction liquid, and the mixture was stirred at room temperature for 1 hour, and then filtered over celite, and the filtrate was concentrated under reduced pressure to remove chloroform, and then methanol was added to the solution to cause crystallization. The off-white powder was filtered, washed with ethanol twice, then washed with heptane, and dried in vacuo to give 2.11 g of Compound (A73-1). The yield was 57% based on the compound (73-d).

¹ H-NMR (CDCl ₃ ) of the compound (A73-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.36 to 2.87 (m, 15H), 3.93 to 3.97 (t, 4H), 4.15 to 4.2 O(t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.45 (m, 2H), 6.87 to 6.99 (m, 8H), 7.13 to 7.16 (d, 1H) ), 7.23 (s, 2H), 7.38 (s, 1H), 7.51 (s, 1H), 7.57 (d, 1H).

The phase transition temperature of the obtained compound (A73-1) was confirmed by pattern observation with a polarizing microscope. The compound (A73-1) showed a highly viscous phase from 82 ° C to 141 ° C at a temperature rise, and a clear nematic phase was obtained from 141 ° C. Further, the compound (A73-1) exhibited a nematic phase at 180 ° C or higher, and when it was cooled, it exhibited a nematic phase at 84 ° C, and slowly crystallized.

(Example 48) <Synthesis Example of Compound (A63-1)>

(1) Synthesis example of 3,4,6-trimethyl salicylaldehyde

20.00 g of 2,3,5-trimethylphenol, 11.03 g of polyoxymethylene, and 20.97 g of anhydrous magnesium chloride were dispersed in 120 g of acetonitrile. After stirring at room temperature for 30 minutes, 29.72 g of triethylamine was added dropwise over two hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 96 hours. The reaction liquid was added to a mixed solvent of 200 ml of ethyl acetate and 400 ml of heptane, and 400 ml of pure water was added. After adding cold 2N-hydrochloric acid to adjust to acidity, the organic layer was recovered. After the organic layer was dehydrated with anhydrous sodium sulfate, 20 g of eucalyptus rubber and 2 g of activated carbon were added, and the mixture was stirred stably for 30 minutes, and the dispersion was subjected to filtration through diatomaceous earth. The filtrate was concentrated under reduced pressure at 40 ° C or less with an evaporator. A pale yellow viscous liquid of 24.69 g of 3,4,6-trimethyl salicylaldehyde was obtained. The yield was 102% based on 2,3,5-trimethylphenol.

(2) Synthesis of 4,6,7-trimethylbenzofuran-2-carboxylic acid

24.11 g of 3,4,6-trimethylsalicylaldehyde and 48.71 g of potassium carbonate were dispersed in 130 ml of N,N'-dimethylacetamide. After warming to 80 ° C, 28.64 g of tributyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 140 ° C for 2 hours. After cooling the reaction mixture to room temperature, 200 ml of methyl isobutyl ketone was added, and the mixture was separated into 1000 ml of pure water. Further, the organic layer was washed twice with 500 ml of 1N-hydrochloric acid water, and the organic layer was collected. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, and 45 g of a hydrobromic acid aqueous solution was added thereto, followed by stirring at 40 ° C for 1 hour. After cooling to room temperature, 150 g of 1N-hydrochloric acid was added, and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, then washed with heptane and toluene, and dried in vacuo to give white powder 4,6,7-trimethylbenzofuran-2-carboxylic acid 14.89. g. The yield is 50% based on 3,4,6-trimethyl salicylaldehyde.

(3) Synthesis example of compound (63-a)

16.75 g of 2,5-dimethoxyaniline and 14.89 g of 4,6,7-trimethylbenzofuran-2-carboxylic acid were dispersed in 75 ml of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 15.37 g of 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride and 100 g of chloroform was added over 4 hours. The reaction was carried out at room temperature for 72 hours. The obtained mixture was concentrated under reduced pressure, and a mixture of 1N-hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added to the residue, and 400 g of heptane was added thereto to cause crystallization. The obtained precipitate was collected by filtration, and a mixed solution of hydrochloric acid and methanol (2 parts by volume of hydrochloric acid and 1 part by volume of methanol) was added. The pale yellow precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixture (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol) and filtered. The compound (63-a) 22.71 g was obtained as a pale yellow powder. The yield was 92% based on the 6-methylbenzofuran-2-carboxylic acid standard.

(4) Synthesis example of compound (63-b)

Mixed compound (63-a) 22.71g, 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide The material (Lawesson's reagent) was 16.24 g and 228 g of toluene, and the mixture was heated to 110 ° C to react the resulting mixture for 6 hours. After cooling, it was washed three times with 500 ml of a 2-N sodium hydroxide aqueous solution in a toluene solution, and the organic layer was collected, and then concentrated, and then heptane was added and crystallized. The pale orange crystals obtained were collected by filtration and dried in vacuo to give a pale yellow powdery compound (63-b) 23.78 g. Although the compound (63-b) contained a decomposition product of Lawesson's reagent, the entire amount was directly used in the next stage.

(5) Synthesis example of compound (63-c)

23.78 g of compound (63-b), 20.48 g of potassium hydroxide and 389 g of water were mixed. Then, 60.09 g of potassium ferricyanide was added to prepare a dispersion containing the compound (63-b). To the dispersion, 77.83 g of methanol was added, and the mixture was reacted at 50 ° C for 4 hours, and reacted at room temperature for 24 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate which was collected by filtration was washed with water and then washed with methanol. The yellow powder was further washed with hot ethanol and filtered. The obtained yellow color was dried under vacuum to give 20.14 g of pale-yellow solid compound (63-c) as a main component. The yield was 86% based on the compound (63-a).

(6) Synthesis example of compound (63-d)

20.14 g of compound (63-c) and 200.1 g of pyridinium chloride were mixed, and the mixture was heated to 180 ° C to carry out a reaction for 3 hours. The resulting mixture was added to ice, and the resulting precipitate was collected by filtration. After washing with water, it was washed with toluene, and then dispersed in a saturated aqueous sodium dithionite solution and chloroform, and stirred at room temperature for 2 hours. The dispersion was filtered, and the precipitate was further washed with pure water, and then dried in vacuo to give 18.9 g of an orange solid compound containing compound (73-d) as a main component. The yield was 102% based on the compound (63-c).

(7) Synthesis example of compound (A63-1)

1.10 g of compound (63-d), 2.97 g of compound (A), 0.04 g of dimethylaminopyridine, 20 ml of chloroform, and 20 ml of toluene were mixed. To the resulting mixture, 1.02 g of N,N'-diisopropylcarbonyldiimide was added under ice cooling. The resulting reaction solution was allowed to react at room temperature overnight. 4 g of tannin extract and 200 mg of activated carbon were added to the reaction liquid, and the mixture was stirred at room temperature for 1 hour, and then filtered over celite, and the filtrate was concentrated under reduced pressure to remove chloroform, and then methanol was added to the solution to cause crystallization. The off-white powder was filtered, washed with ethanol twice, then washed with heptane, and dried in vacuo to give the compound (A63-1) 2.65 g. The yield was 70% based on the compound (63-d).

¹ H-NMR (CDCl ₃ ) of the compound (A63-1): δ (ppm) 1.47 to 1.82 (m, 24H), 2.36 to 2.52 (m, 17H), 2.52 to 2.85 (m, 4H), 3.93 to 3.97 (t, 4H), 4.16 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.45 (m, 2H), 6.87 to 7.05 (m, 9H) , 7.23 (s, 2H), 7.53 (s, 1H).

The phase transition temperature of the obtained compound (A63-1) was confirmed by pattern observation with a polarizing microscope. The compound (A63-1) showed a highly viscous phase from 136 ° C to 139 ° C at a temperature rise, and a clear nematic phase was obtained from 139 ° C. Further, the compound (A63-1) exhibited a nematic phase at 180 ° C or higher, and when it was cooled, it exhibited a nematic phase at 125 ° C and was crystallized.

(Examples 49 to 51, Comparative Example 1)

<Example of Manufacturing Optical Film>

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and after drying, a film having a thickness of 89 nm was formed. Then, the surface of the obtained film was rubbed, and the composition of the composition of Table 17 was applied by spin coating on the surface on which the rubbing treatment was performed, and dried at the drying temperature shown in Table 18 for 1 minute, and then dried. The temperature was increased to the temperature at the time of light irradiation described in Table 18, and the ultraviolet ray of the integrated light amount shown in Table 18 was irradiated to form an optical film of the film thickness shown in Table 19.

LC242: same as above

Polymerization initiator: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.: fluorenylphosphine oxide compound)

Coating agent: BYK361N (made by BYK Japan)

Solvent: cyclopentanone

<Measurement of optical characteristics>

The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Further, since the glass substrate used for the substrate has no birefringence, the film of the glass substrate is measured by a measuring machine, and the front surface difference value of the optical film produced on the glass substrate can be obtained. The obtained optical measurement front-end retardation values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re(447.3)/Re(546.9)] (as α) and [Re(627.8)/Re ( 546.9)] (as β). Further, the film thickness d (μm) of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.). The results are shown in Table 19. The value of Δn system Re (546.9) was calculated by dividing the film thickness (Δn = Re (546.9) / d).

(industrial availability)

The optical film of the present invention can perform the same polarization conversion in a wide frequency band region.

1, 1’. . . Color filter

2, 2’. . . Optical diaphragm

3, 3’. . . Oriented film

4, 4’. . . Color filter layer

5. . . Liquid crystal display device

6,10. . . Polarizer

7,11. . . Substrate

8. . . Counter electrode

9. . . Liquid crystal layer

12. . . TFT, insulating layer

13. . . Transparent electrode

13’. . . Reflective electrode

30, 30a, 30b, 30c, 30d, 30e. . . Polarizer

14, 14’. . . Laminated body

15. . . Polarizing film

16, 16’. . . Support substrate

17, 17’. . . Oriented film

18, 18’. . . Optical diaphragm

19, 19', 22, 25. . . Subsequent layer

20. . . LCD panel

twenty one. . . Fitting

twenty three. . . Organic EL panel

twenty four. . . Luminous layer

Fig. 1 is a schematic view showing a color filter 1 of the present invention.

Fig. 2 is a schematic view showing a liquid crystal display device 5 of the present invention.

Fig. 3 (a) to (e) are schematic views showing a polarizing plate 30 of the present invention.

Fig. 4 is a schematic view showing a bonding product 21 of a liquid crystal panel 20 and a polarizing plate 30 of a liquid crystal display device of the present invention.

Fig. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device of the present invention.

Since the drawings in this case are for illustrative purposes only, they are not representative of the case.

Therefore, there is no designated representative map in this case.

Claims (23)

A compound having a divalent group represented by formula (1-1): (wherein Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and a carbon number of 1 to An alkylsulfonyl group of 6, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an N-alkylamino group having 1 to 6 carbon atoms N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms or -COOH; Q ¹ represents -S-; D ¹ and D ² each independently represent a single bond or a divalent linking group; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group may also have a halogen An atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and -CH ₂ - of the alicyclic hydrocarbon group may also be -O-, -S- or -NH-substituted; Y ¹ is a group represented by the formula (Y ^1-1 ): Wherein Z ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms; Sulfosyl group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N,N-dialkylamino group having 2 to 8 carbon atoms N-alkylamino group having 1 to 4 carbon atoms, amine sulfonyl group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dialkylamine sulfonium having 2 to 12 carbon atoms Or -COOH; V ¹ represents -CO-, -S-, -NR ³ -, -O-, -Se- or -SO ₂ -; W ¹ , W ² , W ³ , W ⁴ and W ⁵ are respectively independent Representing -CR ³ = or -N=, R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; however, at least at least V ¹ , W ¹ , W ² , W ³ , W ⁴ and W ⁵ One line contains S, N, O or Se; a each independently represents an integer from 0 to 3. The compound of claim 1, wherein the compound has a divalent group represented by formula (2-1): Wherein, Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² respectively have the same meanings as defined in the first claim of the patent scope; E ¹ and E ² Each of which independently represents a single bond or a divalent linking group; and B ¹ and B ² each independently represent a single bond or a divalent linking group; and A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; The cyclic hydrocarbon group and the aromatic hydrocarbon group may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a fluorine having 1 to 4 carbon atoms. Alkoxy, cyano or nitro; k and l each independently represent an integer from 0 to 3. For example, the compound of claim 1 is represented by formula (3-1): Wherein Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k and l respectively represent the same meaning as defined in the first and second claims of the patent application; F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms; and the alkanediyl group may also have a carbon number of 1 to 5 An alkyl group, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, the -CH ₂ - of the alkanediyl group may also be substituted by -O- or -CO-; and P ¹ and P ² each independently represent a hydrogen atom or a polymerization. Sexual basis. A compound according to claim 1, wherein the group represented by the formula (Y ¹ -1) is a group represented by the formula (Y ³ -1): In the formula, Z ³ , a, V ¹ and W ² respectively have the same meanings as defined in the first item of the patent application. The compound of claim 1, wherein V ¹ is -S-, -NR ³ -, or -O-. The compound of claim 1, wherein G ¹ and G ² are trans-1,4-cyclohexanediyl. The compound of claim 2, wherein A ¹ and A ² are each independently represented by a 1,4-phenylene group or a 1,4-cyclohexanediyl group, and the 1,4-phenylene group and the 1, The 4-cyclohexanediyl group may also have a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a cyano group or a nitro group. The patentable scope of application of the compound of item 3, wherein B is only bound to A ^{1 1} and A ² binds only to the B ² each independently represent _{-CH 2 -CH 2 -, - CO} -O -, - O-CO -, - CO-NH -, - NH-CO -, - O-CH 2 -, - CH 2 -O- or a single bond, binding to the B ¹ F ¹ and F ² binding to the B ² each independently represent - O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or a single bond. The compound of claim 3, wherein P ¹ and P ² each independently represent a hydrogen atom, an acryloxy group or a methacryloxy group, and P ¹ and P ^{2 are} not hydrogen atoms at the same time. A composition comprising the compound of the first application of the patent application and the liquid crystal compound of the formula (20), which is different from the compound of the first aspect of the patent application: In the formula, A ¹¹ each independently represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group may have a halogen atom or a carbon. An alkyl group of 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, a nitro group, Cyano or thio; B ¹¹ and B ¹² independently represent -CR ¹⁴ R ¹⁵ -, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, - C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S)- O-, -OC(=S)-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O)- , -OCH ₂ -, -OCF ₂ -, -NR ¹⁶ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-, -OC(=O)-CH =CH- or a single bond, and R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, or R ¹⁴ and R ^{15 are} bonded together to represent an alkyl 2 group having 4 to 7 carbon atoms; And R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms; the alkanediyl group may also have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to a halogen atom or an alkoxy group of 6; P ¹¹ represents a polymerizable group; G represents a hydrogen atom a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, and a carbon number of 2 to 26 An N,N-dialkylamino group, a cyano group or a nitro group, or an alkyl group having 1 to 18 carbon atoms having a polymerizable group, and the alkyl group may have an alkoxy group having 1 to 6 carbon atoms or a halogen atom; t represents an integer from 1 to 5. The composition of claim 10, further comprising a polymerization initiator. The composition of claim 11, wherein the polymerization initiator contains an acetophenone compound. An optical film obtained by polymerizing a compound of claim 1 of the patent application. An optical film obtained by polymerizing the composition of any one of claims 10 to 12. An optical film according to claim 13 or 14 which is used for a λ/4 plate having a phase difference (Re (550)) at a wavelength of 550 nm of 113 to 163 nm. An optical film according to claim 13 or 14, which is a λ/2 plate having a phase difference (Re (550)) of 550 nm in the range of 250 to 300 nm. A polarizing plate comprising the optical film and the polarizing film of any one of claims 13 to 16. A color filter formed on an alignment film coated on a color filter substrate, wherein the optical film of any one of claims 13 to 16 is formed. A liquid crystal display device comprising the color filter of claim 18 of the patent application. A flat panel display device comprising a liquid crystal panel including a polarizing plate of claim 17 of the patent application. An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate of claim 17 of the patent application. A method for producing an unpolymerized film, which comprises applying a solution containing a compound of the first application of the patent application to a support substrate or an oriented film formed on a support substrate, followed by drying. A method for producing an optical film, characterized in that the unpolymerized film obtained by the production method of claim 22 of the patent application is cured.