WO2013133178A1 - 化合物、液晶組成物、高分子材料およびフィルム - Google Patents
化合物、液晶組成物、高分子材料およびフィルム Download PDFInfo
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- WO2013133178A1 WO2013133178A1 PCT/JP2013/055720 JP2013055720W WO2013133178A1 WO 2013133178 A1 WO2013133178 A1 WO 2013133178A1 JP 2013055720 W JP2013055720 W JP 2013055720W WO 2013133178 A1 WO2013133178 A1 WO 2013133178A1
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- 0 C*c(cc1)ccc1-c1ccc(*)cc1 Chemical compound C*c(cc1)ccc1-c1ccc(*)cc1 0.000 description 4
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Definitions
- the present invention uses compounds useful for various applications including materials for various optical members such as optically anisotropic films and heat shielding films, liquid crystal compositions and polymer materials containing the compounds, and these. Related to film.
- the liquid crystal aligns regularly when applied on a film (alignment film) that has been subjected to an alignment treatment.
- the alignment state of the liquid crystal can be controlled by sandwiching the liquid crystal between two alignment films. Therefore, in a liquid crystal display device comprising a liquid crystal cell comprising rod-like liquid crystalline molecules and two substrates for encapsulating them, and an electrode layer for applying a voltage to the rod-like liquid crystalline molecules, the liquid crystal display device comprises two substrates. Since the rod-like liquid crystalline molecules are injected into the gap between the formed alignment films, the alignment state of the rod-like liquid crystalline molecules can be controlled relatively easily.
- an optical compensation sheet (retardation plate) is disposed between the liquid crystal cell and the polarizing plate for the purpose of expanding the viewing angle of the liquid crystal display device or eliminating the coloring.
- an optically anisotropic element having an optically anisotropic layer formed from liquid crystalline molecules on a transparent support is used as the optical compensation sheet.
- the optically anisotropic layer is formed by aligning liquid crystal molecules and fixing the alignment state.
- the liquid crystalline molecules are aligned by a single alignment film provided between the transparent support and the optically anisotropic layer.
- Patent Document a technology has been developed to uniformly align the liquid crystal without giving an alignment film on the non-aligned interface (air interface) side.
- the alignment of the liquid crystal molecules is controlled by adding a liquid crystal alignment accelerator having a long core fluorinated alkyl group at the end of the disk-shaped core.
- the liquid crystal composition which a liquid crystalline molecule aligns easily and uniformly by using a liquid crystal alignment promoter is provided.
- the usable concentration range and solubility of the liquid crystal alignment accelerator described in Patent Document 1 are not always sufficient, and there is still room for improvement.
- the object was to provide compounds.
- Another object of the present invention is to provide a new liquid crystal composition capable of lowering the haze of the resulting film by liquid crystal molecules being easily and uniformly aligned.
- the present invention relates to a compound useful for various applications including a material for various optical members such as an optically anisotropic film and a heat-shielding film, a liquid crystal composition containing the compound, a polymer material, and these.
- a material for various optical members such as an optically anisotropic film and a heat-shielding film
- a liquid crystal composition containing the compound a polymer material, and these.
- the purpose is to provide a used film.
- a liquid crystal composition comprising a compound represented by the following general formula (1) and liquid crystal molecules.
- B 1 is an n-valent chain linking group having 1 to 40 carbon atoms (the chain linking group includes at least one —CR 101 R 102 — (R 101 and R 102 are each Independently represents a hydrogen atom, a halogen atom, —COOH, —SO 3 H, —SH, —NH 3 or —OH, and does not include a cyclic structure ⁇
- L 1 and L 2 are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —C ( ⁇ S) O—, —NR 0 CO— or —CONR 0 — (R 0 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
- a 1 represents a divalent aromatic hydrocarbon group
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Hb 1 represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms
- n represents an integer of 2 to 6
- m represents an integer of 0 to 2
- l represents 2 or 3
- L 1 , L 2 , A 1 , A 2 , Sp 1 , Hb 1 , m, and l that appear multiple times in the general formula (1) may be the same or different.
- B 1 preferably contains at least one unsubstituted methylene group.
- n is 2
- the hydrogen atom of the alkylene group may be substituted with a halogen atom, —
- n is 2
- B 1 represents an alkylene group having 1 to 40 carbon atoms, methylene group -O non-adjacent -, - S -, - CO -, - COO -, - OCO -, - COS -, - SCO -, - NR 5 CO -, - CONR 5 - or -NR 5 CONR 5 -(R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), the hydrogen atom of the alkylene group may be substituted with a halogen atom, and B 1 is It is preferable not to include a cyclic structure.
- n 2
- B 1 represents an alkylene group having 1 to 40 carbon atoms
- Non-adjacent methylene groups are substituted with —O—, —S—, —NR 6 — or —NR 6 CONR 6 —
- R 6 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the hydrogen atom of the alkylene group may be preferably substituted with a halogen atom.
- the compound represented by the general formula (1) is a compound represented by the following general formula (2): Is preferred.
- the alkylene group contains at least one unsubstituted methylene group.
- L 11 represents —COO—, —COS— or —CONR 10 —
- L 12 represents a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO.
- R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- a 11 represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group
- a 12 represents an s + 1 valent aromatic hydrocarbon group
- Sp 11 is a single bond or an alkylene group having 1 to 10 carbon atoms (non-adjacent methylene groups in the alkylene are —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO).
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- the hydrogen atom of the alkylene group is substituted with a halogen atom
- Hb 11 represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms
- t represents an integer of 0 to 2
- s represents 2 or 3.
- L 11 , L 12 , A 11 , A 12 , Sp 11 , Hb 11 , s and t appearing a plurality of times in the general formula (2) may be the same or different from each other.
- liquid crystal composition according to [6] is preferably 3 in the general formula (2).
- t represents 0 or 1
- L 11 and L 12 are both —COO—.
- the liquid crystal molecules are preferably polymerizable rod-like liquid crystal molecules.
- the liquid crystal composition according to any one of [1] to [9] preferably contains at least one chiral compound.
- the film according to [12] or [13] preferably exhibits optical anisotropy.
- the film according to any one of [12] to [14] preferably exhibits selective reflection characteristics.
- the film according to [15] preferably exhibits selective reflection characteristics in an infrared wavelength region.
- the alkylene group contains at least one unsubstituted methylene group.
- L 11 represents —COO—, —COS— or —CONR 10 —
- L 12 represents a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO.
- R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- a 11 represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group
- a 12 represents an s + 1 valent aromatic hydrocarbon group
- Sp 11 is a single bond or an alkylene group having 1 to 10 carbon atoms (non-adjacent methylene groups in the alkylene are —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO).
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- the hydrogen atom of the alkylene group is substituted with a halogen atom
- Hb 11 represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms
- s represents an integer of 0 to 2
- t represents 2 or 3
- L 11 , L 12 , A 11 , A 12 , Sp 11 , Hb 11 , s and t appearing a plurality of times in the general formula (2) may be the same or different from each other.
- s is preferably 3 in the general formula (2).
- t represents 0 or 1
- L 11 and L 12 are both —COO—.
- FIG. 1 represents the transmission spectrum of the film of Example 11.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the liquid crystal composition of the present invention includes a compound represented by the following general formula (1) and liquid crystal molecules.
- General formula (1) B 1 is an n-valent chain linking group having 1 to 40 carbon atoms (the chain linking group includes at least one —CR 101 R 102 — (R 101 and R 102 are each Independently represents a hydrogen atom, a halogen atom, —COOH, —SO 3 H, —SH, —NH 3 or —OH, and does not include a cyclic structure ⁇
- L 1 and L 2 are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —C ( ⁇ S) O—, —NR 0 CO— or —CONR 0 — (R 0 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
- a 1 represents a divalent aromatic hydrocarbon group or a
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Hb 1 represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms
- n represents an integer of 2 to 6
- m represents an integer of 0 to 2
- l represents 2 or 3
- L 1 , L 2 , A 1 , A 2 , Sp 1 , Hb 1 , m, and l that appear multiple times in the general formula (1) may be the same or different.
- the liquid crystal composition of the present invention can reduce the haze of the resulting film.
- a molecule having a chain linking group as a core linking moiety has a high degree of freedom, and a compound having this skeleton can align liquid crystal molecules even under high concentration due to its flexible structure.
- the alignment stabilization latitude for liquid crystal molecules is wide and the alignment stabilization ability is high.
- the surface uneven distribution of the compound represented by the general formula (1) is enhanced, and the alignment of the liquid crystal molecules can be promoted.
- the liquid crystal alignment accelerator means that when the compound is added to the liquid crystal composition and then cured by alignment, the liquid crystal composition is added without adding the compound and cured. Means a compound that reduces haze.
- the liquid crystal alignment accelerator is sometimes called a haze reducing agent or a haze reducing agent.
- the compound represented by the general formula (1) described later can be preferably added to the liquid crystal composition of the present invention as a liquid crystal alignment accelerator (that is, a haze reducing agent or a haze reducing agent).
- B 1 is an n-valent chain linking group having 1 to 40 carbon atoms (the chain linking group is at least one —CR 101 R 102 — (R 101 and R 102 are each independently Represents a hydrogen atom, a halogen atom, —COOH, —SO 3 H, —SH, —NH 3 or —OH), and does not include a cyclic structure.
- the chain linking group means that it does not include a cyclic structure such as an aromatic ring, an aliphatic ring or a heterocyclic ring, and the chain linking group may be branched or linear. Since the compound represented by the general formula (1) has B 1 having such a structure as a chain linking group as a core linking moiety, the effect of the present invention is exhibited.
- R 101 and R 102 each independently preferably represents a hydrogen atom, a halogen atom, —COOH, —SO 3 H, —SH or —OH, more preferably a hydrogen atom or a halogen atom, It is particularly preferable to represent a fluorine atom, and it is particularly preferable to represent a hydrogen atom. That is, in the liquid crystal composition of the present invention, in the general formula (1), B 1 preferably contains at least one unsubstituted methylene group.
- the n-valent chain linking group having 1 to 40 carbon atoms represented by B 1 contains at least one —CR 101 R 102 —, preferably two or more, and contains 2 to 20 carbon atoms. It is more preferable that 2 to 10 are included.
- linking groups other than —CR 101 R 102 — may be contained.
- R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 6 are each independently hydrogen atoms Or an alkyl group having 1 to 6 carbon atoms
- R 2 preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group, It is more particularly preferable to represent a hydrogen atom.
- the alkyl group that R 2 can take may be linear or branched.
- R 5 and R 6 each independently preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably represents a hydrogen atom or a methyl group, and particularly preferably represents a hydrogen atom.
- the alkyl group that R 5 and R 6 can take may be linear or branched.
- the n-valent chain linking group having 1 to 40 carbon atoms represented by B 1 preferably contains 0 to 20 other linking groups other than the —CR 101 R 102 —, and has 0 to 10 linking groups. More preferably, 0 to 5 are included.
- n represents an integer of 2 to 6, preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.
- B 1 has at least one trivalent to hexavalent linking group.
- R is a hydrogen atom or an arbitrary substituent
- -* is a bond (* is an arbitrary bonding site, and is directly or via an additional optional linking group to L 1 .
- RC (-*) 3 and C (-*) 4 are preferable. Since these tri- to hexavalent linking groups are not cyclic, they are treated as part of the chain linking group in this specification.
- B 1 represents a divalent chain linking group having 1 to 40 carbon atoms.
- B 1 represents an alkylene group having 1 to 40 carbon atoms
- the hydrogen atom of the alkylene group may be substituted with a halogen atom, —COOH, —SO 3 H, —SH, —NH 3 or —OH.
- B 1 is at least one —CR 101 R 102 — (R 101 and R 102 are each independently a hydrogen atom, a halogen atom, —COOH, —SO 3 H, —SH, —NH 3 or —OH. Represents).
- L 1 and L 2 are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —C. ( ⁇ S) O—, —NR 0 CO— or —CONR 0 — (R 0 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), more preferably a single bond, —O—, —S.
- R 10 is independently a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Represents a group).
- L 1 particularly preferably represents —O—, —COO—, —COS— or —CONR 10 —, more particularly preferably represents —O— or —COO—, and even more preferably represents —COO—. Particularly preferred.
- L 2 particularly preferably represents a single bond, —O—, —COO— or —OCO—, more preferably represents —O— or —COO—, and even more particularly preferably represents —COO—.
- the combination of L 1 and L 2 includes a combination in which L 1 represents —O— and L 2 represents —O—, L 1 represents —COO—, and L 2 represents —COO—.
- a combination in which L 1 represents —COO— and L 2 represents —COO— is more preferable.
- R 0 and R 10 each independently preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably represents a hydrogen atom or a methyl group, and particularly preferably represents a hydrogen atom.
- the alkyl group that R 5 and R 6 can take may be linear or branched.
- a 1 represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group, and more preferably a divalent aromatic hydrocarbon.
- the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, still more preferably 6 to 10 carbon atoms, and still more preferably 6.
- the divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring.
- a 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is most preferable.
- a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
- the heterocycle is preferably an aromatic heterocycle.
- the aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable.
- heterocyclic rings examples include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline Ring, pyrazolidine ring, triazole ring, triazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring included.
- the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 may have a substituent.
- substituents include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or a group containing an ester structure.
- the alkyl group that can be substituted by the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. 3 is more preferable.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
- the divalent aromatic hydrocarbon group represented by A 1 or the divalent heterocyclic group the divalent aromatic hydrocarbon group represented by A 1 or Reference can be made to the description and preferred ranges of the substituent alkyl group of the divalent heterocyclic group.
- the halogen atom that can be substituted for the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- An atom and a bromine atom are preferable.
- Examples of the group containing an ester structure that can be substituted by a divalent aromatic hydrocarbon group represented by A 1 or a divalent heterocyclic group include a group represented by R′COO—.
- Examples of R ′ include an alkyl group having 1 to 8 carbon atoms.
- explanation and preferred explanation of the alkyl group that R ′ can take explanation and preferred explanation of the alkyl group that can be taken by the substituent of the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 above. You can refer to the range.
- Specific examples of the ester include CH 3 COO— and C 2 H 5 COO—.
- Preferred examples of the substituent for the divalent aromatic hydrocarbon group or divalent heterocyclic group include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, and a cyano group.
- a 2 represents an l + 1 valent aromatic hydrocarbon group.
- the carbon number of the l + 1 valent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 14, still more preferably 6 to 10, and still more preferably 6.
- the number of carbon atoms of the l + 1 valent aromatic hydrocarbon group is 6, it is preferable to have a bond at the meta position or the para position, more preferably at least a bond at the para position. It is particularly preferable to have a bond.
- the l + 1 valent aromatic hydrocarbon group represented by A 2 may have a substituent.
- substituents examples include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group, or a group containing an ester structure.
- substituents of the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 above Preferred examples of the substituent for the l + 1 valent aromatic hydrocarbon group represented by A 2 include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, and a cyano group.
- Sp 1 is a single bond or an alkylene group having 1 to 10 carbon atoms (non-adjacent methylene groups in the alkylene are —O—, —S—, —CO—, —COO—, —OCO— , —COS—, —SCO—, —NR 1 CO—, —CONR 1 — (wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or the like.
- the hydrogen atom of the alkylene group may be substituted with a halogen atom or a hydroxyl group ⁇ , more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, and still more preferably a single bond or carbon number. 1 to 5 alkylene groups.
- the alkylene group may or may not be branched, but a linear alkylene group having no branch is preferred.
- R 1 preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably represents a hydrogen atom or a methyl group, and particularly preferably represents a hydrogen atom.
- the alkyl group that R 1 can take may be linear or branched.
- a non-adjacent methylene group in a single bond represented by Sp 1 or an alkylene group having 1 to 10 carbon atoms is substituted, it is preferably substituted with —O—, —COO—, or —OCO—.
- the number of non-adjacent methylene groups in the single bond or the alkylene group having 1 to 10 carbon atoms represented by Sp 1 is preferably 0 to 2, and preferably 0 or 1 1 is particularly preferable.
- a hydrogen atom of a single bond represented by Sp 1 or an alkylene group having 1 to 10 carbon atoms is substituted, it is preferably substituted with a halogen atom (more preferably a fluorine atom).
- a halogen atom more preferably a fluorine atom
- Hb 1 represents a fluorinated alkyl group having 2 to 30 carbon atoms, more preferably a fluorinated alkyl group having 4 to 30 carbon atoms, and particularly preferably a fluorinated alkyl group having 4 to 10 carbon atoms. It is.
- the fluorinated alkyl group may or may not be substituted with hydrogen.
- the fluorinated alkyl group may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear.
- Preferred examples of the fluorinated alkyl group include those having a perfluoroalkyl group at the end. That is, it is preferably a group represented by the following general formula.
- p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
- q is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 5.
- p + q is preferably 3 to 30.
- a group represented by H— (C p F 2p ) — (C p H 2q ) — instead of a perfluoroalkyl group can also be used as the fluorinated alkyl group. If Hb 1 there are a plurality, the plurality of Hb 1 may have a different structure may be the same structure, but are preferably the same structure.
- m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
- l is 2 or 3, and is preferably 3.
- L 1 , L 2 , A 1 , A 2 , Sp 1 , Hb 1 , m, and l that appear multiple times in the general formula (1) may be the same or different.
- l and m represent 2 or more, the structure in the parenthesis which exists respectively 1 and m may mutually be same or different.
- the compound represented by the general formula (1) may or may not have a symmetrical molecular structure.
- the symmetry here means one corresponding to any of point symmetry, line symmetry, or rotational symmetry
- asymmetry means one not corresponding to any of point symmetry, line symmetry, or rotational symmetry.
- Hb 1 -Sp 1-at the molecular end of the compound represented by the general formula (1) is preferably a group represented by any one of the following general formulas.
- p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
- q is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 5.
- p + q is preferably 3 to 30.
- r is preferably from 1 to 10, and more preferably from 1 to 4.
- the compound represented by the following general formula (2) is a novel compound and is also preferable from the viewpoint of the effects of the present invention.
- the alkylene group contains at least one unsubstituted methylene group ⁇ , L 11 represents —COO—, —COS— or —CONR 10 —, and L 12 represents a single bond, —O
- R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- a 11 represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group
- a 12 represents an s + 1 valent aromatic hydrocarbon group
- Sp 11 is a single bond or an alkylene group having 1 to 10 carbon atoms (non-adjacent methylene groups in the alkylene are —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO).
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- the hydrogen atom of the alkylene group is substituted with a halogen atom
- Hb 11 represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms
- s represents an integer of 0 to 2
- t represents 2 or 3
- L 11 , L 12 , A 11 , A 12 , Sp 11 , Hb 11 , s and t appearing a plurality of times in the general formula (2) may be the same or different from each other.
- the preferable range of B 11 in the general formula (2) is the same as the preferable range of B 1 in the general formula (1).
- L 11 in the general formula (2) represents —COO—, —COS— or —CONR 10 —, and is preferably —COO—.
- L 12 in the general formula (2) is a single bond, —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —NR 10 CO— or —CONR 10 —.
- R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- the preferred range of L 12 is the same as the preferred range of L 2 in the general formula (1).
- the combination of L 11 and L 12 in the general formula (2) is preferably a combination in which L 11 represents —COO— and L 12 represents —COO—.
- the preferred range of A 11 in the general formula (2) is the same as the preferred range of A 1 in the general formula (1).
- the preferred range of A 12 in the general formula (2) is the same as the preferred range of A 2 in the general formula (1).
- the preferred range of Sp 11 in the general formula (2) is the same as the preferred range of Sp 1 in the general formula (1).
- the preferable range of Hb 11 in the general formula (2) is the same as the preferable range of Hb 1 in the general formula (1).
- t represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
- s is 2 or 3, and is preferably 3.
- L 11 , L 12 , A 11 , A 12 , Sp 11 , Hb 11 , s and t appearing a plurality of times in the general formula (2) may be the same or different from each other.
- s and t represent 2 or more, the structures in parentheses where there are s and t, respectively, may be the same or different.
- the compound represented by the general formula (1) can be synthesized by appropriately selecting and combining the synthesis methods described in JP-A No. 2002-129162 and the literature cited therein. Moreover, it can synthesize
- Two or more compounds represented by the general formula (1) may be used in the liquid crystal composition of the present invention, and the compound represented by the general formula (1) and other liquid crystal alignment accelerators are used in combination. May be.
- the compound represented by the general formula (1) is preferably used in an amount of 0.01 to 20% by mass of the amount of liquid crystal molecules.
- the amount of the compound represented by the general formula (1) is more preferably 0.1 to 5% by mass with respect to the liquid crystal molecules. In some cases, the amount of the compound represented by the general formula (1) is preferably 0.15 to 3% by mass with respect to the liquid crystal molecules.
- the liquid crystal composition of the present invention contains liquid crystal molecules.
- the liquid crystal molecules are preferably polymerizable liquid crystal molecules having a polymerizable group.
- one or more kinds of polymerizable liquid crystal molecules and one or more kinds of non-polymerizable liquid crystal molecules may be used in combination.
- the polymerizable liquid crystalline molecule it is preferable to use a discotic liquid crystalline molecule or a rod-like liquid crystalline molecule.
- Discotic liquid crystalline molecules are described in various documents C. Destrade et al. , Mol. Crysr. Liq. Cryst. , Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, quarterly chemistry review, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994); Kohne et al. , Angew. Chem. Soc. Chem. Comm. , Page 1794 (1985); Zhang et al. , J. et al. Am. Chem. Soc. , Vol. 116, page 2655 (1994)).
- the polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284.
- the discotic liquid crystalline molecule having a polymerizable group is preferably a compound represented by the following formula. D (-L D -Q) d Where D is a discotic core; L D is a divalent linking group; Q is a polymerizable group; d is an integer from 4 to 12.
- LQ means a combination of a divalent linking group (L D ) and a polymerizable group (Q).
- triphenylene (D4) is particularly preferable.
- linking group L D and a polymerizable group Q can be referred to [0161] ⁇ [0171] of JP 2002-129162.
- Examples of the polymerizable rod-like liquid crystalline molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted compounds. Phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
- the birefringence of the polymerizable rod-like liquid crystal molecule is preferably 0.001 to 0.7.
- the rod-like liquid crystal molecules preferably have a molecular structure that is substantially symmetric with respect to the minor axis direction. For that purpose, it is preferable to have a polymerizable group at both ends of the rod-like molecular structure. Specific examples of rod-like liquid crystalline molecules are shown below.
- the liquid crystal composition may be a solvent, a compound containing an asymmetric carbon atom, or a polymerizable initiator (described later) or others, if necessary.
- Other additives eg, cellulose esters.
- Optically active compound chiral agent
- the liquid crystal composition preferably exhibits a cholesteric liquid crystal phase, and for that purpose, it preferably contains an optically active compound.
- the rod-like liquid crystal compound is a molecule having an illegitimate carbon atom
- a cholesteric liquid crystal phase may be stably formed without adding an optically active compound.
- the optically active compound includes various known chiral agents (eg, Liquid Crystal Device Handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 42nd Committee, 1989). Description).
- the optically active compound generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as a chiral agent.
- the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
- the optically active compound (chiral agent) may have a polymerizable group.
- the optically active compound has a polymerizable group and the rod-like liquid crystal compound used in combination also has a polymerizable group, it is derived from the rod-like liquid crystal compound by a polymerization reaction of the polymerizable optically active compound and the polymerizable rod-like liquid crystal compound.
- a polymer having a repeating unit and a repeating unit derived from an optically active compound can be formed.
- the polymerizable group possessed by the polymerizable optically active compound is preferably the same group as the polymerizable group possessed by the polymerizable rod-like liquid crystal compound.
- the polymerizable group of the optically active compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group.
- the optically active compound may be a liquid crystal compound.
- the optically active compound in the liquid crystal composition is preferably 1 to 30 mol% with respect to the liquid crystal compound used in combination. A smaller amount of the optically active compound is preferred because it often does not affect liquid crystallinity. Therefore, the optically active compound used as the chiral agent is preferably a compound having a strong twisting power so that a twisted orientation with a desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include those described in JP-A-2003-287623, which can be preferably used in the present invention.
- organic solvent examples include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane).
- amides eg N, N-dimethylformamide
- sulfoxides eg dimethyl sulfoxide
- heterocyclic compounds eg pyridine
- hydrocarbons eg benzene, hexane
- alkyl halides eg , Chloroform, dichloromethane
- esters eg
- a film can be formed by forming the liquid crystal composition of the present invention by a method such as coating.
- An optically anisotropic element can also be produced by applying a liquid crystal composition on an alignment film to form a liquid crystal layer.
- the film of the present invention preferably exhibits optical anisotropy.
- the liquid crystal composition can be applied by a known method (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, bar coating method).
- the liquid crystalline molecules are preferably fixed while maintaining the alignment state.
- the immobilization is preferably performed by a polymerization reaction of the polymerizable group (Q) introduced into the liquid crystal molecule.
- the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator.
- a photopolymerization reaction is preferred.
- photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos.
- the amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.
- Light irradiation for polymerization of discotic liquid crystalline molecules is preferably performed using ultraviolet rays.
- the irradiation energy is preferably 20 mJ / cm 2 to 50 J / cm 2 , and more preferably 100 to 800 mJ / cm 2 .
- light irradiation may be performed under heating conditions.
- the thickness is preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 30 ⁇ m, and most preferably from 2 to 20 ⁇ m.
- the total coating amount of the compound represented by the general formula (1) in the liquid crystal layer is preferably 0.1 to 500 mg / m 2 , and preferably 0.5 to 450 mg / m 2. m 2 is more preferable, 0.75 to 400 mg / m 2 is further preferable, and 1.0 to 350 mg / m 2 is most preferable.
- the film of the present invention is also preferably a layer formed by fixing the cholesteric liquid crystal phase of the liquid crystal composition of the present invention, in which case it preferably exhibits selective reflection characteristics, and exhibits selective reflection characteristics in the infrared wavelength region. It is particularly preferred. Details of the light reflecting layer formed by fixing the cholesteric liquid crystal phase are described in the methods described in JP 2011-107178 A and JP 2011-018037 A, and can be preferably used in the present invention.
- the film of the present invention is also preferably a laminate comprising a plurality of layers formed by fixing the cholesteric liquid crystal phase of the liquid crystal composition of the present invention. Since the liquid crystal composition of the present invention has good lamination properties, such a laminate can be easily formed.
- the alignment film is an organic compound (eg, ⁇ -tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field or light irradiation is also known. An alignment film formed by a polymer rubbing treatment is particularly preferable.
- an organic compound eg, ⁇ -tricosanoic acid
- the rubbing treatment is carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth.
- the type of polymer used for the alignment film is determined according to the alignment (particularly the average tilt angle) of the liquid crystal molecules.
- a polymer that does not decrease the surface energy of the alignment film ordinary alignment film polymer
- a polymer that lowers the surface energy of the alignment film is used.
- the thickness of the alignment film is preferably 0.01 to 5 ⁇ m, and more preferably 0.05 to 1 ⁇ m.
- the liquid crystal layer may be transferred onto the transparent support.
- the liquid crystalline molecules fixed in the alignment state can maintain the alignment state even without the alignment film. Further, in the case of orientation with an average inclination angle of less than 5 °, rubbing treatment is unnecessary and an orientation film is not necessary.
- an alignment film (described in JP-A-9-152509) forming a chemical bond with the liquid crystalline molecules at the interface may be used.
- an alignment film is used for the purpose of improving adhesion, rubbing treatment need not be performed.
- the liquid crystal layer formed on the transparent support can also function as an alignment film for the liquid crystal layer provided thereon.
- the optically anisotropic element having the film of the present invention or the film of the present invention may have a transparent support.
- a transparent support a glass plate or a polymer film, preferably a polymer film is used. That the support is transparent means that the light transmittance is 80% or more.
- an optically isotropic polymer film is used as the transparent support.
- the optical isotropy preferably has an in-plane retardation (Re) of less than 10 nm, more preferably less than 5 nm.
- the retardation (Rth) in the thickness direction is preferably less than 10 nm, and more preferably less than 5 nm.
- the in-plane retardation (Re) and the thickness direction retardation (Rth) of the transparent support are respectively defined by the following formulas.
- Re (nx ⁇ ny) ⁇ d
- Rth [ ⁇ (nx + ny) / 2 ⁇ -nz] ⁇ d
- nx and ny are in-plane refractive indexes of the transparent support
- nz is the refractive index in the thickness direction of the transparent support
- d is the thickness of the transparent support.
- the transparent support preferably has optical uniaxiality or optical biaxiality.
- optical uniaxial support even if it is optically positive (the refractive index in the optical axis direction is larger than the refractive index in the direction perpendicular to the optical axis), it is negative (the refractive index in the optical axis direction is It may be smaller than the refractive index in the vertical direction.
- refractive indices nx, ny and nz in the above formula are all different values (nx ⁇ ny ⁇ nz).
- the in-plane retardation (Re) of the optically anisotropic transparent support is preferably 10 to 1000 nm, more preferably 15 to 300 nm, and most preferably 20 to 200 nm.
- the thickness direction retardation (Rth) of the optically anisotropic transparent support is preferably 10 to 1000 nm, more preferably 15 to 300 nm, and still more preferably 20 to 200 nm.
- the material for forming the transparent support is determined depending on whether it is an optical isotropic support or an optical anisotropic support.
- an optically isotropic support glass or cellulose ester is generally used.
- an optically anisotropic support a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin) is generally used.
- optical properties may be reduced by (1) using a retardation increasing agent, (2) reducing the acetylation degree of cellulose acetate, or (3) producing a film by the cooling dissolution method described in the specification of European Patent 0911656A2.
- An isotropic (high retardation) cellulose ester film can also be produced.
- the transparent support made of a polymer film is preferably formed by a solvent cast method.
- an optically anisotropic transparent support it is preferable to perform a stretching process on the polymer film.
- a normal uniaxial stretching process or biaxial stretching process may be performed.
- an optical biaxial support it is preferable to perform an unbalanced biaxial stretching process.
- unbalanced biaxial stretching the polymer film is stretched in a certain direction (for example, 3 to 100%, preferably 5 to 30%) and further in the direction perpendicular thereto (for example, 6 to 200%, preferably 10 to 90%).
- the bi-directional stretching process may be performed simultaneously.
- the stretching direction (the direction in which the stretching ratio is high in unbalanced biaxial stretching) and the slow axis in the plane of the stretched film are substantially the same direction.
- the angle between the stretching direction and the slow axis is preferably less than 10 °, more preferably less than 5 °, and most preferably less than 3 °.
- the thickness of the transparent support is preferably 10 to 500 ⁇ m, more preferably 50 to 200 ⁇ m.
- surface treatment eg, glow discharge treatment, corona discharge treatment, ultraviolet light ( UV) treatment, flame treatment.
- An ultraviolet absorber may be added to the transparent support.
- An adhesive layer undercoat layer
- the adhesive layer is described in JP-A-7-333433.
- the thickness of the adhesive layer is preferably from 0.1 to 2 ⁇ m, and more preferably from 0.2 to 1 ⁇ m.
- Carboxylic acid (3d) can be synthesized from compound (3c) by the route shown in the above scheme by a known synthesis method. Furthermore, carboxylic acid (3d) was derived into acid chloride using thionyl chloride and reacted with gallic acid hydrate to obtain carboxylic acid (3e). This carboxylic acid (3e) was derived into acid chloride using thionyl chloride, and reacted with diol (3d) in the presence of DIPEA to obtain compound (24).
- 1 H NMR 300 MHz, CDCl 3 ) ⁇ 2.4-2.6 (m, 12H), 2.7-2.8 (m, 12H), 2.9-3.1 (m, 12H), 4. 4-4.5 (m, 12H), 4.8 (t, 4H), 7.3 (d, 4H), 7.9 (s, 3H), 8.1 (d, 4H)
- Example 11 to 22 and Comparative Example 1 Using the liquid crystal alignment accelerator described in Table 1 below, films of Examples and Comparative Examples showing optical anisotropy were formed and evaluated.
- a coating solution having the following composition was prepared.
- the concentration of the liquid crystal alignment accelerator was adjusted to 0.10 parts by mass or 0.20 parts by mass with respect to the rod-like liquid crystal compound.
- the following rod-shaped liquid crystal compound 1 100 parts by mass
- the following chiral agent (A) 5.0 parts by mass IRGACURE 819 (manufactured by Ciba Japan) 3 parts by mass Liquid crystal alignment accelerators described in Table 1 Solvents described in the above Table 1 The amount that makes the concentration 25% by mass
- the coating solution prepared above was weighed out by 50 ⁇ l using a micropipette and dropped onto glass with alignment film (SE-130) and spin-coated at a rotation speed of 2000 rpm. After heating at 85 ° C. for 2 minutes and allowing to cool for 1 minute, ultraviolet irradiation (ultraviolet light intensity: 500 mJ / m 2 ) is performed in a nitrogen atmosphere to form films of Examples and Comparative Examples showing optical anisotropy. did.
- the film thicknesses of the films of Examples and Comparative Examples showing optical anisotropy were both about 5 ⁇ m.
- the transmission spectrum of the film of Example 11 was measured using a spectrophotometer UV-3100PC manufactured by SHIMADZU. The results are shown in FIG. From FIG. 1, it was found that the film prepared in Example 11 is a selective reflection film having a central wavelength in the near infrared region near 900 nm and exhibits optical anisotropy.
- the compound of the present invention has a large haze-reducing effect and high solubility in a solvent even when the concentration is increased.
- a haze reduction is because the liquid crystal alignment action of the compound of the present invention is large, so that the alignment of the liquid crystal is good even on the air interface side, that is, the compound of the present invention.
- the same tendency was observed when a film was formed in the same manner as in Examples 11 to 22, except that the solvent type was changed to methyl ethyl ketone and the solute concentration was changed to 33%, and a liquid crystal haze reduction test was similarly conducted. It was confirmed that the compound of the present invention has a wide application range of the coating solvent and high suitability for use.
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Abstract
Description
[1] 下記一般式(1)で表される化合物と、液晶分子とを含むことを特徴とする液晶組成物。
一般式(1)
L1およびL2はおのおの独立して単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-C(=S)O-、-NR0CO-または-CONR0-(R0は水素原子または炭素数1~6のアルキル基を表す)を表し、
A1は2価の芳香族炭化水素基または2価の複素環基を表し、
A2はl+1価の芳香族炭化水素基を表し、
Sp1は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR1CO-、-CONR1-(R1は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子またはヒドロキシル基で置換されていてもよい}を表し、
Hb1は炭素数4~30のフッ素置換アルキル基を表し、
nは2~6の整数を表し、
mは0~2の整数を表し、
lは2または3を表す。一般式(1)中で複数回登場するL1、L2、A1、A2、Sp1、Hb1、mおよびlは同じであっても異なっていてもよい。]
[2] [1]に記載の液晶組成物は、前記一般式(1)中、B1が少なくとも1つの無置換のメチレン基を含むことが好ましい。
[3] [1]または[2]に記載の液晶組成物は、前記一般式(1)中、nが2であり、B1が炭素数1~40のアルキレン基を表し、該アルキレン基中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR2CO-、-CONR2-、-NR2CONR2-、-NR2-、-CR2=CR2-、-C≡C-または-CR2R2-(R2はそれぞれ独立して水素原子または炭素数1~10のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子、-COOH、-SO3H、-SH、-NH3または-OHで置換されていてもよく、B1が環状構造を含まないことが好ましい。
[4] [1]または[2]に記載の液晶組成物は、前記一般式(1)中、nが2であり、B1が炭素数1~40のアルキレン基を表し、該アルキレン基中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR5CO-、-CONR5-または-NR5CONR5-(R5はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよく、B1が環状構造を含まないことが好ましい。
[5] [1]または[2]に記載の液晶組成物は、前記一般式(1)中、nが2であり、B1が炭素数1~40のアルキレン基を表し、該アルキレン基中の隣接しないメチレン基は-O-、-S-、-NR6-または-NR6CONR6-(R6はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよいことが好ましい。
[6] [1]~[5]のいずれか一項に記載の液晶組成物は、前記一般式(1)で表される化合物が、下記一般式(2)で表される化合物であることが好ましい。
一般式(2)
L11は-COO-、-COS-または-CONR10-を表し、L12は単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR10CO-または-CONR10-(R10はそれぞれ独立して水素原子または炭素数1~6のアルキル基を表す)を表し、
A11は2価の芳香族炭化水素基または2価の複素環基を表し、
A12はs+1価の芳香族炭化水素基を表し、
Sp11は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR11CO-または-CONR11-(R11は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよい}を表し、
Hb11は炭素数が4~30のフッ素置換アルキル基を表し、
tは0~2の整数を表し、
sは2または3を表す。一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。]
[7] [6]に記載の液晶組成物は、前記一般式(2)中、sが3であることが好ましい。
[8] [6]または[7]に記載の液晶組成物は、前記一般式(2)中、tが0または1を表し、L11およびL12がともに-COO-であることが好ましい。
[9] [1]~[8]のいずれか一項に記載の液晶組成物は、前記液晶分子が重合性棒状液晶分子であることが好ましい。
[10] [1]~[9]のいずれか一項に記載の液晶組成物は、少なくとも1種のキラル化合物を含有することが好ましい。
[11] [1]~[10]のいずれか1項に記載の液晶組成物を重合させてなることを特徴とする高分子材料。
[12] [11]に記載の高分子材料の少なくとも1種を含有することを特徴とするフィルム。
[13] [1]~[10]のいずれか1項に記載の液晶組成物のコレステリック液晶相を固定してなることを特徴とするフィルム。
[14] [12]または[13]に記載のフィルムは、光学異方性を示すことが好ましい。
[15] [12]~[14]のいずれか1項に記載のフィルムは、選択反射特性を示すことが好ましい。
[16] [15]に記載のフィルムは、赤外線波長域に選択反射特性を示すことが好ましい。
[17] 下記一般式(2)で表されることを特徴とする化合物。
一般式(2)
L11は-COO-、-COS-または-CONR10-を表し、L12は単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR10CO-または-CONR10-(R10はそれぞれ独立して水素原子または炭素数1~6のアルキル基を表す)を表し、
A11は2価の芳香族炭化水素基または2価の複素環基を表し、
A12はs+1価の芳香族炭化水素基を表し、
Sp11は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR11CO-または-CONR11-(R11は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよい}を表し、
Hb11は炭素数が4~30のフッ素置換アルキル基を表し、
sは0~2の整数を表し、
tは2または3を表す。一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。]
[18] [17]に記載の化合物は、前記一般式(2)中において、sが3であることが好ましい。
[19] [17]または[18]に記載の化合物は、前記一般式(2)中において、tが0または1を表し、L11およびL12がともに-COO-であることが好ましい。
以下に記載する構成要件の説明は、本発明の代表的な実施態様や具体例に基づいてなされることがあるが、本発明はそのような実施態様や具体例に限定されるものではない。なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本発明の液晶組成物は、下記一般式(1)で表される化合物と、液晶分子とを含むことを特徴とする。
一般式(1)
L1およびL2はおのおの独立して単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-C(=S)O-、-NR0CO-または-CONR0-(R0は水素原子または炭素数1~6のアルキル基を表す)を表し、
A1は2価の芳香族炭化水素基または2価の複素環基を表し、
A2はl+1価の芳香族炭化水素基を表し、
Sp1は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR1CO-、-CONR1-(R1は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子またはヒドロキシル基で置換されていてもよい}を表し、
Hb1は炭素数4~30のフッ素置換アルキル基を表し、
nは2~6の整数を表し、
mは0~2の整数を表し、
lは2または3を表す。一般式(1)中で複数回登場するL1、L2、A1、A2、Sp1、Hb1、mおよびlは同じであっても異なっていてもよい。]
このような構成を有することにより、本発明の液晶組成物は、得られるフィルムのヘイズを低下させることができる。いかなる理論に拘泥するものでもないが、鎖状連結基をコア連結部分として有する分子は自由度が大きく、この骨格を有する化合物は柔軟な構造のため高濃度下でも液晶分子を配向させることができ、液晶分子に対する配向安定化ラティチュードが広く、配向安定化能力が高い。さらに、フッ化アルキル基を分子の両末端に2本以上有することにより、一般式(1)で表される化合物の表面偏在性が高まり、液晶分子の配向を促進できる。
以下、本発明の液晶組成物に用いられる一般式(1)で表される化合物の好ましい構造、一般式(1)で表される化合物の合成方法、その他の本発明の液晶組成物の好ましい組成などについて、説明する。
ここで、鎖状連結基とは、芳香環や脂肪族環や複素環などの環状構造を含まないことを意味し、鎖状連結基は分枝であっても直鎖であってもよい。
一般式(1)で表される化合物はこのような構造のB1を鎖状連結基としてコア連結部分として有するため、本発明の効果を奏する。
前記-CR101R102-以外のその他の連結基としては特に制限はないが、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR2CO-、-CONR2-、-NR2CONR2-、-NR2-、-CR2=CR2-、-C≡C-または-CR2R2-(R2はそれぞれ独立して水素原子または炭素数1~10のアルキル基を表す)が好ましく、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR5CO-、-CONR5-または-NR5CONR5-(R5はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)がより好ましく、-O-、-S-、-NR6-または-NR6CONR6-(R6はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)が特に好ましい。
R2は水素原子または炭素数1~6のアルキル基を表すことが好ましく、水素原子または炭素数1~3のアルキル基を表すことがより好ましく、水素原子またはメチル基を表すことが特に好ましく、水素原子を表すことがより特に好ましい。上記のR2がとりうるアルキル基は、直鎖状であっても分枝状であってもよい。
R5およびR6はそれぞれ独立に水素原子または炭素数1~3のアルキル基を表すことが好ましく、水素原子またはメチル基を表すことがより好ましく、水素原子を表すことが特に好ましい。上記のR5およびR6がとりうるアルキル基は、直鎖状であっても分枝状であってもよい。
なお、これらの3~6価の連結基は環状でないため、鎖状連結基の一部として本明細書中では扱う。
このとき、B1は炭素数1~40のアルキレン基を表すことが好ましく、該アルキレン基中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR2CO-、-CONR2-、-NR2CONR2-、-NR2-、-CR2=CR2-、-C≡C-または-CR2R2-(R2はそれぞれ独立して水素原子または炭素数1~10のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子、-COOH、-SO3H、-SH、-NH3または-OHで置換されていてもよいことが好ましい。
また、B1は炭素数1~40のアルキレン基を表すとき、該アルキレン基の水素原子はハロゲン原子、-COOH、-SO3H、-SH、-NH3または-OHで置換されていてもよいが、当然B1は少なくとも1つの-CR101R102-(R101およびR102はそれぞれ独立して水素原子、ハロゲン原子、-COOH、-SO3H、-SH、-NH3または-OHを表す)を含む。
L1は-O-、-COO-、-COS-または-CONR10-を表すことが特に好ましく、-O-または-COO-を表すことがより特に好ましく、-COO-を表すことがさらにより特に好ましい。
L2は単結合、-O-、-COO-または-OCO-を表すことが特に好ましく、-O-または-COO-を表すことがより特に好ましく、-COO-を表すことがさらにより特に好ましい。
L1およびL2の組み合わせとしては、L1が-O-を表し、かつL2が-O-を表す組み合わせ、L1が-COO-を表し、かつL2が-COO-を表す組み合わせが好ましく、L1が-COO-を表し、かつL2が-COO-を表す組み合わせがより好ましい。
R0およびR10はそれぞれ独立に水素原子または炭素数1~3のアルキル基を表すことが好ましく、水素原子またはメチル基を表すことがより好ましく、水素原子を表すことが特に好ましい。上記のR5およびR6がとりうるアルキル基は、直鎖状であっても分枝状であってもよい。
A1で表される2価の芳香族炭化水素基または2価の複素環基は置換基を有していてもよい。そのような置換基の例として、炭素数1~8のアルキル基、アルコキシ基、ハロゲン原子、シアノ基またはエステル構造を含む基を挙げることができる。A1で表される2価の芳香族炭化水素基または2価の複素環基の置換基がとりうるアルキル基の炭素数は1~8であり、1~5であることが好ましく、1~3であることがより好ましい。アルキル基は、直鎖状、分枝状、環状のいずれであってもよく、直鎖状または分枝状であることが好ましい。好ましいアルキル基として、メチル基、エチル基、n-プロピル基、イソプロピル基などを例示することができる。
A1で表される2価の芳香族炭化水素基または2価の複素環基の置換基がとりうるアルコキシ基のアルキル部分については、A1で表される2価の芳香族炭化水素基または2価の複素環基の置換基アルキル基の説明と好ましい範囲を参照することができる。
A1で表される2価の芳香族炭化水素基または2価の複素環基の置換基がとりうるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、塩素原子、臭素原子が好ましい。
A1で表される2価の芳香族炭化水素基または2価の複素環基の置換基がとりうるエステル構造を含む基としては、R’COO-で表される基を例示することができる。R’としては炭素数1~8のアルキル基を挙げることができる。R’がとりうるアルキル基の説明と好ましい範囲については、上記のA1で表される2価の芳香族炭化水素基または2価の複素環基の置換基がとりうるアルキル基の説明と好ましい範囲を参照することができる。エステルの具体例として、CH3COO-、C2H5COO-を挙げることができる。
2価の芳香族炭化水素基または2価の複素環基に対する置換基としては、例えばメチル基、エチル基、メトキシ基、エトキシ基、臭素原子、塩素原子、シアノ基などを好ましく挙げることができる。
A2で表されるl+1価の芳香族炭化水素基は置換基を有していてもよい。そのような置換基の例として、炭素数1~8のアルキル基、炭素数1~8のアルコキシ基、ハロゲン原子、シアノ基またはエステル構造を含む基を挙げることができる。これらの基の説明と好ましい範囲については、上記のA1で表される2価の芳香族炭化水素基または2価の複素環基の置換基の対応する記載を参照することができる。A2で表されるl+1価の芳香族炭化水素基に対する置換基としては、例えばメチル基、エチル基、メトキシ基、エトキシ基、臭素原子、塩素原子、シアノ基などを好ましく挙げることができる。
R1は水素原子または炭素数1~3のアルキル基を表すことが好ましく、水素原子またはメチル基を表すことがより好ましく、水素原子を表すことが特に好ましい。上記のR1がとりうるアルキル基は、直鎖状であっても分枝状であってもよい。
Sp1が表す単結合または炭素数1~10のアルキレン基中の隣接しないメチレン基が置換されている場合は-O-、-COO-、-OCO-で置換されていることが好ましい。
Sp1が表す単結合または炭素数1~10のアルキレン基中の隣接しないメチレン基が上記の2価の連結基で置換されている数は0~2であることが好ましく、0または1であることが好ましく、1であることが特に好ましい。
Sp1が表す単結合または炭素数1~10のアルキレン基の水素原子が置換されている場合はハロゲン原子(その中でもフッ素原子がより好ましい)で置換されていることが好ましいが、前記一般式(1)で表される化合物は、Sp1が表す単結合または炭素数1~10のアルキレン基の水素原子が無置換であることがより好ましい。
(CpF2p+1)-(CpH2q)-
上式において、pは1~30であることが好ましく、1~20であることがより好ましく、1~10であることがさらに好ましい。qは0~20であることが好ましく、0~10であることがより好ましく、0~5であることがさらに好ましい。p+qは3~30であることが好ましい。
なお、本発明ではフッ化アルキル基として末端がパーフルオロアルキル基ではなく、H-(CpF2p)-(CpH2q)-で表される基も用いることができる。
Hb1が複数存在する場合、複数のHb1は同一構造であっても異なる構造であってもよいが、同一構造であることが好ましい。
一般式(1)中、lは2または3であり、3であることが好ましい。
一般式(1)中で複数回登場するL1、L2、A1、A2、Sp1、Hb1、mおよびlは同じであっても異なっていてもよい。また、l、mが2以上を表す場合、それぞれlおよびm個ずつ存在する括弧内の構造は互いに同じでも異なっていてもよい。
(CpF2p+1)-(CqH2q)-
(CpF2p+1)-(CqH2q)-O-(CrH2r)-
(CpF2p+1)-(CqH2q)-COO-(CrH2r)-
(CpF2p+1)-(CqH2q)-OCO-(CrH2r)-
上式において、pは1~30であることが好ましく、1~20であることがより好ましく、1~10であることがさらに好ましい。qは0~20であることが好ましく、0~10であることがより好ましく、0~5であることがさらに好ましい。p+qは3~30であることが好ましい。rは1~10であることが好ましく、1~4であることがより好ましい。
L11は-COO-、-COS-または-CONR10-を表し、L12は単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR10CO-または-CONR10-(R10はそれぞれ独立して水素原子または炭素数1~6のアルキル基を表す)を表し、
A11は2価の芳香族炭化水素基または2価の複素環基を表し、
A12はs+1価の芳香族炭化水素基を表し、
Sp11は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR11CO-または-CONR11-(R11は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよい}を表し、
Hb11は炭素数が4~30のフッ素置換アルキル基を表し、
sは0~2の整数を表し、
tは2または3を表す。一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。]
一般式(2)中、sは2または3であり、3であることが好ましい。
一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。また、sおよびtが2以上を表す場合、それぞれsおよびt個ずつ存在する括弧内の構造は互いに同じでも異なっていてもよい。
前記一般式(1)で表される化合物の好ましい合成法としては、後述の本明細書中における実施例に記載した方法を挙げることができる。
本発明の液晶組成物は、液晶分子を含む。
前記液晶分子は重合性基を有する重合性液晶分子であることが好ましい。
本発明の液晶組成物では、1種類以上の重合性液晶分子と1種類以上の非重合性液晶分子を併用してもよい。
D(-LD-Q)d
上式中、Dは円盤状コアであり;LDは二価の連結基であり;Qは重合性基であり;dは4~12の整数である。上記式の円盤状コア(D)の具体例を以下に示す。以下の各具体例において、LQ(またはQL)は、二価の連結基(LD)と重合性基(Q)との組み合わせを意味する。以下の具体例の中では、トリフェニレン(D4)が特に好ましい。
液晶組成物は、重合性液晶性分子および前記一般式(1)で表される化合物に加えて、必要に応じて溶媒、不斉炭素原子を含む化合物、あるいは重合性開始剤(後述)や他の添加剤(例えば、セルロースエステル)を含むことができる。
前記液晶組成物は、コレステリック液晶相を示すものであることが好ましく、そのためには、光学活性化合物を含有しているのが好ましい。但し、上記棒状液晶化合物が不正炭素原子を有する分子である場合には、光学活性化合物を添加しなくても、コレステリック液晶相を安定的に形成可能である場合もある。前記光学活性化合物は、公知の種々のキラル剤(例えば、液晶デバイスハンドブック、第3章4-3項、TN、STN用カイラル剤、199頁、日本学術振興会第一42委員会編、1989に記載)から選択することができる。光学活性化合物は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物あるいは面性不斉化合物もカイラル剤として用いることができる。軸性不斉化合物または面性不斉化合物の例には、ビナフチル、ヘリセン、パラシクロファンおよびこれらの誘導体が含まれる。光学活性化合物(キラル剤)は、重合性基を有していてもよい。光学活性化合物が重合性基を有するとともに、併用する棒状液晶化合物も重合性基を有する場合は、重合性光学活性化合物と重合性棒状液晶合物との重合反応により、棒状液晶化合物から誘導される繰り返し単位と、光学活性化合物から誘導される繰り返し単位とを有するポリマーを形成することができる。この態様では、重合性光学活性化合物が有する重合性基は、重合性棒状液晶化合物が有する重合性基と、同種の基であることが好ましい。従って、光学活性化合物の重合性基も、不飽和重合性基、エポキシ基又はアジリジニル基であることが好ましく、不飽和重合性基であることがさらに好ましく、エチレン性不飽和重合性基であることが特に好ましい。
また、光学活性化合物は、液晶化合物であってもよい。
液晶組成物の溶媒としては、有機溶媒が好ましく用いられる。有機溶媒の例には、アミド(例、N,N-ジメチルホルムアミド)、スルホキシド(例、ジメチルスルホキシド)、ヘテロ環化合物(例、ピリジン)、炭化水素(例、ベンゼン、ヘキサン)、アルキルハライド(例、クロロホルム、ジクロロメタン)、エステル(例、酢酸メチル、酢酸ブチル)、ケトン(例、アセトン、メチルエチルケトン、シクロヘキサノン)、エーテル(例、テトラヒドロフラン、1,2-ジメトキシエタン)が含まれる。アルキルハライドおよびケトンが好ましい。二種類以上の有機溶媒を併用してもよい。
[フィルム]
本発明の液晶組成物を塗布等の方法により製膜することによりフィルムを形成することができる。液晶組成物を配向膜の上に塗布し、液晶層を形成することにより光学異方性素子を作製することもできる。本発明のフィルムは、光学異方性を示すことが好ましい。
液晶組成物の塗布は、公知の方法(例、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、ダイコーティング法、バーコーティング法)により実施できる。液晶性分子は、配向状態を維持して固定することが好ましい。固定化は、液晶性分子に導入した重合性基(Q)の重合反応により実施することが好ましい。
光重合開始剤の例には、α-カルボニル化合物(米国特許2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許2722512号明細書記載)、多核キノン化合物(米国特許3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許4239850号明細書記載)、オキサジアゾール化合物(米国特許4212970号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、特開平10-29997号公報記載)が含まれる。
本発明のフィルムは、本発明の液晶組成物のコレステリック液晶相を固定してなる層であることも好ましく、その場合は選択反射特性を示すことがより好ましく、赤外線波長領域に選択反射特性を示すことが特に好ましい。コレステリック液晶相を固定してなる光反射層については、特開2011-107178号公報および特開2011-018037号公報に記載の方法に詳細が記載されており、本発明でも好ましく用いることができる。
本発明のフィルムは、本発明の液晶組成物のコレステリック液晶相を固定してなる層を複数積層してなる積層体とすることも好ましい。本発明の液晶組成物は積層性も良好であるため、このような積層体を容易に形成することができる。
配向膜は、有機化合物(好ましくはポリマー)のラビング処理、無機化合物の斜方蒸着、マイクログルーブを有する層の形成、あるいはラングミュア・ブロジェット法(LB膜)による有機化合物(例、ω-トリコサン酸、ジオクタデシルメチルアンモニウムクロライド、ステアリル酸メチル)の累積のような手段で、設けることができる。さらに、電場の付与、磁場の付与あるいは光照射により、配向機能が生じる配向膜も知られている。ポリマーのラビング処理により形成する配向膜が特に好ましい。ラビング処理は、ポリマー層の表面を、紙や布で一定方向に、数回こすることにより実施する。配向膜に使用するポリマーの種類は、液晶性分子の配向(特に平均傾斜角)に応じて決定する。液晶性分子を水平(平均傾斜角:0~50゜)に配向させるためには、配向膜の表面エネルギーを低下させないポリマー(通常の配向膜用ポリマー)を用いる。液晶性分子を垂直(平均傾斜角:50~90゜)に配向させるためには、配向膜の表面エネルギーを低下させるポリマーを用いる。配向膜の表面エネルギーを低下させるためには、ポリマーの側鎖に炭素数が10~100の炭化水素基を導入することが好ましい。
本発明のフィルムや本発明のフィルムを有する光学異方性素子は、透明支持体を有していてもよい。透明支持体として、ガラス板またはポリマーフィルム、好ましくはポリマーフィルムが用いられる。支持体が透明であるとは、光透過率が80%以上であることを意味する。透明支持体として、一般には、光学等方性のポリマーフィルムが用いられている。光学等方性とは、具体的には、面内レターデーション(Re)が10nm未満であることが好ましく、5nm未満であることがさらに好ましい。また、光学等方性透明支持体では、厚み方向のレターデーション(Rth)も、10nm未満であることが好ましく、5nm未満であることがさらに好ましい。透明支持体の面内レターデーション(Re)と厚み方向のレターデーション(Rth)は、それぞれ下記式で定義される。
Re=(nx-ny)×d
Rth=[{(nx+ny)/2}-nz]×d
式中、nxおよびnyは、透明支持体の面内屈折率であり、nzは透明支持体の厚み方向の屈折率であり、そしてdは透明支持体の厚さである。
アルコール(1a)(45.7ml,300mmol)とパラトルエンスルホニルクロライド(60.1g,315mmol)を120mlの塩化メチレン中、氷冷下で1時間反応させた。反応液を分液操作に施し、有機層をエバポレーターにより濃縮し、粗体として黄色液体のトシルエーテル体(1b)を得た。このまま精製せずに次工程の原料として使用した。
1H NMR(300MHz、CDCl3)δ2.4(s,3H), 3.6(d,2H), 4.2(d,2H), 4.4(s,2H), 7.1-7.4(d×3,s×1,7H), 7.8(d,2H)
トシル誘導体(1b)(16.2g,50mmol)と2-(パーフルオロヘキシル)エタノール(12.1ml,55ml)をトルエン100mlに加え、ベンジルトリメチルアンモニウムヒドロキサイド水溶液105ml加えた。70℃に昇温して30分攪拌した後、水酸化カリウム水溶液(3.1g/水20ml)を添加した。その後、80℃に昇温し、5時間反応させた。酢酸エチルを100ml、水を50mlを加えて分液した後濃縮し、粗体としてエーテル(1c)を得た。このまま精製せずに次工程の原料として使用した。
1H NMR(300MHz、CDCl3)δ2.5(m,2H), 3.8(d,2H), 4.0(d,2H), 4.4(s,2H), 7.1-7.4(m,5H)
エーテル(1c)(20.0g,40mmol)を酢酸エチル40ml中で、パラジウム触媒(1.2g,5%パラジウム/活性炭素、デグサタイプE 101 O/W 5%Pd,wako社製)存在下、水素と反応させた。反応終了後、セライトろ過によりパラジウム触媒を除去し、濃縮し、粗体のアルコール(1d)を得た。このまま精製せずに次工程の原料として使用した。
1H NMR(400MHz、CDCl3)δ2.4(m,2H), 3.6(d,2H), 3.7(d,2H), 3.8(d,2H)
アルコール(1d)(18.0g,45mmol)を酢酸エチル30ml中に添加し、氷冷した。反応系内の温度を20℃以下に保って、メタンスルホニルクロライド(3.8ml,49.5mmol)を滴下した。室温で3時間反応させ、酢酸エチルと水によって分液し、濃縮し、粗体のメタンスルホン酸エステル(1e)を得た。このまま精製せずに次工程の原料として使用した。
エステル(1e)(10.6g,21.6mmol)と没食子酸メチルエステル(1.28g,7.0mmol)を炭酸カリウム(3.0g,21.6mmol)存在下、DMAc40ml中、90℃で反応させた。酢酸エチル/水系で分液操作後、カラム精製により、オイル状の没食子酸エステル(1f)(8.0g, 84%)を得た。
1H NMR(400MHz、CDCl3)δ2.3-2.6(m,6H), 3.7-4.0(m,15H), 4.2(m,6H), 7.4(s,2H)
エステル(1f)(7.8g, 5.8mmol)をエタノール40ml、水4ml中に加えた。この溶液に水酸化カリウム(0.48g, 8.6mmol)を添加し2時間加熱還流した。この反応液を酢酸エチル/水系で分液し、有機層を濃縮固化させ、カルボン酸(1g)(5.6g, 72%)
を得た。
カルボン酸(1g)(2.0g,1.5mmol)をトルエン10mlと触媒量のDMF中で塩化チオニル(0.16ml,2.2mmol)と反応させて酸クロライドとし、過剰の塩化チオニル及びトルエン除去後、THF5ml、触媒量のDMAPを系中に添加した。そこへ、THF5ml及びジイソプロピルエチルアミン0.28ml、ジエチレングリコール(79mg,0.75mmol)を滴下した。酢酸エチル/水系で分液操作後、エバポレーターにて濃縮し、カラム精製し、酢酸エチル/メタノール系で再結晶して化合物(1)(1.4g,70%)を得た。
1H NMR(300MHz、CDCl3)δ2.3-2.5(m,12H), 3.7-3.9(m,28H), 4.1-4.2(m,12H), 4.4-4.5(m,4H), 7.3(s,4H)
1H NMR(300MHz、CDCl3)δ2.3-2.5(m,12H), 3.7-3.9(m,24H), 4.1-4.2(m,12H), 4.6(s,4H), 7.3(s,4H)
4-ヒドロキシチオフェノール(1e)(10.0g,79.3mmol)と1,2-ビス(クロロエトキシ)エタン(7.06g,37.76mmol)を炭酸カリウム(11.0g,79.3mmol)存在下、DMAc35ml中、50℃で反応させた。酢酸エチル/水系で分液操作後、カラム精製により、結晶状のジオール(2b)(5.7g, 42%)を得た。
上記(1-7)における化合物(1)の合成でジエチレングリコールの代わりにジオール(2b)を用いた以外は実施例1と同様の操作により化合物(21)を得た。
1H NMR(300MHz、CDCl3)δ2.3-2.5(m,12H), 3.1(t,4H), 3.6(s,4H), 3.7(t,4H), 3.8-3.9(m,24H), 4.2-4.3(m,12H), 7.1(d,4H), 7.4(d,4H), 7.5(s,4H)
2,2,3,3,4,4,5,5,6,6,7,7-ドデカフルオロ-1,8-オクタンジオール(18.1g,50mmol)とp-ヒドロキシ安息香酸(3a)(13.8g,100mmol)をパラトルエンスルホン酸一水和物(4.8g,25mmol)存在下、トルエン100ml中、加熱還流下で反応させた。酢酸エチル/水系で分液操作後、カラム精製により、結晶状のジオール(3b)(21.1g,70%)を得た。
カルボン酸(3d)は既知の合成法により、化合物(3c)から上記スキームに示したルートで合成できる。さらにカルボン酸(3d)を、塩化チオニルを用いて酸クロライドへと誘導し、没食子酸水和物と反応させてカルボン酸(3e)を得た。このカルボン酸(3e)を、塩化チオニルを用いて酸クロライドへと誘導し、DIPEA存在下ジオール(3d)と反応させて化合物(24)を得た。
1H NMR(300MHz、CDCl3)δ2.4-2.6(m,12H), 2.7-2.8(m,12H), 2.9-3.1(m,12H), 4.4-4.5(m,12H), 4.8(t,4H), 7.3(d,4H), 7.9(s,3H), 8.1(d,4H)
1H NMR(300MHz、CDCl3)δ2.3-2.5(m,12H), 2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.8-3.9(m.4H), 4.3-4.4(m,12H), 4.4-4.5(m,4H), 7.8(s,4H)
1H NMR(300MHz、CDCl3)δ1.8-1.9(m,2H), 2.3-2.5(m,12H),2.7-2.8(m,12H), 2.9-3.0(m,12H), 4.3-4.4(m,4H), 4.4-4.5(m,12H), 7.8(s,4H)
1H NMR(300MHz、CDCl3)δ1.8-1.9(m,4H), 2.4-2.6(m,12H),2.7-2.8(m,12H), 2.9-3.0(m,12H), 4.3-4.4(m,4H), 4.4-4.5(m,12H), 7.8(s,4H)
1H NMR(300MHz、CDCl3)δ1.4-1.5(m,2H), 1.6-1.7(m,4H), 2.4-2.6(m,12H),2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.4-3.5(m,4H), 4.3-4.5(m,12H), 6.3(t,2H), 7.6(s,4H)
1H NMR(300MHz、CDCl3)δ2.4-2.6(m,12H), 2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.5-3.7(m,12H), 4.3-4.5(m,12H), 6.9-7.0(m,2H), 7.6(s,4H)
1H NMR(300MHz、CDCl3)δ2.4-2.6(m,12H),2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.2-3.3(m,4H), 3.5-3.6(m,4H),3.8-4.0(m,4H), 4.3-4.5(m,12H),7.8(s,4H)
1H NMR(300MHz、CDCl3)δ1.8-1.9(m,4H),2.4-2.6(m,12H),2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.5-3.7(m,16H), 4.3-4.4(m,12H), 7.6(s,4H)
1H NMR(300MHz、CDCl3)δ2.4-2.6(m,12H),2.7-2.8(m,12H), 2.8-3.0(m,12H), 3.4-3.5(m,4H), 3.8-3.9(m,1H),3.9-4.0(m,1H), 4.3-4.5(m,1H),7.8(s,4H)
下記表1に記載した液晶配向促進剤を用いて、光学異方性を示す各実施例および比較例のフィルムを形成して評価した。
まず、下記組成の塗布液を調製した。液晶配向促進剤の濃度は、棒状液晶化合物に対して0.10質量部または0.20質量部となるように調製した。
下記の棒状液晶化合物1 100質量部
下記のキラル剤(A) 5.0質量部
IRGACURE819(チバジャパン社製) 3質量部
表1に記載した液晶配向促進剤 上記の量
表1に記載した溶媒 溶質濃度が25質量%となる量
上記にて調製した塗布液をマイクロピペッターを用いて50μl量り取り、配向膜付ガラス上(SE―130)に滴下して2000rpmの回転速度でスピンコートした。85℃で2分間加熱し、1分間放冷したのち、窒素雰囲気下で紫外線照射(紫外線強度:500mJ/m2)することで、光学異方性を示す各実施例および比較例のフィルムを形成した。光学異方性を示す各実施例および比較例のフィルムの膜厚はいずれも約5μmであった。
なお、代表例として実施例11のフィルムの透過スペクトルを、SHIMADZU社製分光光度計UV-3100PCを用いて測定した。その結果を図1に示した。図1より、実施例11で作成したフィルムは900nm付近の近赤外領域に中心波長を有する選択反射膜であり、光学異方性を示すことがわかった。
製造した各実施例および比較例のフィルムの配向性を目視及びヘイズで評価した。ヘイズは、日本電飾社製ヘイズメータNDH2000を用いて測定した。
配向試験では、液晶配向促進剤の濃度が0.10質量%、0.20質量%であるフィルムのヘイズ値により下記の2段階で配向促進作用を評価した。評価が高いものは、配向促進作用が大きいことを示している。
○ 1.00未満
× 1.00以上
得られた結果を下記表1に記載した。
なお、溶媒の種類をメチルエチルケトンに代え、溶質濃度を33%に変更した以外は実施例11~22と同様にしてフィルムを製膜し、同様に液晶ヘイズ低下試験を行った場合も同じ傾向を示しており、本発明の化合物が塗布溶媒の適用範囲が広くて、使用適性が高いことが確認された。
Claims (19)
- 下記一般式(1)で表される化合物と、液晶分子とを含むことを特徴とする液晶組成物。
一般式(1)
L1およびL2はおのおの独立して単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-C(=S)O-、-NR0CO-または-CONR0-(R0は水素原子または炭素数1~6のアルキル基を表す)を表し、
A1は2価の芳香族炭化水素基または2価の複素環基を表し、
A2はl+1価の芳香族炭化水素基を表し、
Sp1は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR1CO-、-CONR1-(R1は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子またはヒドロキシル基で置換されていてもよい}を表し、
Hb1は炭素数4~30のフッ素置換アルキル基を表し、
nは2~6の整数を表し、
mは0~2の整数を表し、
lは2または3を表す。一般式(1)中で複数回登場するL1、L2、A1、A2、Sp1、Hb1、mおよびlは同じであっても異なっていてもよい。] - 前記一般式(1)中、B1が少なくとも1つの無置換のメチレン基を含むことを特徴とする請求項1に記載の液晶組成物。
- 前記一般式(1)中、nが2であり、
B1が炭素数1~40のアルキレン基を表し、
該アルキレン基中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR2CO-、-CONR2-、-NR2CONR2-、-NR2-、-CR2=CR2-、-C≡C-または-CR2R2-(R2はそれぞれ独立して水素原子または炭素数1~10のアルキル基を表す)で置換されていてもよく、
該アルキレン基の水素原子はハロゲン原子、-COOH、-SO3H、-SH、-NH3または-OHで置換されていてもよく、
B1が環状構造を含まないことを特徴とする請求項1または2に記載の液晶組成物。 - 前記一般式(1)中、nが2であり、
B1が炭素数1~40のアルキレン基を表し、
該アルキレン基中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR5CO-、-CONR5-または-NR5CONR5-(R5はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、
該アルキレン基の水素原子はハロゲン原子で置換されていてもよく、
B1が環状構造を含まないことを特徴とする請求項1または2に記載の液晶組成物。 - 前記一般式(1)中、nが2であり、
B1が炭素数1~40のアルキレン基を表し、
該アルキレン基中の隣接しないメチレン基は-O-、-S-、-NR6-または-NR6CONR6-(R6はそれぞれ独立に水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、
該アルキレン基の水素原子はハロゲン原子で置換されていてもよいことを特徴とする請求項1または2に記載の液晶組成物。 - 前記一般式(1)で表される化合物が、下記一般式(2)で表される化合物であることを特徴とする請求項1~5のいずれか一項に記載の液晶組成物。
一般式(2)
L11は-COO-、-COS-または-CONR10-を表し、L12は単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR10CO-または-CONR10-(R10はそれぞれ独立して水素原子または炭素数1~6のアルキル基を表す)を表し、
A11は2価の芳香族炭化水素基または2価の複素環基を表し、
A12はs+1価の芳香族炭化水素基を表し、
Sp11は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR11CO-または-CONR11-(R11は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよい}を表し、
Hb11は炭素数が4~30のフッ素置換アルキル基を表し、
sは0~2の整数を表し、
tは2または3を表す。一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。] - 前記一般式(2)中、sが3であることを特徴とする請求項6に記載の液晶組成物。
- 前記一般式(2)中、tが0または1を表し、L11およびL12がともに-COO-であることを特徴とする請求項6または7に記載の液晶組成物。
- 前記液晶分子が重合性棒状液晶分子であることを特徴とする請求項1~8のいずれか一項に記載の液晶組成物。
- 少なくとも1種のキラル化合物を含有することを特徴とする請求項1~9のいずれか一項に記載の液晶組成物。
- 請求項1~10のいずれか1項に記載の液晶組成物を重合させてなることを特徴とする高分子材料。
- 請求項11に記載の高分子材料の少なくとも1種を含有することを特徴とするフィルム。
- 請求項1~10のいずれか1項に記載の液晶組成物のコレステリック液晶相を固定してなることを特徴とするフィルム。
- 光学異方性を示すことを特徴とする請求項12または13に記載のフィルム。
- 選択反射特性を示すことを特徴とする請求項12~14のいずれか1項に記載のフィルム。
- 赤外線波長域に選択反射特性を示すことを特徴とする請求項15に記載のフィルム。
- 下記一般式(2)で表されることを特徴とする化合物。
一般式(2)
L11は-COO-、-COS-または-CONR10-を表し、L12は単結合、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR10CO-または-CONR10-(R10はそれぞれ独立して水素原子または炭素数1~6のアルキル基を表す)を表し、
A11は2価の芳香族炭化水素基または2価の複素環基を表し、
A12はs+1価の芳香族炭化水素基を表し、
Sp11は単結合または炭素数1~10のアルキレン基{該アルキレン中の隣接しないメチレン基は-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-SCO-、-NR11CO-または-CONR11-(R11は水素原子または炭素数1~6のアルキル基を表す)で置換されていてもよく、該アルキレン基の水素原子はハロゲン原子で置換されていてもよい}を表し、
Hb11は炭素数が4~30のフッ素置換アルキル基を表し、
sは0~2の整数を表し、
tは2または3を表す。一般式(2)中で複数回登場するL11、L12、A11、A12、Sp11、Hb11、sおよびtはそれぞれ独立に同じであっても異なっていてもよい。] - 前記一般式(2)中において、sが3であることを特徴とする請求項17に記載の化合物。
- 前記一般式(2)中において、tが0または1を表し、L11およびL12がともに-COO-であることを特徴とする請求項17または18に記載の化合物。
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