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WO2019181433A1 - Composé, composition, objet durci, objet optiquement anisotrope, et film réfléchissant - Google Patents

Composé, composition, objet durci, objet optiquement anisotrope, et film réfléchissant Download PDF

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Publication number
WO2019181433A1
WO2019181433A1 PCT/JP2019/008045 JP2019008045W WO2019181433A1 WO 2019181433 A1 WO2019181433 A1 WO 2019181433A1 JP 2019008045 W JP2019008045 W JP 2019008045W WO 2019181433 A1 WO2019181433 A1 WO 2019181433A1
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group
compound
composition
substituent
general formula
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Japanese (ja)
Inventor
優子 鈴木
啓祐 小玉
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/23—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same unsaturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a compound, a composition, a cured product, an optical anisotropic body, and a reflective film.
  • a compound exhibiting liquid crystallinity can be applied to various applications.
  • the liquid crystalline compound is applied to the production of an optical anisotropic body typified by a retardation film or the production of a reflection film formed by fixing a cholesteric liquid crystal phase.
  • a cholesteric liquid crystal phase is formed by adding a chiral compound to a nematic liquid crystal.
  • Patent Document 1 discloses a polymerizable chiral compound having a binaphthyl skeleton as a polymerizable chiral compound having a strong helical twisting power (HTP).
  • the present inventors examined the chiral compound described in Patent Document 1, and found that the chiral compound described in Patent Document 1 has a degree of intensity change of HTP caused by exposure (hereinafter referred to as “HTP change rate”). )) Has not yet reached the desired level.
  • HTP change rate a degree of intensity change of HTP caused by exposure
  • this invention makes it a subject to provide the compound which is excellent in the change rate of HTP by exposure. Moreover, this invention makes it a subject to provide the composition, hardened
  • [1] A compound represented by the following general formula (1).
  • at least one of X 1 , X 3 and X 5 represents a substituent having a group represented by —OCO—C (CN) ⁇ CH—
  • m represents an integer of 1 to 3.
  • composition according to [9] wherein the liquid crystal compound has two polymerizable groups.
  • [11] [8] A cured product obtained by curing the composition according to any one of [10].
  • [12] An optically anisotropic body obtained by curing the composition according to [9] or [10].
  • the compound which is excellent in the change rate of HTP by exposure can be provided.
  • cured material, an optical anisotropic body, and a reflecting film can be provided.
  • 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.
  • (meth) acryloyloxy group is a notation representing both an acryloyloxy group and a methacryloyloxy group.
  • the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • substituent T when simply referred to as a substituent, examples of the substituent include the following substituent T.
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • alkyl group cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano Group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocycl
  • those having a hydrogen atom may be further substituted with any of the above substituents on the hydrogen atom portion in the substituent.
  • the bonding direction of the divalent group represented in this specification is not limited unless otherwise specified.
  • Compound of the present invention As a feature of the compound of the present invention, it has a structure in which condensed rings are linked, and further has a group represented by —OCO—C (CN) ⁇ CH— (hereinafter also referred to as “specific linking group”). It has one or more groups.
  • specific linking group —OCO—C (CN) ⁇ CH—
  • the reason why the problem of the present invention can be solved by having the structure of the compound of the present invention is not necessarily clear, but the present inventors have introduced a cyano group into a specific linking group, and thus light ( In particular, it is considered that the absorption efficiency of light having a wavelength of 365 nm is improved, photoisomerization is likely to occur upon exposure, and the change rate of HTP is improved.
  • the cyano group has good light absorption efficiency, but also has a small bulk as a substituent, so that adverse effects on HTP before exposure to the compound (hereinafter also referred to as “initial HTP”) are suppressed.
  • the present inventors are thinking. Hereinafter, the compound of the present invention will be described.
  • the compound of the present invention is a compound represented by the general formula (1).
  • the part where the solid line and the broken line are parallel represents a single bond or a double bond.
  • the general formula (1) is represented by the following general formula (1-1) when the portion where the solid line and the broken line are parallel is a single bond, and the portion where the solid line and the broken line are parallel In the case of a double bond, it is represented by the following general formula (1-2).
  • the compound of the present invention is preferably in the form represented by the general formula (1-2).
  • general formula (1-1) and X 1 ⁇ X 6 in the general formula (1-2) and X 1 ⁇ X 6 in the general formula (1), and the same meaning.
  • X 1 to X 6 each independently represents a hydrogen atom or a substituent. However, at least one of X 1 to X 6 represents a substituent having a specific linking group (—OCO—C (CN) ⁇ CH—) (hereinafter, also referred to as “group having a specific linking group”). .
  • group having a specific linking group is 1 to 6, preferably 2 or 4, and more preferably 2.
  • at least one of X 1 , X 3 , and X 5 is a group having a specific linking group
  • at least one of X 2 , X 4 , and X 6 is a group having a specific linking group.
  • X 1 and X 2 and / or X 5 and X 6 are preferably groups having a specific linking group.
  • at least one of X 1 and X 2 is preferably a group having a specific linking group, and more preferably both are groups having a specific linking group.
  • the group having the specific linking group is not particularly limited as long as it has the specific linking group.
  • it is a group represented by the general formula (2) because the rate of change in HTP is more excellent. preferable. * -Z 1 -(-A 1 -Z 2- ) m -A 2 -R 1 (2)
  • m represents an integer of 0 to 3, preferably 1 to 3, and more preferably 1 from the viewpoint that the change rate of HTP is better and the initial HTP is also better.
  • R 1 represents a hydrogen atom or a substituent.
  • substituent represented by R 1 include a group having a polymerizable group or an alkoxy group (which may be linear or branched, and may have a cyclic structure. 5) is preferred.
  • Examples of the polymerizable group in the group having a polymerizable group include known polymerizable groups. From the viewpoint of reactivity, a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or ring polymerization is preferable. A sex group is more preferred.
  • Examples of the polymerizable group include a (meth) acryloyloxy group, a vinyl group, a maleimide group, an acetyl group, a styryl group, an allyl group, an epoxy group, an oxetane group, and a group containing these groups.
  • the hydrogen atom in each said group may be substituted by other substituents, such as a halogen atom.
  • the polymerizable group include groups represented by the following general formulas (P-1) to (P-20).
  • * represents a bonding position.
  • Ra represents a hydrogen atom or a methyl group.
  • Me represents a methyl group, and Et represents an ethyl group.
  • the group having a polymerizable group is not particularly limited as long as it has the above-described polymerizable group.
  • Specific examples of the group having a polymerizable group include groups represented by the following general formula (PA). * -L A -P (PA)
  • L A represents a single bond or a divalent linking group.
  • P represents a group represented by the general formulas (P-1) to (P-20) described above. * Represents the bonding position to A 2.
  • Examples of the divalent linking group represented by L A for example, linear or branched alkylene group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms linear or branched
  • One or more —CH 2 — in the alkylene group is selected from the group consisting of —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —OCO—, and —COO—.
  • a divalent linking group substituted with one or more of the above groups is preferred.
  • Z 1 and a plurality of Z 2 which may be present are each independently a single bond, —OCO—C (CN) ⁇ CH—, —COO—C (CN) ⁇ CH—, —O—, —S—, —CH 2 O—, —CO—, —COO—, —CO—S—, —O—CO—O—, —CO—NH—, —CH 2 S—, —CF 2 O—, —CF 2 S—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —COO—CH 2 — , —OCO—CH 2 CH 2 —, —COO—CH 2 — , —OCO—CH 2 —, —CH ⁇ CH—, —N ⁇ N—, —CH ⁇ NN—CH—, —CF ⁇ CF—, or —C ⁇ C—.
  • At least one of Z 1 and a plurality of Z 2 which may be present represents a specific linking group (—OCO—C (CN) ⁇ CH—).
  • Z 1 may be a specific linking group
  • one of the plurality of Z 2 may be a specific linking group.
  • Z 1 is a particular linking group.
  • Z 2 is also preferred specific linking groups. In the group represented by the general formula (2), only one or a plurality of the specific linking groups Z 1 and Z 2 may be present.
  • Z 1 and a plurality of Z 2 which may be present are preferably each independently a single bond, —COO— or —CH ⁇ CH—COO—.
  • a 1 and A 2 each independently represent a hydrocarbon ring group that may have a substituent or a heterocyclic group that may have a substituent.
  • Examples of the hydrocarbon ring group include an aliphatic hydrocarbon ring group and an aromatic hydrocarbon ring group.
  • the number of ring members is preferably 5 to 10.
  • the aliphatic hydrocarbon ring constituting the aliphatic hydrocarbon ring group may be either a monocyclic structure or a polycyclic structure.
  • the aliphatic hydrocarbon ring has a polycyclic structure, it is preferable that at least one of the rings included in the polycyclic structure is a 5-membered ring or more.
  • the number of carbon atoms in the aliphatic hydrocarbon ring is not particularly limited, but is preferably 5 to 12, more preferably 5 to 10, and still more preferably 5 or 6.
  • the aliphatic hydrocarbon ring examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornene ring, and an adamantane ring. Among these, a cyclohexane ring is preferable.
  • the aliphatic hydrocarbon ring constitutes an aliphatic hydrocarbon ring group by removing two hydrogen atoms on the ring.
  • the aromatic hydrocarbon ring constituting the aromatic hydrocarbon ring group may be either a monocyclic structure or a polycyclic structure.
  • the aromatic hydrocarbon ring has a polycyclic structure
  • it is preferable that at least one of the rings included in the polycyclic structure is a 5-membered ring or more.
  • the number of carbon atoms in the aromatic hydrocarbon ring is not particularly limited, but is preferably 6 to 18, and more preferably 6 to 10.
  • Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a benzene ring is preferable.
  • the aromatic hydrocarbon ring constitutes an aromatic hydrocarbon ring group by removing two hydrogen atoms on the ring. Of these, the hydrocarbon ring group is preferably a benzene ring group.
  • heterocyclic group examples include an aliphatic heterocyclic group and an aromatic heterocyclic group.
  • the number of ring members is not particularly limited, but is often 5 to 10.
  • the aliphatic heterocyclic ring constituting the aliphatic heterocyclic group may be either a monocyclic structure or a polycyclic structure.
  • the aliphatic heterocyclic ring has a polycyclic structure, it is preferable that at least one of the rings included in the polycyclic structure is a 5-membered ring or more.
  • a hetero atom which the said aliphatic heterocyclic ring contains a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the number of carbon atoms in the aliphatic heterocyclic ring is not particularly limited, but is preferably 5 to 10.
  • Specific examples of the aliphatic heterocyclic ring include an oxolane ring, an oxane ring, a piperidine ring, and a piperazine ring.
  • the aliphatic heterocyclic ring may be a ring in which —CH 2 — constituting the ring is substituted with —CO—, and examples thereof include a phthalimide ring.
  • the aliphatic heterocyclic ring forms an aliphatic heterocyclic group by removing two hydrogen atoms on the ring.
  • the aromatic heterocyclic ring constituting the aromatic heterocyclic group may be either a monocyclic structure or a polycyclic structure.
  • the aromatic heterocycle has a polycyclic structure, it is preferable that at least one of the rings included in the polycyclic structure is a 5-membered ring or more.
  • a hetero atom which the said aromatic heterocyclic group contains a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the number of carbon atoms in the aromatic heterocyclic ring is not particularly limited, but 5-18 is preferable.
  • aromatic heterocyclic ring examples include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, and an imidazole ring.
  • said aromatic heterocyclic ring comprises an aromatic heterocyclic group by removing two hydrogen atoms on a ring.
  • the above-mentioned hydrocarbon ring group and heterocyclic group may or may not have a substituent.
  • the number of substituents may be one or plural.
  • the substituent is preferably a monovalent substituent.
  • * represents a bonding position with X 1 to X 6 .
  • examples of the group other than the group represented by the general formula (2) include a group represented by “-specific linking group— (hydrogen atom or substituent)”.
  • the substituent is preferably an alkyl group (which may be linear or branched, and may have a cyclic structure, preferably having 1 to 5 carbon atoms).
  • substituent of X 1 to X 6 as a substituent other than a group having a specific linking group, for example, a hydroxyl group is preferable.
  • a plurality of groups selected from X 1 to X 6 may be bonded to each other to form a ring.
  • a combination of two groups selected from X 1 to X 6 is preferably bonded to each other to form a ring.
  • a plurality of combinations of the above two groups may exist among X 1 to X 6 .
  • X 1 and X 3 may combine with each other to form a ring
  • X 2 and X 4 may combine with each other to form a ring.
  • the combination of two groups selected from X 1 to X 6 is preferably a combination of X 1 and X 3 , X 1 and X 2 , and X 2 and X 4 .
  • X 1 and X 2 are bonded to each other to form a ring.
  • the group formed by combining two groups selected from X 1 to X 6 is not particularly limited, and examples thereof include a single bond and a divalent linking group.
  • the divalent linking group include an ether group, a carbonyl group, an ester group, a thioether group, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), divalent carbonization, and the like.
  • Examples thereof include a hydrogen group (for example, an alkylene group, an alkenylene group (eg, —CH ⁇ CH—), an alkynylene group (eg, —C ⁇ C—) and an arylene group), and a combination thereof.
  • a hydrogen group for example, an alkylene group, an alkenylene group (eg, —CH ⁇ CH—), an alkynylene group (eg, —C ⁇ C—) and an arylene group
  • a divalent linking group for example, an alkylene group, an alkenylene group (eg, —CH ⁇ CH—), an alkynylene group (eg, —C ⁇ C—) and an arylene group
  • -ether group-alkylene group preferably having 1 to 3 carbon atoms
  • the compound of the present invention can be synthesized by a known method.
  • the compound of this invention may be R body, S body, and the mixture of R body and S body may be sufficient as it.
  • the compound of the present invention is preferably a so-called chiral compound.
  • the compound of the present invention can be applied to various uses.
  • a cholesteric liquid crystal phase can be formed by using a composition obtained by mixing the compound of the present invention and a liquid crystal compound.
  • a composition is explained in full detail.
  • the composition of the present invention is a composition comprising the compound of the present invention.
  • the composition of the present invention is preferably a composition containing a liquid crystal compound (liquid crystal composition).
  • liquid crystal composition a liquid crystal compound
  • the composition of the present invention comprises a compound of the present invention.
  • the compound of the present invention is as described above.
  • the content of the compound of the present invention in the composition is not particularly limited, but is preferably 1 to 20% by mass, more preferably 2 to 15% by mass with respect to the total mass of the liquid crystal compound in the composition. More preferred is 10% by mass.
  • the liquid crystal compound will be described later.
  • the compound of the present invention may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total content is in the said range.
  • the composition of the present invention contains a liquid crystal compound.
  • the said liquid crystalline compound means the compound which shows liquid crystallinity which is compounds other than the compound of this invention.
  • the compound exhibits liquid crystallinity means that the compound has a property of developing an intermediate phase between the crystal phase (low temperature side) and the isotropic phase (high temperature side) when the temperature is changed.
  • the optical anisotropy and fluidity derived from the liquid crystal phase are confirmed by observing the compound with a hot stage system FP90 manufactured by METTLER TOLEDO or the like while heating or lowering the temperature under a polarizing microscope. it can.
  • the liquid crystal compound is not particularly limited as long as it has liquid crystallinity, and examples thereof include a rod-like nematic liquid crystal compound.
  • rod-like nematic liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted compounds.
  • examples thereof include phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitriles.
  • not only a low molecular liquid crystalline compound but also a high molecular liquid crystalline compound can be used.
  • the liquid crystalline compound may be polymerizable or non-polymerizable, and is preferably polymerizable.
  • a liquid crystalline compound having one or more polymerizable groups is preferable in that a cholesteric liquid crystal phase can be fixed, and a liquid crystalline compound having two or more polymerizable groups is more preferable.
  • a liquid crystalline compound having a group is more preferable.
  • the rod-like liquid crystal compound having no polymerizable group is described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28). is there.
  • the polymerizable rod-like liquid crystalline compound can be obtained by introducing a polymerizable group into the rod-like liquid crystalline compound.
  • the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, an unsaturated polymerizable group is preferable, and an ethylenically unsaturated polymerizable group is more preferable.
  • the polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods.
  • the number of polymerizable groups contained in the polymerizable rod-like liquid crystalline compound is preferably 1 to 6, more preferably 1 to 3, and still more preferably 2.
  • Two or more kinds of polymerizable rod-like liquid crystalline compounds may be used in combination. When two or more kinds of polymerizable rod-like liquid crystal compounds are used in combination, the alignment temperature can be lowered.
  • liquid crystalline compound a compound represented by the following general formula (3) is preferable.
  • P 11 and P 12 each independently represent a hydrogen atom or a polymerizable group. However, at least one of P 11 and P 12 represents a polymerizable group.
  • L 11 and L 12 each independently represents a single bond or a divalent linking group.
  • a 11 to A 15 each independently represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent.
  • Z 11 to Z 14 each independently represents a single bond or a divalent linking group.
  • m 3 and m 4 each independently represents an integer of 0 or 1.
  • the polymerizable groups represented by P 11 and P 12 are not particularly limited.
  • the polymerizable groups represented by the above general formulas (P-1) to (P-20) Is mentioned.
  • At least one of P 11 and P 12 represents a polymerizable group, and preferably both represent a polymerizable group.
  • the divalent linking group represented by L 11 and L 12 is not particularly limited.
  • each independently a linear or branched alkylene group having 1 to 20 carbon atoms.
  • one or more —CH 2 — in a linear or branched alkylene group having 1 to 20 carbon atoms is —O—, —S—, —NH—, —N (CH 3 ) —, —
  • the divalent linking group represented by L 11 and L 12 one or more —CH 2 — in the linear or branched alkylene group having 1 to 20 carbon atoms is independently —O—.
  • a group substituted with is preferred.
  • a 11 to A 15 are each independently an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Represents.
  • the definitions of the aromatic hydrocarbon ring group and the aromatic heterocyclic group are the same as the definitions of the aromatic hydrocarbon ring group and the aromatic heterocyclic group described above for A 1 and A 2 .
  • the above hydrocarbon ring group and heterocyclic group may or may not have a substituent.
  • the number of substituents may be one or plural.
  • the substituent is preferably a monovalent substituent.
  • the substituent is preferably a fluorine atom, a chlorine atom, a fluoroalkyl group, an alkoxy group, or an alkyl group in terms of further improving the solubility of the compound represented by the general formula (3).
  • An alkoxy group or an alkyl group is more preferable.
  • the number of carbon atoms in the fluoroalkyl group and the alkyl group and the number of carbon atoms of the alkyl group in the alkoxy group are not particularly limited, but are preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3. Is particularly preferred.
  • the fluoroalkyl group is a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom, and all the hydrogen atoms are preferably substituted with fluorine atoms (so-called perfluoroalkyl group). Is preferred).
  • a 11 to A 15 are preferably an aromatic hydrocarbon ring group which may have a substituent, and more preferably a phenylene group bonded at the 1-position and the 4-position.
  • the divalent linking group represented by Z 11 to Z 14 is not particularly limited.
  • the divalent linking group described for Z 1 and Z 2 described above Z 1 and Z And the same groups as those described in 2 ) except for a single bond.
  • Z 11 to Z 14 are particularly preferably —COO— or —CH ⁇ CH—.
  • n 3 and m 4 each independently represent an integer of 0 or 1, and 0 is preferable.
  • the compound represented by the general formula (3) can be synthesized by a known method. Specific examples of the liquid crystal compound are shown below.
  • the content of the liquid crystal compound in the composition is not particularly limited, but is preferably 5 to 99% by mass, more preferably 25 to 98% by mass, and more preferably 75 to 98% with respect to the total mass of the solid content in the composition. More preferred is mass%.
  • solid content intends components (nonvolatile content) other than the solvent in a composition. If it is other than a solvent, even if the property is a liquid component, it is regarded as a solid content.
  • one kind of liquid crystalline compound may be used alone, or two or more kinds thereof may be used. When using 2 or more types, it is preferable that the total content is in the said range.
  • the composition may contain a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and among them, a photopolymerization initiator that can start a polymerization reaction by ultraviolet irradiation is preferable.
  • the photopolymerization initiator include alkylphenone compounds, ⁇ -carbonyl compounds, acyloin ethers, ⁇ -hydrocarbon substituted aromatic acyloin compounds, polynuclear quinone compounds, phenazine compounds, and oxadiazole compounds.
  • the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 20% by mass, and preferably 1 to 8% by mass with respect to the total mass of the liquid crystal compound. % Is more preferable.
  • one kind of polymerization initiator may be used alone, or two or more kinds thereof may be used. When using 2 or more types, it is preferable that the total content is in the said range.
  • the composition may contain a surfactant that contributes to the formation of a stable or rapid liquid crystal phase (eg, nematic phase, cholesteric phase).
  • a surfactant that contributes to the formation of a stable or rapid liquid crystal phase (eg, nematic phase, cholesteric phase).
  • the surfactant include fluorine-containing (meth) acrylate-based polymers, compounds represented by general formulas (X1) to (X3) described in WO2011 / 162291, and paragraphs 0082 to 0090 of JP2014-119605A. And the compounds described in paragraphs 0020 to 0031 of JP2013-47204A (Patent No. 5774518). These compounds can reduce the tilt angle of the molecules of the liquid crystal compound at the air interface of the layer, or can substantially horizontally align the liquid crystal compound.
  • horizontal alignment means that the molecular axis of the liquid crystal compound (corresponding to the major axis of the liquid crystal compound when the liquid crystal compound is a rod-like liquid crystal compound) and the film surface are parallel. However, it is not required to be strictly parallel, and in this specification, it means an orientation having an inclination angle of less than 20 degrees with the film surface.
  • the liquid crystalline compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, and thus transparency in the visible light region is increased.
  • the molecules of the liquid crystalline compound are aligned at a large tilt angle, for example, when the cholesteric phase is formed, the spiral axis is deviated from the film surface normal, so that the reflectivity is reduced or a fingerprint pattern is generated. This is not preferable because haze is increased or diffraction is exhibited.
  • the fluorine-containing (meth) acrylate-based polymer that can be used as the surfactant include the polymers described in paragraphs 0018 to 0043 of JP-A-2007-272185.
  • the content of the surfactant is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.05 to 3% by mass with respect to the total mass of the liquid crystal compound. preferable.
  • one type of surfactant may be used alone, or two or more types may be used. When using 2 or more types, it is preferable that the total content is in the said range.
  • the composition may contain a solvent. It is preferable that the solvent can dissolve each component of the composition. Examples thereof include methyl ethyl ketone, cyclohexanone, and mixed solvents thereof.
  • the content of the solvent in the composition is preferably such that the solid content concentration of the composition is 5 to 50% by mass, and more preferably 10 to 40% by mass.
  • one type of solvent may be used alone, or two or more types may be used. When using 2 or more types, it is preferable that the total content is in the said range.
  • the composition includes an antioxidant, an ultraviolet absorber, a sensitizer, a stabilizer, a plasticizer, a chain transfer agent, a polymerization inhibitor, an antifoaming agent, a leveling agent, a thickener, and a flame retardant.
  • Dispersants, polymerizable monomers, and other additives such as coloring materials such as dyes and pigments.
  • the present invention also includes a cured product obtained by curing the composition as described above.
  • the method for curing (polymerization curing) the composition is not particularly limited, and a known method can be adopted.
  • a process X for forming a composition layer on a substrate by bringing a predetermined substrate into contact with the composition a process Y for exposing the composition layer, and a process Z for performing a curing process on the composition layer
  • the composition is a liquid crystal composition containing a liquid crystal compound
  • the liquid crystal compound can be fixed in an aligned state, and a so-called optical anisotropic body or cholesteric liquid crystal phase can be obtained.
  • a layer formed by immobilizing can be formed.
  • Process X is a process of forming a composition layer on a substrate by bringing the substrate into contact with the composition.
  • substrate used is not restrict
  • substrate (For example, a resin substrate, a glass substrate, a ceramic substrate, a semiconductor substrate, and a metal substrate) is mentioned.
  • the method for bringing the substrate into contact with the composition is not particularly limited, and examples thereof include a method of applying the composition on the substrate and a method of immersing the substrate in the composition.
  • a drying process in order to remove a solvent from the composition layer on a board
  • heat treatment may be performed in order to promote the alignment of the liquid crystal compound and to obtain a liquid crystal phase.
  • Step Y is a step of performing an exposure process using i-line or the like on the composition layer. It is preferable that the compound of the present invention undergoes photoisomerization by the exposure treatment and changes in HTP. In this exposure process, the degree of change in HTP can also be adjusted by appropriately adjusting the exposure amount and / or the exposure wavelength. After the exposure, a heat treatment may be further carried out in order to promote the alignment of the liquid crystal compound and bring it into a liquid crystal phase.
  • the helical pitch (and thus the selective reflection wavelength, etc.) of the liquid crystal phase obtained here reflects the HTP adjusted in the above exposure process.
  • Step Z is a step of applying a curing treatment to the composition layer (preferably the composition layer in a liquid crystal phase) that has undergone Step Y.
  • the method for the curing treatment is not particularly limited, and examples thereof include photocuring treatment and thermosetting treatment. Among these, photocuring treatment is preferable.
  • the composition preferably contains a photopolymerization initiator.
  • the wavelength of the light irradiated in the photocuring process is preferably different from the wavelength of the light used in the exposure process described above, and the photopolymerization initiator is sensitive to the wavelength of the light used in the exposure process. Preferably not.
  • the cured product obtained by the above treatment is preferably a layer formed by fixing a liquid crystal phase.
  • a layer formed by fixing a cholesteric liquid crystal phase is typically formed. These layers no longer need to exhibit liquid crystallinity. More specifically, for example, the state in which the cholesteric liquid crystal phase is “fixed” is the most typical and preferred mode in which the orientation of the liquid crystalline compound that is the cholesteric liquid crystal phase is maintained. More specifically, the layer has no fluidity in a temperature range of usually 0 to 50 ° C., and -30 to 70 ° C. under harsher conditions, and the orientation form is changed by an external field or an external force. It is preferable that the fixed orientation form can be kept stable.
  • Optical anisotropic body, reflective film A cured product is obtained by subjecting the composition to a curing treatment as described above.
  • curing the composition of this invention can be applied to various uses, for example, an optical anisotropic body and a reflecting film are mentioned.
  • an optically anisotropic body or a reflective film obtained by curing the above composition can be mentioned as a preferred embodiment.
  • an optical anisotropic body intends the substance which has optical anisotropy.
  • the reflective film corresponds to a layer formed by fixing the above-described cholesteric liquid crystal phase, and can reflect light in a predetermined reflection band.
  • HTP change rate
  • HTP change rate is 60% or more.
  • B HTP change rate is 40% or more and less than 60%.
  • C HTP change rate is 30% or more and less than 40%.
  • D HTP change rate is 20% or more and less than 30%.
  • E HTP change rate is less than 20%.
  • the following table shows the evaluation results of Examples using compositions prepared by adding each compound.
  • the column of “specific linking group-containing group” indicates the position of the group having the specific linking group when the specific compound used in each example is applied to the general formula (1).
  • the column of “general formula (2)” when the specific compound used in each example is applied to the general formula (1), at least one of X 1 to X 6 is represented by the general formula (2). It is shown whether it has the group made. The case where this requirement is satisfied is A, and the case where this requirement is not satisfied is B.
  • the column “m” indicates the value of m in the group represented by the general formula (2) when the requirement of the “general formula (2)” is satisfied.
  • the column of “specific linking group position” indicates which group in general formula (2) is the specific linking group when the requirement of “general formula (2)” is satisfied.
  • the column of “X 1 , X 2 linked ring” indicates whether X 1 and X 2 are bonded to each other to form a ring when the specific compound used in each example is applied to the general formula (1). Indicates whether or not. The case where this requirement is satisfied is A, and the case where this requirement is not satisfied is B.
  • Surfactant S-1 is a compound described in Japanese Patent No. 5774518 and has the following structure.
  • Polymerization initiator X IRGACURE 907 (manufactured by BASF)
  • a polyimide alignment film material SE-130 (manufactured by Nissan Chemical Industries, Ltd.) was applied on the cleaned glass substrate to form a coating film. After baking the obtained coating film, the board
  • the composition layer in which the liquid crystalline compound is aligned light having a wavelength of 365 nm is 0.4 mW / cm 2 from a light source (manufactured by UVP, 2UV / transilluminator) through a mask having an opening. For 1 minute (corresponding to the process of changing the HTP of CD-1). Due to the difference between the opening portion and the non-opening portion of the mask, the composition layer is in a state where a portion irradiated with light having a wavelength of 365 nm and a portion not irradiated are present.
  • the composition layer was cured by irradiating with ultraviolet rays (310 nm) at a dose of 500 mJ / cm 2 in a nitrogen atmosphere at 25 ° C. with the mask removed, and a reflective film (cholesteric) It corresponds to a layer formed by fixing the liquid crystal phase). It was confirmed that the obtained reflective film had different selective reflection wavelengths (the cholesteric layer had a different helical pitch) between the portion irradiated with light having a wavelength of 365 nm and the portion not irradiated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un composé présentant un grand changement de HTP lors de l'exposition à la lumière. La présente invention concerne en outre une composition comprenant le composé, un objet durci, un objet optiquement anisotrope et un film réfléchissant. Le composé de la présente invention est représenté par la formule générale (1).
PCT/JP2019/008045 2018-03-23 2019-03-01 Composé, composition, objet durci, objet optiquement anisotrope, et film réfléchissant Ceased WO2019181433A1 (fr)

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WO2021020114A1 (fr) * 2019-07-29 2021-02-04 富士フイルム株式会社 Composé, composition de cristaux liquides, produit durci, corps optiquement anisotrope et film réfléchissant
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WO2020050322A1 (fr) * 2018-09-07 2020-03-12 富士フイルム株式会社 Composé, mélange, composition de cristaux liquides, objet durci, objet optiquement anisotrope, et film réfléchissant
WO2021020114A1 (fr) * 2019-07-29 2021-02-04 富士フイルム株式会社 Composé, composition de cristaux liquides, produit durci, corps optiquement anisotrope et film réfléchissant
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US20230002679A1 (en) * 2020-02-18 2023-01-05 Fujifilm Corporation Compound and liquid crystal composition
US12037530B2 (en) * 2020-02-18 2024-07-16 Fujifilm Corporation Compound and liquid crystal composition

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