WO2014157267A1 - Pigment d'interférence optique et son procédé de production - Google Patents

Pigment d'interférence optique et son procédé de production Download PDF

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WO2014157267A1
WO2014157267A1 PCT/JP2014/058401 JP2014058401W WO2014157267A1 WO 2014157267 A1 WO2014157267 A1 WO 2014157267A1 JP 2014058401 W JP2014058401 W JP 2014058401W WO 2014157267 A1 WO2014157267 A1 WO 2014157267A1
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liquid crystal
group
interference pigment
light interference
light
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PCT/JP2014/058401
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Japanese (ja)
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和宏 沖
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富士フイルム株式会社
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Priority to CN201480017178.5A priority Critical patent/CN105073907A/zh
Publication of WO2014157267A1 publication Critical patent/WO2014157267A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/107—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azomethine dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a light interference pigment and a method for producing the same.
  • Patent Document 1 discloses that a light-reflecting film in which a cholesteric liquid crystal phase is fixed by being cured by ultraviolet irradiation is pulverized by peeling off from a carrier and classified by sieving, thereby obtaining UV-A and / or UV.
  • Patent Document 2 describes a method for producing a light protective agent preparation in which a light reflecting film obtained by curing and fixing a cholesteric liquid crystal phase by ultraviolet irradiation is pulverized and mixed with a pigment.
  • Patent Document 3 describes a method for producing a liquid crystal polyester obtained by granulating a polycondensate, and further describes that the particles are washed with an acidic aqueous solution after being granulated, and further washed with water.
  • Patent Document 4 describes a method for producing a flat polyester powder by washing porous polyester before granulation with high-temperature ethylene glycol or hot water, drying it, and then pulverizing it into particles. Yes.
  • Patent Document 5 the PTFE coarse particles obtained by suspension polymerization of polytetrafluoroethylene (PTFE) are finely pulverized in a wet state and then washed with water (pure water) to efficiently produce a powder for molding PTFE. It describes that the amount of impurities can be reduced.
  • PTFE polytetrafluoroethylene
  • Patent Documents 1 and 2 it has not been studied in the past, including Patent Documents 1 and 2, to wash the obtained light interference particles after crushing the light reflecting film in which the cholesteric liquid crystal phase is cured and fixed.
  • the film obtained by curing and solidifying the polymerizable liquid crystal compound is still used as a functional film as a member of other products.
  • the first place unlike the case of pulverizing a non-film-like polycondensate as in Patent Documents 3 to 5, there is no known need to remove impurities by washing after film formation, and examples of washing after film formation are also included. Little was known.
  • Patent Document 6 discloses a light reflection film in which a cholesteric liquid crystal phase is cured and fixed. It was only described that it was immersed in a container containing an organic solvent and washed.
  • the present invention aims to ameliorate the above problems and satisfy the demands. That is, the problem to be solved by the present invention is to provide a method for producing a light interference pigment having good light reflection performance at a selective reflection wavelength when dispersed in a dispersion medium.
  • a light-reflective cholesteric liquid crystal film obtained by curing and fixing a polymerizable liquid crystal compound is As a countermeasure against problems peculiar to lamination such as wavelength shift and wavelength shift, there are many uncured monomers and additives in the film to adjust the curing and add additives. In this case, when the pigment is dispersed in the dispersion medium, these uncured monomers and additives are expected to elute and adversely affect various performances.
  • cholesteric liquid crystals also have the problem that the optical characteristics at the selective reflection wavelength are further deteriorated (the selective reflection wavelength is shifted and the light reflectance is lowered).
  • the main factor is that the film having a cholesteric liquid crystal structure is used as an optical interference pigment.
  • the free volume (space) of the liquid crystal structure of the light interference pigment widens, and as a result, the gap between the light interference pigments It was found that ⁇ n (refractive index) of the light interference pigment was lowered by the surrounding material (for example, resin) entering the dispersion medium.
  • the present invention which is means for solving the above problems, is as follows. [1] A step of producing a film having a cholesteric liquid crystal structure in which the alignment state of the polymerizable liquid crystal compound is cured and fixed; Crushing a film having a cholesteric liquid crystal structure to produce light interference particles; Washing the optical interference particles with an organic solvent having an SP value of at least 8.5 to 12 (cal / cm 3 ) 1/2 at a temperature of 35 ° C.
  • V represents the molar molecular volume of the solvent and ⁇ E represents the cohesive energy;
  • a method for producing a light interference pigment [2] The method for producing a light interference pigment according to [1] reflects right-handed circularly polarized light obtained by curing a film having a cholesteric liquid crystal structure and fixing the alignment state of at least one polymerizable liquid crystal compound.
  • the method for producing a light interference pigment according to [1] or [2] is preferably cleaned by immersing the light interference particles in an organic solvent.
  • the filtration accuracy of the filter used for filtering the organic solvent is 0.3 to 6 ⁇ m.
  • the washing temperature is preferably 40 ° C. or higher and the boiling point of the organic solvent or lower.
  • the light interference particles preferably have a flat plate shape.
  • the selective reflection wavelength of the light interference pigment is preferably 420 nm or less.
  • the thickness of the light interference particles is preferably 4 to 10 ⁇ m.
  • the substrate is preferably a plastic film having a glass transition temperature of 150 ° C. or lower.
  • the polymerizable liquid crystal compound is preferably a compound represented by the following general formula (X).
  • the manufacturing method of the light interference pigment which has the favorable light reflection performance in the selective reflection wavelength when it makes it disperse
  • FIG. 1 is a schematic view showing a cross section of an example of a film having a cholesteric liquid crystal structure, which is used when manufacturing optical interference particles used for manufacturing the optical interference pigment of the present invention.
  • 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 solid containing the polymerizable liquid crystal compound may be composed of a crystal of the polymerizable liquid crystal compound or may be an amorphous form that is not a crystal.
  • other components such as a polymerization initiator and a chiral agent, may also be included. In some cases, all or some of these may be mixed.
  • the SP value represents the solubility parameter value ⁇ calculated by the Hoy method, and is defined by the square root of the cohesive energy density represented by the following formula (1).
  • ⁇ ( ⁇ E / V) 1/2 formula (1)
  • V represents the molar molecular volume of the solvent
  • ⁇ E represents the cohesive energy (evaporation energy).
  • the SP value ( ⁇ ) was calculated according to J. Hildebrand, R. Scott: “The Solubility of Non-electrolytes”, 3rd Ed. , P.119-133, Reinhold Publishing Corp. (1949).
  • the Hoy method represents the content described in “Polymer Handbook (4th. Edition)”.
  • the method for producing a light interference pigment according to the present invention includes a step of producing a film having a cholesteric liquid crystal structure in which an alignment state of a polymerizable liquid crystal compound is cured and fixed, and crushing a film having a cholesteric liquid crystal structure to produce light interference particles. And a step of cleaning the optical interference particles using an organic solvent having an SP value of at least 8.5 to 12 (cal / cm 3 ) 1/2 at a temperature of 35 ° C. or higher.
  • the SP value represents the solubility parameter ⁇ measured by the Hoy method and is represented by the following formula (1)).
  • This measured value is a value when the optical performance of a film coated with a thin dispersion liquid containing a light interference pigment and a dispersion medium is measured, and is substantially the value of the dispersion liquid containing the light interference pigment and the dispersion medium. It is equal to the optical performance.
  • materials used in the method for producing a light interference pigment of the present invention and preferred production conditions will be described.
  • the method for producing a light interference pigment of the present invention includes a step of producing a film having a cholesteric liquid crystal structure in which the alignment state of the polymerizable liquid crystal compound is cured and fixed.
  • a liquid containing a cholesteric liquid crystal material is applied on a substrate, the solvent is evaporated, and then heated to align the liquid crystal.
  • a method in which the step of irradiating with ultraviolet rays is repeated once or a plurality of times is preferable. Details of a method for manufacturing a film having a cholesteric liquid crystal structure will be described below.
  • the film having a cholesteric liquid crystal structure is formed by forming an alignment film on a substrate as necessary, and applying, drying, aligning and fixing a cholesteric liquid crystal composition coating solution containing a solvent described later on the surface thereof.
  • the coating can be performed by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method) using a cholesteric liquid crystal composition coating solution. Alternatively, it may be formed by discharging using an inkjet apparatus.
  • a plastic film as a substrate, and to use a plastic film having a glass transition temperature of 170 ° C. or lower reduces the production cost by using a resin having low heat resistance. From the viewpoint of being able to do so.
  • the glass transition temperature of the plastic film used as the substrate is more preferably 40 to 160 ° C., and particularly preferably 60 to 150 ° C.
  • As the substrate it is preferable to use PET.
  • the state of “fixed” is the most typical and preferred mode in which the orientation of the liquid crystal compound contained in the film having a cholesteric liquid crystal structure is maintained, but is not limited thereto, specifically, Usually, the film having the cholesteric liquid crystal structure has no fluidity in the temperature range of 0 ° C. to 50 ° C., and -30 ° C. to 70 ° C. under severer conditions, and changes in the alignment form by an external field or external force. The state which can maintain the fixed orientation form stably without being pointed out.
  • a liquid containing a polymerizable liquid crystal compound (hereinafter also referred to as a liquid crystal composition) is once heated to the liquid crystal phase formation temperature, and then cooled while maintaining the alignment state. By doing so, it can be formed by fixing without impairing the alignment form in the liquid crystal state.
  • the liquid crystal composition to which the polymerization initiator is added can be formed by heating and aligning to the liquid crystal phase formation temperature and then fixing the alignment state of the liquid crystal state by polymerization.
  • the latter polymerization reaction is preferably performed, and the photopolymerization reaction is more preferably performed using a photopolymerization initiator.
  • a low-molecular liquid crystal compound may have a group that reacts with heat, light, or the like, and as a result, it may be polymerized or cross-linked by reaction with heat, light, or the like to increase the molecular weight and lose liquid crystallinity.
  • the liquid crystal composition is preferably obtained by mixing a polymerizable liquid crystal compound, an optically active compound (in the present invention, synonymous with a chiral agent and a chiral agent), a polymerization initiator, and a solvent.
  • a polymerizable liquid crystal compound may be used.
  • the liquid crystal composition may contain a non-polymerizable liquid crystal compound as long as it contains a polymerizable liquid crystal compound.
  • a polymerizable liquid crystal compound and a non-polymerizable liquid crystal compound can be used in combination.
  • a low molecular weight polymerizable liquid crystal compound and a polymer liquid crystal compound can be used in combination.
  • liquid crystal composition in order to improve alignment uniformity, coating suitability, and film strength.
  • the liquid crystal composition may further contain a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer and the like as long as the optical performance is not deteriorated.
  • the liquid crystal temperature range of the liquid crystal composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C., from the viewpoint of production suitability and the like.
  • a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a cholesteric liquid crystal phase.
  • a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting a cholesteric liquid crystal phase, which is disadvantageous from waste of heat energy, deformation of the substrate, and alteration.
  • Polymerizable liquid crystal compounds As the polymerizable liquid crystal compound, a polymerizable rod-like liquid crystal compound is preferable.
  • Polymerizable rod-shaped liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines.
  • Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
  • the orientation of the polymerizable rod-like liquid crystal compound is fixed by polymerization, and the rod-like liquid crystal compound is more preferably a polymerizable rod-like nematic liquid crystal compound.
  • the polymerizable rod-like liquid crystal compound include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, WO 95/22586, 95/24455, 97/97. No. 0600, No. 98/23580, No.
  • the polymerizable liquid crystal compound is preferably a compound represented by the following general formula (X).
  • Formula (X) Q 1 -L 1 -Cy 1 -L 2- (Cy 2 -L 3 ) n -Cy 3 -L 4 -Q 2 (In General Formula (X), Q 1 and Q 2 are each independently a polymerizable group, L 1 and L 4 are each independently a divalent linking group, and L 2 and L 3 are each independently a single group. A bond or a divalent linking group, Cy 1 , Cy 2 and Cy 3 are divalent cyclic groups, and n is 0, 1, 2, or 3.)
  • the compound (polymerizable rod-like liquid crystal compound) represented by the general formula (X) will be further described below.
  • Q 1 and Q 2 are each independently a polymerizable group.
  • the polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization.
  • the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.
  • L 1 and L 4 are each independently a divalent linking group.
  • L 1 and L 4 each independently comprises —O—, —S—, —CO—, —NR—, —C ⁇ N—, a divalent chain group, a divalent cyclic group, and combinations thereof.
  • a divalent linking group selected from the group is preferred.
  • R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.
  • the example of the bivalent coupling group which consists of a combination is shown below. Here, the left side is coupled to Q (Q 1 or Q 2 ), and the right side is coupled to Cy (Cy 1 or Cy 3 ).
  • L-1 —CO—O—divalent chain group —O— L-2: —CO—O—divalent chain group —O—CO— L-3: —CO—O—divalent chain group —O—CO—O— L-4: —CO—O—divalent chain group—O—divalent cyclic group— L-5: —CO—O—divalent chain group —O—divalent cyclic group —CO—O— L-6: —CO—O—divalent chain group —O—divalent cyclic group —O—CO— L-7: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group— L-8: —CO—O—divalent chain group—O—divalent cyclic group—divalent chain group —CO—O— L-9: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group—O—CO— L-10: —CO
  • the alkylene group may have a branch.
  • the alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
  • the alkenylene group may have a branch.
  • the alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkylene part of the substituted alkylene group is the same as the above alkylene group.
  • the substituent include a halogen atom.
  • the alkynylene group may have a branch.
  • the alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
  • the alkynylene part of the substituted alkynylene group is the same as the above alkynylene group.
  • Examples of the substituent include a halogen atom.
  • divalent chain group examples include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.
  • divalent cyclic group is the same as those of Cy 1 , Cy 2 and Cy 3 described later.
  • R 2 is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and a hydrogen atom. Most preferred.
  • L 2 or L 3 each independently represents a single bond or a divalent linking group.
  • L 2 and L 3 each independently comprises —O—, —S—, —CO—, —NR—, —C ⁇ N—, a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group.
  • R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom.
  • the divalent chain group and the divalent cyclic group have the same definitions as L 1 and L 4 .
  • Preferred divalent linking groups as L 2 or L 3 include —COO—, —OCO—, —OCOO—, —OCONR—, —COS—, —SCO—, —CONR—, —NRCO—, —CH 2. CH 2 —, —C ⁇ C—COO—, —C ⁇ N—, —C ⁇ N—N ⁇ C—, and the like.
  • n is 0, 1, 2, or 3.
  • two L 3 may be the same or different, and two Cy 2 may be the same or different.
  • n is preferably 1 or 2, and more preferably 1.
  • Cy 1 , Cy 2 and Cy 3 are each independently a divalent cyclic group.
  • the ring contained in the cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.
  • the ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
  • the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring.
  • Examples of the aromatic ring include a benzene ring and a naphthalene ring.
  • Examples of the aliphatic ring include a cyclohexane ring.
  • Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
  • As the cyclic group having a benzene ring 1,4-phenylene is preferable.
  • As the cyclic group having a naphthalene ring naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable.
  • the cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene.
  • cyclic group having a pyridine ring pyridine-2,5-diyl is preferable.
  • the cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.
  • the cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms.
  • Examples of the polymerizable liquid crystal compound represented by the general formula (X) are shown below. The present invention is not limited to these.
  • the rod-like liquid crystal compound in addition to the polymerizable rod-like liquid crystal compound represented by the general formula (X), at least one compound represented by the following general formula (V) may be mixed.
  • Formula (V) M 1- (L 1 ) p -Cy 1 -L 2- (Cy 2 -L 3 ) n -Cy 3- (L 4 ) q -M 2
  • M 1 and M 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, —SCN, —CF 3 , It represents a nitro group or Q 1 , but at least one of M 1 and M 2 represents a group other than Q 1 .
  • Q 1, L 1, L 2, L 3, L 4, Cy 1, Cy 2, Cy 3 and n have the same meanings as the group represented by the general formula (X).
  • P and q are 0 or 1.
  • M 1 and M 2 do not represent Q 1 , they are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group, more preferably a carbon number It is preferably an alkyl group of 1 to 4 or a phenyl group, and p and q are preferably 0.
  • optically active compounds As the optically active compound, a known chiral agent (for example, liquid crystal device handbook, chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989) is used. be able to.
  • 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 may have a polymerizable group.
  • a polymer having a rod-like nematic liquid crystalline repeating unit and an optically active structure can be formed by a polymerization reaction of the polymerizable rod-like nematic liquid crystalline compound.
  • the polymerizable group of the optically active compound is preferably the same group as the polymerizable group of the polymerizable rod-like nematic liquid crystalline 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.
  • a commercially available chiral agent may be used as the chiral agent, and LC-756 (manufactured by BASF) can be preferably used when forming a light reflection layer that reflects right circularly polarized light.
  • the chiral agent may have liquid crystallinity.
  • the amount of chiral agent used is preferably 1 to 30 mol% of the amount of the polymerizable liquid crystal compound. A smaller amount of chiral agent is preferred because it often does not affect liquid crystallinity. Therefore, it is preferable that the chiral agent has a strong twisting force.
  • a chiral agent having a strong twisting force for example, the chiral agents described in JP-A Nos. 2003-287623 and 4287599 can be used.
  • the film-forming liquid crystal composition having a cholesteric liquid crystal structure is preferably a curable composition, and for that purpose, it preferably contains a polymerization initiator.
  • the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. To prevent the substrate from being deformed or altered by heat, The polymerization reaction by photopolymerization reaction and electron beam irradiation is preferred.
  • the alignment state of the polymerizable liquid crystal compound is fixed by a curing reaction that proceeds by irradiating the composition containing the polymerizable liquid crystal compound and the photopolymerization initiator with ultraviolet rays. It is preferable to do.
  • photopolymerization initiators examples 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 aromatics.
  • Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US patent) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970) and the like .
  • the amount of the photopolymerization initiator used is preferably from 0.1 to 20% by mass, more preferably from 1 to 8% by mass, based on the liquid crystal composition (solid content in the case of a coating liquid).
  • Light irradiation for the polymerization of the liquid crystal compound is preferably performed using ultraviolet rays. Irradiation energy is preferably 10mJ / cm 2 ⁇ 50J / cm 2, further preferably 50mJ / cm 2 ⁇ 800mJ / cm 2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
  • oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air, it is preferable to reduce the oxygen concentration by a method such as nitrogen substitution.
  • a preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.
  • the polymerization reaction rate is preferably 70% or more, and preferably 80% or more from the viewpoint of maintaining the mechanical strength of the film having a cholesteric liquid crystal structure and suppressing unreacted substances from flowing into the liquid crystal layer and the like. More preferably, it is more preferably 90% or more.
  • a method of increasing the irradiation amount of ultraviolet rays to be irradiated and polymerization under a nitrogen atmosphere or heating conditions are effective.
  • polymerization temperature, and pushing a reaction further by thermal polymerization reaction, and the method of irradiating an ultraviolet-ray again can be used.
  • the polymerization reaction rate can be measured by comparing the absorption intensity of the infrared vibration spectrum of the polymerization reactive bonding group before and after the polymerization.
  • a compound described in [0012] to [0030] of JP2012-211306A, a fluorine-containing (meth) acrylate, or [0037] to [0044] of JP2012-101999A By containing at least one of these compounds, it is preferable to reduce the tilt angle of the molecules of the liquid crystal compound at the air interface or to substantially horizontally align it.
  • “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it is not required to be strictly parallel. An orientation with an inclination angle of less than 20 degrees is meant.
  • the alignment control agent used in the present invention the compounds described in Japanese Patent Application No. 2003-331269 (Japanese Patent Laid-Open No. 2005-099258) can be used, and the synthesis method of these compounds is also described in the specification. ing.
  • first alignment control agent a compound having at least one perfluoroalkyl chain can be exemplified.
  • the first orientation control agent preferably has an embossing ratio represented by the following formula (1) of 50% or less.
  • A is the lower layer That is, it represents the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of the one-layer product, and B represents the fluorine atom content ratio relative to the total amount of carbon atoms and fluorine atoms present on the surface of the upper layer, ie, the two-layer product. Represents.
  • the measurement method for the fluorine atom content relative to the total amount of carbon atoms and fluorine atoms present on the surface of each layer used when measuring the protrusion ratio of the alignment control agent is not limited.
  • fluorine atoms / carbon atoms (F / C) existing on the surface of each layer were measured by X-ray photoelectron spectroscopy, and the calculation was performed based on these values.
  • the first alignment control agent is preferably non-polymerizable. It is preferable that the first alignment control agent has at least two perfluoroalkyl chains, and it is more preferable that the first alignment control agent has two perfluoroalkyl chains.
  • the first alignment control agent is preferably contained in an amount of 0.03% by mass or more, more preferably 0.10% by mass or more, based on the polymerizable liquid crystal compound in the liquid crystal composition.
  • the first alignment control agent is preferably represented by the following general formula (I).
  • the compound of the following formula (I) is characterized by having a divalent group at the center and a fluorinated alkyl group at the terminal.
  • a compound having a fluorinated alkyl group at the terminal is effective as an alignment accelerator, but conventionally known alignment control agents have a limited use concentration range and a low solubility, limiting their use. It had been. Since the compound of the following formula (I) exhibits the same or better orientation performance in a wider concentration range and good solubility, a composition containing them has an advantage that it is easy to use in production.
  • L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO. —, —COS—, —SCO—, —NRCO—, —CONR— (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), more preferably —O—, —S—, —CO—. , —COO—, —OCO—, —COS—, —SCO—, and more preferably —O—, —CO—, —COO—, —OCO—.
  • the alkyl group which R can take may be linear or branched.
  • the number of carbon atoms is more preferably 1 to 3, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.
  • Sp represents a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, still more preferably a single bond or an alkylene group having 1 to 4 carbon atoms,
  • Non-adjacent methylene groups in the alkylene are substituted with —O—, —S—, —CO—, —COO—, —OCO—, —COS—, —SCO—, —NRCO—, —CONR—, —OH. It may be.
  • the alkylene group may or may not be branched, but a linear alkylene group having no branch is preferred.
  • a 1 and A 2 each represent 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, more preferably 6 to 10, and still more preferably a phenylene group. .
  • a phenylene group it is preferable to have a bond at the meta or para position, and it is particularly preferable to have a bond at the para position.
  • 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 and A 2 may have a substituent.
  • a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group.
  • the substituent for the divalent aromatic hydrocarbon group or divalent heterocyclic group represented by A 1 or 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. Examples include groups. A 1 and A 2 are preferably the same.
  • T is (X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, Ya, Yb, Yc Yd each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), more preferably And more preferably It is.
  • the alkyl group which X can take has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • 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 description and preferred range of the alkyl group that X can take can be referred to.
  • the halogen atom that X can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.
  • the ester group that X can take include a group represented by RCOO—.
  • R include an alkyl group having 1 to 8 carbon atoms.
  • the description and preferred range of the alkyl group that R can take can be referred to.
  • Specific examples of the ester include CH 3 COO— and C 2 H 5 COO—.
  • the alkyl group having 1 to 4 carbon atoms which Ya, Yb, Yc and Yd can take may be linear or branched.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like can be exemplified.
  • the divalent aromatic heterocyclic group the following explanation and description regarding the aromatic heterocyclic group of A 1 and A 2 can be referred to.
  • Hb represents a fluorinated alkyl group having 3 to 30 carbon atoms, more preferably a fluorinated alkyl group having 3 to 20 carbon atoms, and still more preferably a fluorinated alkyl group having 3 to 10 carbon atoms.
  • 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 3 to 30.
  • k, l, m, n, and p are integers greater than or equal to 0, and o is an integer from 1 to 4. Further, when k, l, m, n, o, and p are 2 or more, a plurality of structures in parentheses may be the same or different. For example, when k is 2, two L 1 existing in the molecule may be the same or different from each other.
  • k, l, m, and n are preferably any integer of 0 to 6, more preferably any integer of 0 to 4, and any of 0 to 3 An integer is more preferable, and an integer of 0 to 2 is even more preferable.
  • o is preferably 1 or 2.
  • p is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the compound represented by the general formula (I) may have a symmetrical molecular structure or may have no symmetry.
  • 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.
  • the two fluorinated alkyl groups (Hb) present in the molecule are preferably the same as each other, and the linking group (L 1 ) k -Sp- (L 2 -A 1 ) l -L 3 present in the molecule and -L 4 - (a 2 -L 5 ) m -Sp- (L 6) n also is preferably identical to each other.
  • the terminal Hb- (L 1 ) k -Sp- and -Sp- (L 6 ) n -Hb are preferably groups 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.
  • terminal Hb- (L 1 ) k -Sp-L 2 -and -L 5 -Sp- (L 6 ) n -Hb are any of the following: A group represented by the general formula is preferred.
  • the compound represented by the general formula (I) is synthesized by appropriately selecting and combining the synthesis methods described in JP-A Nos. 2002-129162, 2002-97170, and references cited therein. can do. Moreover, it can synthesize
  • the liquid crystal composition preferably contains a second alignment control agent.
  • a second alignment control agent There is no restriction
  • the second alignment control agent is non-polymerizable.
  • the protrusion ratio represented by the formula (1) of the second alignment control agent is preferably more than 50%, more preferably more than 50% and 90% or less.
  • the second alignment control agent has a perfluoroalkyl chain, and it is preferable that the second alignment control agent has 6 perfluoroalkyl chains.
  • the second alignment control agent is preferably contained in an amount of 0.003 to 1.0% by mass, more preferably 0.005 to 1.0% by mass, based on the polymerizable liquid crystal compound in the liquid crystal composition. .
  • the second alignment controller is preferably represented by the following general formula (II).
  • the composition containing the compound represented by the following general formula (II) has an advantage of being easy to use in production.
  • L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are each independently a single bond, —O—, —S—, —CO—, —COO—, —OCO. —, —COS—, —SCO—, —NRCO—, —CONR— (in the general formula (II), R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NRCO—, — CONR- has the effect of reducing the solubility, and has a tendency to increase the haze value during film formation.
  • the alkyl group which R can take may be linear or branched.
  • the number of carbon atoms is more preferably 1 to 3, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.
  • Sp 1 , Sp 2 , Sp 3 and Sp 4 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, and more preferably A single bond or an alkylene group having 1 to 4 carbon atoms.
  • the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
  • the alkylene group may or may not be branched, but a linear alkylene group having no branch is preferred. From the viewpoint of synthesis, it is preferable that Sp 1 and Sp 4 are the same, and Sp 2 and Sp 3 are the same.
  • a 1 and A 2 are trivalent or tetravalent aromatic hydrocarbons.
  • the carbon number of the trivalent or tetravalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 14, further preferably 6 to 10, and further preferably 6. More preferred.
  • the trivalent or tetravalent aromatic hydrocarbon group represented by A 1 or A 2 may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group. For the explanation and preferred ranges of these groups, the corresponding description of T below can be referred to.
  • Examples of the substituent for the trivalent or tetravalent aromatic hydrocarbon group represented by A 1 or 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. be able to.
  • a molecule having a large number of perfluoroalkyl moieties in the molecule can orient the liquid crystal with a small addition amount, leading to a decrease in haze. Therefore, A 1 and A 2 are tetravalent so as to have a large number of perfluoroalkyl groups in the molecule. It is preferable that From the viewpoint of synthesis, A 1 and A 2 are preferably the same.
  • T is (X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, Ya, Yb, Yc Yd each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), more preferably And more preferably And even more preferably It is.
  • the alkyl group which X can take has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • Examples of preferable alkyl groups include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among them, a methyl group is preferable.
  • the alkyl part of the alkoxy group that X can take the description and preferred range of the alkyl group that X can take can be referred to.
  • the halogen atom that X can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.
  • Examples of the ester group that X can take include a group represented by R′COO—.
  • R ′ examples include an alkyl group having 1 to 8 carbon atoms.
  • the description and preferred range of the alkyl group that R ′ can take the description and preferred range of the alkyl group that X can take can be referred to.
  • Specific examples of the ester include CH 3 COO— and C 2 H 5 COO—.
  • the alkyl group having 1 to 4 carbon atoms which Ya, Yb, Yc and Yd can take may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like can be exemplified.
  • the divalent aromatic 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.
  • As the hetero atom constituting the heterocyclic ring 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 heterocyclic group may have a substituent.
  • substituents that can be taken by the trivalent or tetravalent aromatic hydrocarbons of A 1 and A 2 .
  • Hb represents a perfluoroalkyl group having 2 to 30 carbon atoms, more preferably a perfluoroalkyl group having 3 to 20 carbon atoms, and still more preferably a perfluoroalkyl group having 3 to 10 carbon atoms.
  • the perfluoroalkyl group may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear.
  • m and n are each independently 2 or 3, and a plurality of parenthesized structures may be the same or different from each other, but are preferably the same.
  • M and n in the general formula (II) are determined by the valences of A 1 and A 2 , and the preferable range is also determined by the preferable ranges of the valences of A 1 and A 2 . It is not limited to any theory that a compound in which m and n are 2 or 3 has a remarkably good alignment control performance and haze reduction performance even if the addition amount is small as compared with a conventionally known compound and n is 1. Although it does not do, it is estimated that it originates in the fluorine content in a compound.
  • o and p are each independently an integer of 0 or more, and when o and p are 2 or more, a plurality of Xs may be the same or different from each other.
  • o is preferably 1 or 2.
  • p is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the compound represented by the general formula (II) may have a symmetrical molecular structure or may have no symmetry.
  • 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.
  • the compound represented by the general formula (II) includes the perfluoroalkyl group (Hb), the linking group-(-Sp 1 -L 1 -Sp 2 -L 2 ) m -A 1 -L 3 -and -L described above. 4 -A 2 - (L 5 -Sp 3 -L 6 -Sp 4 -) n -, and is preferably a compound which is a combination of T is a divalent group having the excluded volume effect.
  • the two perfluoroalkyl groups (Hb) present in the molecule are preferably the same as each other, and the linking group present in the molecule-(-Sp 1 -L 1 -Sp 2 -L 2 ) m -A 1 -L 3 - and -L 4 -A 2 - (L 5 -Sp 3 -L 6 -Sp 4 -) n - also is preferably identical to each other.
  • the terminal Hb-Sp 1 -L 1 -Sp 2 -and -Sp 3 -L 6 -Sp 4 -Hb are preferably groups represented by any one of the following general formulas.
  • a is preferably from 2 to 30, more preferably from 3 to 20, and even more preferably from 3 to 10.
  • b is preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5.
  • a + b is 3 to 30.
  • r is preferably from 1 to 10, and more preferably from 1 to 4.
  • Hb-Sp 1 -L 1 -Sp 2 -L 2 -and -L 5 -Sp 3 -L 6 -Sp 4 -Hb at the end of the general formula (II) are represented by any one of the following general formulas.
  • the compound represented by the general formula (II) is synthesized by appropriately selecting and combining the synthesis methods described in JP-A No. 2002-129162, JP-A No. 2002-97170, and literatures cited therein. can do. Moreover, it can synthesize
  • the liquid crystal composition can contain a solvent and other additives (for example, cellulose ester) as necessary.
  • organic solvent As the solvent for the liquid crystal composition, an organic solvent is preferably used.
  • organic solvents 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). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
  • the film forming method of the film having a cholesteric liquid crystal structure is not particularly limited, and a film having a cholesteric liquid crystal structure can be formed by forming a liquid crystal composition containing a polymerizable liquid crystal compound by a method such as coating.
  • a film having a cholesteric liquid crystal structure can be produced by applying a coating liquid containing a polymerizable liquid crystal compound on the substrate, and a liquid containing a cholesteric liquid crystal material is applied on the alignment film to form a liquid crystal layer.
  • a film having a cholesteric liquid crystal structure can also be produced.
  • a film having a cholesteric liquid crystal structure by coating a coating liquid containing a polymerizable liquid crystal compound on a substrate.
  • the film having a cholesteric liquid crystal structure preferably exhibits optical anisotropy.
  • Light irradiation for the polymerization of the liquid crystal compound 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 .
  • limiting in particular about the time which irradiates a coating film with an ultraviolet-ray it will be determined from the viewpoint of both sufficient intensity
  • light irradiation may be performed under heating conditions.
  • An example of a manufacturing method is (A) Applying a liquid crystal composition containing an alignment control agent and a polymerizable (curable) liquid crystal compound to the surface of a substrate such as a transparent plastic resin film to form a cholesteric liquid crystal phase; (B) irradiating the liquid crystal composition with ultraviolet rays to advance a curing reaction, fixing the cholesteric liquid crystal phase, and forming a light reflection layer;
  • a production method comprising at least
  • the method for producing a light interference pigment of the present invention comprises a light reflecting layer that reflects right-handed circularly polarized light obtained by curing a film having a cholesteric liquid crystal structure and fixing the alignment state of at least one polymerizable liquid crystal compound, and at least It is preferable to manufacture by laminating
  • a film having a cholesteric liquid crystal structure having the structure shown in FIG. 1 (the substrate is not shown in FIG. 1) is manufactured on the substrate. It is possible to form a film (light reflecting layer) having a cholesteric liquid crystal structure in which the number of stacked layers is further increased by repeating the process.
  • a liquid crystal composition is applied to the surface of the substrate or the lower light reflection layer.
  • the liquid crystal composition is preferably prepared as a coating solution in which a material is dissolved and / or dispersed in a solvent.
  • the liquid crystal composition applied to the surface to become a coating film is in a cholesteric liquid crystal phase.
  • the coating film may be dried and the solvent may be removed to obtain a cholesteric liquid crystal phase.
  • the cholesteric liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the cholesteric liquid crystal phase transition temperature.
  • the liquid crystal phase transition temperature of the liquid crystal composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C., from the viewpoint of production suitability and the like.
  • a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase.
  • a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting the liquid crystal phase, which is disadvantageous from waste of thermal energy, deformation of the substrate, and alteration.
  • (B) Process it is preferable to irradiate an ultraviolet-ray to the coating film used as the state of the cholesteric liquid crystal phase, and to advance hardening reaction.
  • a light source such as an ultraviolet lamp is used.
  • the curing reaction of the liquid crystal composition proceeds by irradiating ultraviolet rays, the cholesteric liquid crystal phase is fixed, and the light reflecting layer is formed.
  • ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a cholesteric liquid crystal phase so that a cholesteric liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.
  • the reaction rate of the curing reaction (for example, polymerization reaction) that proceeds by irradiation with ultraviolet rays is 70% or more from the viewpoint of maintaining the mechanical strength of the layer and suppressing unreacted substances from flowing out of the layer. Preferably, it is 80% or more, more preferably 90% or more.
  • a method of increasing the irradiation amount of ultraviolet rays to be irradiated and polymerization under a nitrogen atmosphere or heating conditions are effective.
  • polymerization temperature, and pushing a reaction further by thermal polymerization reaction, and the method of irradiating an ultraviolet-ray again can also be used.
  • the reaction rate can be measured by comparing the absorption intensity of the infrared vibration spectrum of a reactive group (for example, a polymerizable group) before and after the reaction proceeds.
  • the cholesteric liquid crystal phase is fixed and the light reflecting layer is formed.
  • the state in which the liquid crystal phase is “fixed” is the most typical and preferred mode in which the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained.
  • the layer has no fluidity and is oriented by an external field or external force. It shall mean a state in which the fixed orientation form can be kept stable without causing a change in form.
  • the alignment state of the cholesteric liquid crystal phase is preferably fixed by a curing reaction that proceeds by ultraviolet irradiation.
  • the liquid crystalline mixture may have a high molecular weight due to a curing reaction and may no longer have liquid crystallinity.
  • a film having a cholesteric liquid crystal structure has a liquid crystal film (hereinafter sometimes abbreviated as a liquid crystal film) formed by fixing a cholesteric liquid crystal phase.
  • the film having a cholesteric liquid crystal structure is preferably a laminate of two or more layers. That is, the liquid crystal film preferably has two or more layers having a cholesteric liquid crystal structure.
  • FIG. 1 shows an example of a laminated structure of a film 1 having a cholesteric liquid crystal structure, and reference numerals 15a and 15b denote light reflecting layers, respectively.
  • the light reflecting layers 15a and 15b are preferably films having a cholesteric liquid crystal structure, and preferably exhibit light selective reflectivity for reflecting light of a specific wavelength based on the helical pitch of the cholesteric liquid crystal phase. In one embodiment of the present invention, it is preferable that the adjacent light reflecting layers 15a and 15b have opposite spiral directions of the respective cholesteric liquid crystal phases and the same reflection center wavelength ⁇ 15 .
  • the selective reflection wavelength is not particularly limited.
  • the spectral distribution of solar energy intensity shows a general tendency that the shorter the wavelength, the higher the energy, but the infrared wavelength.
  • the selective reflection wavelength of the film having a cholesteric liquid crystal structure is preferably 420 nm or less.
  • each light reflecting layer is about 1 ⁇ m to 8 ⁇ m (preferably about 3 to 7 ⁇ m). However, it is not limited to these ranges.
  • a light reflecting layer having a desired helical pitch can be formed.
  • the thickness of a layer can be made into a desired range by adjusting the application quantity.
  • the adjacent light reflecting layers 15a and 15b have the spiral directions of the respective cholesteric liquid crystal phases opposite to each other.
  • the adjacent light reflecting layers 16a and 16b have the spiral directions of the respective cholesteric liquid crystal phases. It is preferable that they are opposite to each other.
  • a light reflection layer made of a cholesteric liquid crystal phase in the opposite direction and having the same selective reflection center wavelength in the vicinity, both the left circularly polarized light and the right circularly polarized light having the same wavelength can be reflected. .
  • the light that has passed through the light reflecting layer 16b (the light that has been reflected by the right circularly polarized light having the wavelength ⁇ 16 and only the left circularly polarized light is transmitted) is selected so that the next light passes through 15a and 15b instead of 16b.
  • the center wavelength of the reflected is not lambda
  • left-handed circularly polarized light component of the wavelength lambda 16 will be the size of the helical pitch passes through different cholesteric liquid crystal layer.
  • the left circularly polarized light component having the wavelength ⁇ 16 is slightly affected by the optical rotation of the cholesteric liquid crystal phase in the other light reflecting layers, and changes such as a shift in the wavelength of the left circularly polarized light component. Occurs.
  • this phenomenon is not limited to the “left circularly polarized light component of wavelength ⁇ 16 ”, but is a change that occurs when circularly polarized light with a certain wavelength passes through cholesteric liquid crystal phases with different helical pitches. is there.
  • the set of light reflecting layers be adjacent to each other.
  • the mode of the film having a cholesteric liquid crystal structure is not limited to the above mode.
  • a structure in which one or a plurality of light reflecting layers are stacked on one surface of the substrate may be used, or one or more pairs of light reflecting layers are stacked on both surfaces of the substrate. There may be.
  • the aspect which has 2 or more sets of light reflection layers which show the same reflection center wavelength may be sufficient.
  • each light reflecting layer constituting the film having a cholesteric liquid crystal structure is preferably 1 to 10 ⁇ m, and more preferably 2 to 7 ⁇ m.
  • the total thickness of the film having a cholesteric liquid crystal structure is preferably 1 to 50 ⁇ m from the viewpoint of controlling the thickness of the light interference particles obtained by crushing the film having the cholesteric liquid crystal structure within a preferable range, and is 3 to 30 ⁇ m. More preferably, it is 4 to 10 ⁇ m.
  • the method for producing a light interference pigment of the present invention includes a step of producing light interference particles by crushing a film having a cholesteric liquid crystal structure.
  • a step of producing light interference particles by crushing a film having a cholesteric liquid crystal structure There is no particular limitation on the process for producing optical interference particles by crushing a film having a cholesteric liquid crystal structure.
  • the substrate is peeled off from the film having a cholesteric liquid crystal structure. It can be produced by crushing the film from which the substrate has been peeled to form a flake, further crushing and crushing to the size of fine particles.
  • the light interference particles can be pulverized by drying or wet pulverizing the immobilized cholesteric liquid crystal structure.
  • the method for producing a light interference pigment of the present invention it is preferable that after interference with a film having a cholesteric liquid crystal structure, light interference particles having an average equivalent circle diameter of 100 ⁇ m or less are collected using a filter.
  • the method of sorting the light interference particles using a filter include a method of classifying using a sieve or a cyclone. Among them, it is possible to select and use light interference particles having an average equivalent circle diameter of 1 to 100 ⁇ m, more preferably 1 to 70 ⁇ m, and particularly preferably 5 to 50 ⁇ m. It is desirable from the viewpoint of the physical performance of the film.
  • the shape of the light interference particles is not particularly limited, and may be spherical, circular, elliptical, polygonal, rod, or fibrous.
  • the light interference particles are preferably flat (flat or flat), more preferably a circular flat.
  • the thickness of the flat or flat plate-like light interference particles is, for example, preferably 1 to 50 ⁇ m, more preferably 3 to 30 ⁇ m, and particularly preferably 4 to 10 ⁇ m.
  • the flat optical interference particles preferably have an aspect ratio (average equivalent circle diameter / thickness) of 0.1 to 150, more preferably 0.5 to 50, and particularly preferably 1 to 10. preferable.
  • the selective reflection wavelength of the light interference particles is preferably 420 nm or less.
  • Examples of the method for measuring the selective reflection wavelength of the light interference particles include the following methods. It can be measured by sealing between two quartz glass plates together with a liquid having the same refractive index as that of the optical interference particles (manufactured by Moritex Co., Ltd., Cargill standard refractive liquid series A).
  • the selective reflection wavelength of the light interference particles cannot be directly obtained, it may be obtained indirectly by measuring the selective reflection wavelength of the interlayer film for laminated glass to which the light interference particles and the resin are added.
  • the method for producing an optical interference pigment according to the present invention comprises at least an SP value of 8.5 to 12 (cal / cm 3 ) 1/2 .
  • a step of washing at a temperature of 35 ° C. or higher using an organic solvent is included.
  • the light interference particles after the film having the cholesteric liquid crystal structure is in contact with the outside interface in the state where the light interference particles are not in contact with the outside interface.
  • the light interference pigment obtained after cleaning is obtained by cleaning, by a specific method, the interface corresponding to the inside of the film that is not in contact with the interface with the outside among the light interference particles.
  • the light reflection performance at the selective reflection wavelength when is dispersed in a dispersion medium is improved.
  • the impurities and unnecessary components removed by such a washing step include light interference particles that are finer than a size that exhibits a sufficient light interference effect (for example, an average equivalent circle diameter of 5 ⁇ m or less), impurities (such as those without a reactive group) originally contained in a polymerizable liquid crystal compound, and the like.
  • the present invention is not limited by the types and amounts of impurities and unnecessary components removed by these washing steps.
  • the light interference pigment and organic solvent used in the cleaning step may contain impurities and unnecessary components, and the present invention provides impurities and unnecessary components contained in the light interference pigment and organic solvent used in these cleaning steps. It is not limited by the type or amount.
  • the method for producing a light interference pigment of the present invention is washed at a temperature of 35 ° C. or higher.
  • the washing temperature is more preferably 40 ° C. or more and the boiling point of the organic solvent or less from the viewpoint of further improving the light reflection performance at the selective reflection wavelength when dispersed in the dispersion medium, A temperature of 40 to 60 ° C. is particularly preferable.
  • the SP value of the organic solvent is 12 (cal / cm 3 ) 1/2 or more, the solubility of the monomer is deteriorated and it is not suitable for washing.
  • the SP value of the organic solvent is more preferably 8.5 to 10 (cal / cm 3 ) 1/2 .
  • a material constituting the film having a cholesteric liquid crystal structure or a material used for forming the film is dissolved in an organic solvent having an SP value in the above range.
  • Examples of the organic solvent having an SP value of 8.5 to 12 (cal / cm 3 ) 1/2 include butyl acetate, toluene, methyl ethyl ketone, and acetone. These organic solvents may be used alone or in combination of two or more. However, when two or more organic solvents are mixed and used, the SP values of all organic solvents used for washing are the above. It is preferable that it is an organic solvent contained in the range.
  • the method for washing the light interference particles using an organic solvent there are no particular restrictions on the method for washing the light interference particles using an organic solvent, and examples include a method of washing by immersing the light interference particles in an organic solvent, and a method of washing by spraying the organic solvent onto the light interference particles. be able to.
  • the method for producing a light interference pigment of the present invention it is preferable to wash the light interference particles by immersing them in an organic solvent.
  • the method for producing a light interference pigment of the present invention it is preferable to collect a residue obtained by immersing light interference particles in an organic solvent and washing, and then filtering the organic solvent through a filter.
  • the light interference particles obtained by pulverization are usually classified by dryness, unnecessary fine particles remain.
  • fine particles of unnecessary size can be removed together.
  • the light reflection performance at the selective reflection wavelength when dispersed in a medium is improved.
  • a series of washing operations of immersing and filtering light interference particles in an organic solvent are repeated twice or more from the viewpoint of further improving the light reflection performance at the selective reflection wavelength when dispersed in a dispersion medium. Also good.
  • the filtration accuracy of the filter used for filtering the organic solvent is preferably 0.3 to 6 ⁇ m, and more preferably 0.5 to 3 ⁇ m. It is more preferable.
  • optical characteristics are greater than when unnecessary particles remain in the filtration residue. The light reflectance at the wavelength is improved.
  • the light interference pigment of the present invention is produced by the method for producing a light interference pigment of the present invention. Therefore, the light interference pigment of the present invention has good light reflection performance at a selective reflection wavelength when dispersed in a dispersion medium.
  • the preferred structure and preferred optical properties of the light interference pigment of the present invention are the same as the preferred structure and preferred optical properties of the light interference particles.
  • the light interference pigment of the present invention is preferably used as a UV reflecting material. There is no restriction
  • the light interference pigment of the present invention can be used for producing a light interference pigment dispersion.
  • the method for producing a light interference pigment dispersion preferably includes a step of dispersing the light interference pigment produced by the method for producing a light interference pigment of the present invention in a dispersion medium containing alcohol.
  • the main factor that causes the selective reflection wavelength and reflection spectrum peak shape of the light interference pigment dispersion to deviate from that of the light interference pigment before the dispersion is used is that the solvent interferes with the light interference pigment (occurs simultaneously with the elution of the residual monomer).
  • the birefringence ⁇ n of the light interference pigment decreases due to the surrounding material (for example, resin) entering the gap.
  • (1) and (2) are repeated in the same manner except that the coating liquid (B) is applied on the lower cholesteric liquid crystal layer film instead of the substrate in (1).
  • the produced two-layer laminated film having a cholesteric liquid crystal structure that reflects ultraviolet light having a wavelength of 380 nm was peeled from the substrate.
  • the peeled two-layer laminated film having a cholesteric liquid crystal structure was crushed into flakes, and further pulverized to the size of fine particles to produce light interference particles.
  • the particle size of the light interference particles was classified using a sieve.
  • the average thickness was 10 ⁇ m and the average equivalent circle diameter was 20 ⁇ m.
  • grains have a cholesteric liquid crystal structure.
  • the selective reflection wavelength of the obtained light interference particles was confirmed using an ultraviolet-visible near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation), it was about 380 nm.
  • Example 7 In Example 1, when the obtained light interference particles were evaluated in the same manner as in Example 1 without solvent washing, the evaluation was C.
  • Example 8 In Example 1, Bencot (Asahi Kasei Co., Ltd.) impregnated with methyl ethyl ketone (same as Example 3, SP value 9.3, boiling point 79.5 ° C.) on the surface of the two-layer laminated film having a cholesteric liquid crystal structure peeled from the substrate. After wiping twice with a product manufactured by Sensui Co., Ltd., it was pulverized into light interference particles in the same manner as in Example 1. Thereafter, the obtained light interference particles were evaluated in the same manner as in Example 1 without solvent washing, and the evaluation was C.
  • Example 9 Instead of a PET film as a base film, on one side of a long film of triacetylcellulose (Fujitack, manufactured by Fuji Film Co., Ltd., thickness: 100 ⁇ m, width: 500 mm, glass transition temperature 145 ° C.) A 5% by weight solution of long-chain alkyl-modified PVA (MP-203, manufactured by Kuraray Co., Ltd.) is applied, dried at 90 ° C. for 4 minutes, and then rubbed to form an alignment film forming resin having a thickness of 2.0 ⁇ m. A film having a layer formed thereon was used. Other than that, a light interference pigment was produced in the same manner as in Example 3, and the light interference pigment was evaluated. The evaluation was also A.
  • Example 10 As a base material, a 5% by weight long-chain alkyl-modified PVA (MP-203, manufactured by Kuraray Co., Ltd.) was applied to one side of a 2 mm thick glass plate instead of PET film as in Example 8. Then, after drying at 90 ° C. for 4 minutes, a film in which a rubbing treatment was performed to form an alignment film-forming resin layer having a thickness of 2.0 ⁇ m was used. Other than that, a light interference pigment was produced in the same manner as in Example 3, and the light interference pigment was evaluated. The evaluation was also A.
  • MP-203 manufactured by Kuraray Co., Ltd.
  • Example 11 A light interference pigment was produced in the same manner as in Example 3 except that RM-257 (manufactured by Merck) was used as the rod-like liquid crystal compound, and the light interference pigment was evaluated. The evaluation was also A.
  • Example 12 A light interference pigment was produced in the same manner as in Example 3 except that LC-242 (manufactured by BASF) was used as the rod-like liquid crystal compound, and the light interference pigment was evaluated. The evaluation was also A.
  • the light interference pigment obtained by the production method of the present invention has good light reflection performance at a selective reflection wavelength when dispersed in a dispersion medium (particularly when a dispersion containing a silicone resin and alcohol).
  • Comparative Example 1 it can be seen from Comparative Example 1 that the light interference pigment produced under conditions where the washing temperature is lower than the lower limit specified in the present invention deteriorates the light reflection performance at the selective reflection wavelength when dispersed in a dispersion medium. It was.
  • Comparative Examples 2 to 4 the light interference pigment produced under the condition that the organic solvent used for cleaning exceeds the upper limit of the SP value defined in the present invention, the light reflection performance at the selective reflection wavelength when dispersed in the dispersion medium It turned out to get worse.
  • the light interference pigment produced under the condition that the organic solvent used for cleaning is lower than the lower limit value of the SP value defined in the present invention has deteriorated light reflection performance at the selective reflection wavelength when dispersed in a dispersion medium.
  • a light interference pigment produced using water, which is a solvent exceeding the upper limit of the SP value defined in the present invention at the time of washing as disclosed in JP2011-132512A and International Publication WO96 / 28498, It was found that the light reflection performance at the selective reflection wavelength when dispersed in a dispersion medium deteriorates.
  • the light interference pigment produced without washing the particles obtained after pulverization as in JP-A-2000-44451 has a light reflection performance at a selective reflection wavelength when dispersed in a dispersion medium. It turns out that it gets worse. From Comparative Example 8, it was produced without washing the particles obtained after pulverization even when the surface was washed without pulverizing a film having a cholesteric liquid crystal structure as in JP 2012-101999 A It was found that the light interference pigment deteriorates the light reflection performance at the selective reflection wavelength when dispersed in the dispersion medium.
  • Film having a cholesteric liquid crystal structure may include a substrate) 15a Light reflecting layer 15b in which the alignment state (cholesteric liquid crystal phase) of the polymerizable liquid crystal compound is fixed 15b Light reflecting layer in which the alignment state (cholesteric liquid crystal phase) of the polymerizable liquid crystal compound is fixed

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Abstract

La présente invention concerne un procédé de production d'un pigment d'interférence optique, ledit procédé étant caractérisé en ce qu'il comprend une étape de durcissement de l'état d'alignement d'un composé cristam liquide polymérisable pour produire un film ayant une structure de cristal liquide cholestérique fixée, une étape de broyage du film ayant une structure cristal liquide cholestérique pour produire des particules d'interférence optique, et une étape de lavage des particules d'interférence optique à une température 35°C ou plus à l'aide d'au moins un solvant organique ayant une valeur de SP de 8,5 à 12 (cal/cm3)1/2, dans laquelle la valeur de SP représente un paramètre de solubilité (δ) tel que mesuré par une méthode de Hoy et est représentée par la formule (1) : δ = (ΔE/V)1/2 (où V représente le volume moléculaire molaire de solvant ; et ΔE représente une énergie cohésive). Le procédé de production permet la fourniture d'un pigment d'interférence optique qui a une bonne performance de réflexion de lumière à une longueur d'onde de réflexion sélective lorsqu'il est dispersé dans un milieu de dispersion.
PCT/JP2014/058401 2013-03-27 2014-03-26 Pigment d'interférence optique et son procédé de production WO2014157267A1 (fr)

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JPWO2017073065A1 (ja) * 2015-10-28 2018-08-16 公益財団法人静岡県産業振興財団 新規抗がん薬
US10517849B2 (en) 2016-10-26 2019-12-31 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US10526287B2 (en) 2015-04-23 2020-01-07 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and uses thereof
US10647661B2 (en) 2017-07-11 2020-05-12 Vertex Pharmaceuticals Incorporated Carboxamides as modulators of sodium channels
US10894797B2 (en) 2018-09-18 2021-01-19 Nikang Therapeutics, Inc. Fused tricyclic ring derivatives as SRC homology-2 phosphatase inhibitors

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CN107272294B (zh) 2017-07-10 2020-08-18 华南师范大学 一种电控智能窗及制备方法、光调节方法
CN113165354A (zh) * 2018-11-29 2021-07-23 3M创新有限公司 复合膜、其制备方法以及包括该复合膜的制品
WO2021020243A1 (fr) * 2019-07-30 2021-02-04 日本ゼオン株式会社 Pigment composite, support d'identification, et procédé de jugement d'authentification
US20220289988A1 (en) * 2019-07-30 2022-09-15 Zeon Corporation Composite pigment, identification medium, and authenticity determination method
CN114573599A (zh) * 2022-02-24 2022-06-03 苏州大学 光致异构手性分子及其在实现彩色液晶膜图案化中的应用

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US10526287B2 (en) 2015-04-23 2020-01-07 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and uses thereof
JPWO2017073065A1 (ja) * 2015-10-28 2018-08-16 公益財団法人静岡県産業振興財団 新規抗がん薬
US10517849B2 (en) 2016-10-26 2019-12-31 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US11013718B2 (en) 2016-10-26 2021-05-25 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US11547695B2 (en) 2016-10-26 2023-01-10 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US10647661B2 (en) 2017-07-11 2020-05-12 Vertex Pharmaceuticals Incorporated Carboxamides as modulators of sodium channels
US11603351B2 (en) 2017-07-11 2023-03-14 Vertex Pharmaceuticals Incorporated Carboxamides as modulators of sodium channels
US10894797B2 (en) 2018-09-18 2021-01-19 Nikang Therapeutics, Inc. Fused tricyclic ring derivatives as SRC homology-2 phosphatase inhibitors
US11034705B2 (en) 2018-09-18 2021-06-15 Nikang Therapeutics, Inc. Fused tricyclic ring derivatives as Src homology-2 phosphate inhibitors
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US11518772B2 (en) 2018-09-18 2022-12-06 Nikang Therapeutics, Inc. Fused tricyclic ring derivatives as Src homology-2 phosphate inhibitors

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