WO2020095275A1 - Film sensible à la température, à humidité élevée, et fenêtre autorégulatrice faisant intervenir celui-ci - Google Patents

Film sensible à la température, à humidité élevée, et fenêtre autorégulatrice faisant intervenir celui-ci Download PDF

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Publication number
WO2020095275A1
WO2020095275A1 PCT/IB2019/059634 IB2019059634W WO2020095275A1 WO 2020095275 A1 WO2020095275 A1 WO 2020095275A1 IB 2019059634 W IB2019059634 W IB 2019059634W WO 2020095275 A1 WO2020095275 A1 WO 2020095275A1
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WIPO (PCT)
Prior art keywords
substrate
film
photoinitiator
liquid crystal
copolymer
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Application number
PCT/IB2019/059634
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English (en)
Inventor
Nadia Grossiord
Ellen Petronella Arnolda VAN HEESWIJK
Joey J.H. KLOOS
Albert P.H.J. SCHENNING
Original Assignee
Sabic Global Technologies B.V.
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Publication of WO2020095275A1 publication Critical patent/WO2020095275A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • 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
    • C08J3/18—Plasticising macromolecular compounds
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • 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
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • 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
    • 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
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • 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
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C09K19/588—Heterocyclic compounds
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • 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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
    • 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/13—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the technical field of thermotropic switches
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • E06B2009/2417—Light path control; means to control reflection
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
    • E06B3/6715—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light
    • E06B3/6722—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light with adjustable passage of light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13718—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a change of the texture state of a cholesteric liquid crystal
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13775—Polymer-stabilized liquid crystal layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/30—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 grating
    • G02F2201/307—Reflective grating, i.e. Bragg grating
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/34—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 reflector
    • G02F2201/346—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 reflector distributed (Bragg) reflector

Definitions

  • This disclosure relates to temperature-responsive films chemisorbed to a substrate.
  • the films are useful for smart window applications.
  • Electrically responsive windows are also available, most of them making use of materials such as liquid crystals, electrochromic molecules, or suspended particle device that are encapsulated between two glass or plastic plates with electrodes.
  • electrically responsive windows are generally responsive to a user, rather than an external change in condition.
  • Temperature- responsive windows based on hydrogels, phase change materials (PCMs), or holographic polymers dispersed in liquid crystals are also known, although these responsive materials are also often sandwiched between two substrates.
  • LCPs Liquid crystal polymers
  • LCPs are responsive to small changes in external conditions, such as temperature, that can trigger phase transitions that cause significant changes in their macroscopic properties.
  • LCPs can be used as coatings on transparent substrates such as glass or polycarbonate, but often have poor adhesion to substrates to such substrates, e.g., physical adsorption. The adhesion can be improved by chemisorption, which includes covalent chemical linkages between the substrate and the coating.
  • polymerization can be conducted at room temperature and atmospheric pressure, with or without a solvent, and with conventional equipment.
  • a layered article comprising a copolymer substrate comprising a Type II photoinitiator covalently linked to the copolymer of the substrate; and a temperature-responsive, cholesteric LCP film chemisorbed to a surface of the copolymer substrate, wherein the LCP film has a broadband response at a relative humidity of 60% to 95%.
  • a method of forming the layered article as described above comprising: providing a copolymer substrate having opposed first and second sides, and comprising a Type II photoinitiator covalently linked to the copolymer; applying a primer composition comprising 0.1 to 7 weight percent, preferably 0.1 to 2 weight percent of a Type II photoinitiator onto a first surface area of the first side of the copolymer substrate to form a primer layer; applying a coating composition comprising a liquid crystal monomer composition onto at least a portion of the primer layer under shear to provide an aligned coating layer;
  • a window includes a frame; and a sheet supported by the frame, wherein the sheet comprises the layered article.
  • FIG. 1 is side cross-sectional view illustrating a liquid crystalline coating on a polycarbonate copolymer substrate according to the present disclosure
  • FIG. 2A is UV-Vis spectra of comparative example 1 at 75% RH and different temperatures
  • FIG. 2B is a graph showing the area of the water peak and the shift of the reflection band versus temperature at a RH of 75% of comparative example 1;
  • FIG. 2C is a graph showing the shift of reflections bands versus temperature at various RH levels ranging from 30 to 75% of comparative Example 1;
  • FIG. 3 an SEM cross-section of an LCP coating of comparative example 2;
  • FIG. 4 is an SEM cross-section of an LCP coating of comparative example 3.
  • FIG. 5 is an SEM cross-section of an LCP coating of inventive example 4.
  • FIG. 6A is a transmission spectrum of the reflection band of example 4, before and after the alkaline treatment, including saturated (wet) and dried coatings after alkaline treatment;
  • FIG. 6B is a transmission spectrum of example 4 after alkaline treatment of the coating at various temperatures (constant RH of 75%);
  • FIG. 6C is a transmission spectrum of example 4 after alkaline treatment of the coatings at -2°C after cooling from 70°C at various time intervals.
  • the inventors hereof have discovered an improved layered article having a temperature- sensitive film chemisorbed to a copolymer substrate and having a temperature- dependent broadband response.
  • the broadband response can be in the ultraviolet (UV), visible, or infrared (IR) region of the spectrum.
  • the film is chemisorbed to a substrate by a method that allows the wider response range.
  • a substrate having a Type II photoinitiator covalently linked to the substrate together with a primer layer comprising a Type II
  • photoinitiator and a modified LC film-forming composition allows the formation of a pitch gradient within the LCP film as described in further detail below.
  • the layered articles can be used to manufacture a self-regulating window.
  • the films and windows have a number of advantageous properties.
  • Responsiveness is high, in that the change from one state to the other begins within a few seconds, and is complete within minutes, e.g., in less than 30 minutes depending on temperature change and other factors.
  • the LCP film has good mechanical properties.
  • the response is autonomous, that is, it does not require user input.
  • Another significant advantage is that no additional energy input is required for the film to function.
  • Deposition of the films can be a one-step process. Moreover, the film does not need to be sandwiched between two glass plates, which can provide a manufacturing and weight savings. Finally, the functionality of the films is optimum at atmospheric relative humidity (RH) levels of 60% to 95%. The films are therefore especially useful in controlled higher humidity
  • the layered article includes a cholesteric LCP.
  • the LCP is designed to have a pitch change, which induces a reflection band shift, and is triggered by water molecule intercalation.
  • the films can absorb more water because water condenses more easily and therefore penetrates the films to a greater extent. Water absorption between the layers results in an increase in the helix pitches, leading to a red shift (towards longer
  • changing the wavelength of the reflection band can be achieved by changing the chiral dopant concentration.
  • the polymers and other aspects of the layered article can be adjusted by changing the chiral dopant concentration to achieve shifts in other regions of the spectrum, for example in the UV-visible region.
  • the liquid crystals in the films described herein can be designed to have a pitch gradient within the film.
  • cholesteric liquid crystals possess a helical structure, and organize in layers with no positional ordering within layers except for a director axis n, which varies with the layers, and tends to be periodic in nature.
  • the period of this variation i.e., the distance over which a full rotation of 360° is completed, defines the pitch of the helix.
  • periodic changes of the refractive index due to the orientation change of the liquid crystal orientation create the parallel planes needed to induce Bragg reflection.
  • Coatings with a pitch gradient can therefore reflect a broader wavelength range.
  • a pitch gradient can be obtained by use of a primer layer having a photoinitiator, for example a Type II photoinitiator, but adhesion between the coating and the substrate may not be sufficient.
  • the LCP film is covalently bound to a substrate as described in more detail below.
  • the LCP films are a thermotropic, cholesteric LCP network that can be prepared by photopolymerizing liquid crystal (LC) monomers containing a polymerizable carbon-carbon double bond of formula (1):
  • each R is independently hydrogen or a substituted or unsubstituted C1-12 alkyl
  • X is a group containing a liquid crystal moiety.
  • the group X contains one reactive end group, referred to herein as a“bifunctional” LC monomer.
  • X also contains at least one additional carbon-carbon double bond, which is referred to herein as a“polyfunctional” LC monomer.
  • R in formula (1) is hydrogen or methyl
  • the liquid crystal moiety in group X is contains at least a thermotropic mesogenic moiety and a flexible spacer moiety between the mesogenic moiety and the polymerizable carbon-carbon double bond.
  • the mesogen can comprise at least one or more aromatic groups.
  • the identity of the spacer moiety and the rigid core can determine the type of phase of the LC monomer (e.g., nematic or smectic); the transition temperatures between e.g. the isotropic and nematic phase; and the flexibility of the LCP network, and thus indirectly the mechanical properties and switching time of the LCP.
  • the LC monomer is a (meth)acrylate LC monomer having a terminal (meth)acrylate group, i.e., a monomer of formula (2):
  • Ri is hydrogen (an acrylate group) or methyl (a methacrylate group); and X is a group containing a liquid crystal moiety as described above.
  • the LC group X comprises at least one mesogenic moiety Y and at least one spacer moiety Z (and usually more than one such moiety).
  • such LC moieties can have the structure of formula (A):
  • each of Z and Y are independently bound to another mesogenic moiety Y, spacer moiety Z, a nonreactive end group, or a reactive end group such as a terminal (meth)acrylate group (2).
  • the combination of the spacer Z and mesogenic Y moieties gives the LC monomers an elongated (i.e., rod-like) shape responsible for the liquid crystalline behavior of the films.
  • a bifunctional monomer can have the general structure: reactive end group-spacer-LC moiety-non-reactive end group.
  • a poly functional monomer can have the following general structure: first reactive end group-first spacer-LC moiety-second spacer-second reactive end group.
  • each spacer moiety Z independently comprises the same or different C 1-30 aliphatic group, preferably a C 1-30 non-cyclic alkyl group.
  • the mesogenic moiety Y of the LC group X comprises at least one aromatic group, which creates flat segments in the LC monomer.
  • the mesogenic moiety Y can comprise one or more derivatives of /i-hydroxybenzoic acid, having the structure of formula (B):
  • the mesogenic moiety Y can further comprise one or more ester, ether, or carbonate linkages.
  • the mesogenic moiety Y is a heterocyclic or fused heterocyclic ring system (i.e., a nonaromatic ring system without a delocalized pi system).
  • the heterocyclic or fused heterocyclic ring system has at least one heteroatom, such as nitrogen, sulfur, selenium, silicon, oxygen, or a combination thereof.
  • a portion of the mesogen moiety Y of LC group X can comprise a moiety having the structure of formula (C):
  • the mesogen moiety Y can comprise a group having of formula (C) linked to a derivative p-hydroxybenzoic acid (B).
  • the LC monomer can be a chiral LC monomer (a“chiral dopant”) having the general structure: first reactive end group- first spacer-first LC moiety-chiral element-second LC moiety-second spacer-second reactive end group.
  • An exemplary chiral LC monomer having a chiral center derived from a group of formula (C) is the polyfunctional monomer of formula (3):
  • chirality is illustrated by the two bonds connecting the fused heterocyclic rings directed in the same direction out of the plane. Chirality can be altered by instead directing one of the bonds connecting the fused heterocyclic rings into the plane. It is further noted that the length of the spacer moieties, while illustrated as being 4 carbon atoms long, can be varied; and while terminal acrylate groups are shown, methacrylate groups can be used. Likewise, the derivatives of /i-hydroxybenzoic acid on either side of the fused heterocyclic rings can be altered.
  • the chirality can likewise be altered by adding a pendent group to the LC monomer wherein the pendant group has a chiral center.
  • An example of a bifunctional, chiral LC monomer having a pendant chiral group has the structure of formula (4a):
  • R 1 is hydrogen or methyl and i is an integer 1 to 10.
  • An exemplary monomer of this type has a structure of formula (4b): (4b).
  • the chiral LC monomers can be bifunctional, having a chiral group on the spacer moiety.
  • An example is the bifunctional monomer having the structure of formula (5) (and its methacrylate analogue), and the monomer formula (6):
  • each R is independently hydrogen or a substituted or unsubstituted C1-12 alkyl, and Y is a mesogenic moiety as defined formula (2).
  • Other examples include the (meth)acrylate analogs of formula (6).
  • the chain length of the spacer and the location of the chiral center can be varied and is not limited to the examples of formulas (4) and (5).
  • the chiral LC monomers can be polyfunctional monomers having a chiral center located on each of the spacer moieties.
  • chirality can be incorporated into the film by adding a chiral dopant, i.e., a chiral molecule that does not participate in polymerization.
  • a chiral dopant i.e., a chiral molecule that does not participate in polymerization.
  • Non-limiting examples of chiral molecules include those of formulas (7), (8), and (9):
  • the LC monomer can comprise a polyfunctional monomer having at least two terminal (meth)acrylate groups.
  • An example of such LC monomers includes bifunctional monomers having the structure of formula (10):
  • each R 1 is independently hydrogen or methyl
  • X is an LC moiety as described above.
  • the polyfunctional monomer having at least two terminal (meth)acrylate groups and can have a structure of the formula (lOa):
  • each R 1 is independently hydrogen or methyl and each spacer moiety Z and mesogenic moiety Y are as defined above.
  • each spacer moiety Z is the same. Without being bound by theory, it is believed that the spacer moieties Z being the same can beneficially result in an improved crystalline nature of the LCP film, facilitating the crystalline stacking of the mesogenic moiety Y of neighboring LC monomers.
  • the polyfunctional monomer can have a structure of formula
  • each R 1 is independently hydrogen or methyl
  • each i is the same or different and is an integer of 1 to 10
  • Y is a mesogenic moiety.
  • i in both instances is the same integer.
  • the bifunctional monomer of the Formula (lOb) can be a bifunctional monomer of the formula (lOb-l): (lOb-l) wherein each R 1 is independently hydrogen or methyl, R 4 is hydrogen, substituted or unsubstituted C1-12 alkyl, and each i is the same and is an integer of 1 to 10.
  • R 4 can be a methyl group and i in both instances can be 3; R 4 can be a methyl group and i in both instances can be 6; R 4 can be hydrogen and i in both instances can be 6; R 4 can be hydrogen and i in both instances can be 3; R 4 can be a hexyl group and i in both instances can be 6.
  • the length of the R 4 group can be adjusted to tune the properties of the LCP film, for example, resulting in an increase or decrease in the transition temperature between the nematic and isotropic phases.
  • Specific LC monomers of this type include the monomers having the structure of formula ( (lOb-2) (l0b-3).
  • Still other specific LC monomers of this type include ((4,4’-((((oxybis(ethane-2, l- diyl))bis(oxy))bis(ethane-2, l-diyl))bis(oxy)bis(benzoyl)) bis(oxy))bis(4,l-phenylene)bis(4-((6- (acryloyloxy)hexyl)oxy)-2-methylbenzoate) of formula (lOb-4):
  • the poly functional monomer can be a light-responsive monomer.
  • the polyfunctional, light-responsive monomer can have the structure of Formula (lOb-7), where the mesogenic moiety Y comprises an azo group.
  • the polyfunctional, light- responsive monomer can have the structure of formula (lOb-7):
  • each R 1 is independently hydrogen or methyl, and each i is the same and is an integer of 1 to 10. In an aspect R 1 is methyl and i is 3.
  • the LC monomer can have at least one terminal nitrile group (- CN) and at least one other terminal group, or at least one terminal ether group and at least one other terminal group.
  • exemplary ether groups include C1-12 alkyl ethers, for example methoxy or octyloxy.
  • Exemplary monomers of this type have structures of formula (11), (12), or (13) (4- methoxyphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate) .
  • the LC monomer can have at least one terminal carboxy group.
  • Exemplary monomers of this type have structures of formula (14) and (15):
  • the LC monomers are present in a coating composition used to form the LCP film as described in further detail below.
  • the coating composition can contain a single LC monomer, a plurality of LC monomers is preferably used.
  • the relative types, amounts, and ratios of LC monomers in the coating composition is adjusted to tune properties of the LCP polymer or coating composition, such as the nematic-isotropic phase transition temperature (T NI ), the degree of cross-linking in the LCP film, the viscosity of the coating composition or film, response to specific stimuli, or the helix pitch of the cholesteric liquid crystalline polymer.
  • T NI nematic-isotropic phase transition temperature
  • chiral dopants such as the monomer of formula (3) can be used to obtain cholesteric LCP films.
  • bifunctional chiral dopants can contribute to providing a gradient, which contributes to the broadband response.
  • Polyfunctional monomers of formulas (lOb-2), (l0b-3), (lOb-4), (l0b-5), or (lOb-6) can be used to obtain a specific degree of cross-linking.
  • Monomers such as those of formula (3), (4a), (14), or (15) can be used to tune the TNI of the films.
  • the coating composition can comprise 1 to 5 wt% of a bifunctional chiral dopant, such as an LC monomer of formulas (4a), (4b), (5), or (6); 10 to 30 wt% of a polyfunctional LC monomer of formulas (lOb-2), (l0b-3), (lOb-4), (l0b-5), or (lOb-6); 20 to 40 wt% of bifunctional LC monomers of formulas (11), (12), (13), or a combination thereof; and 30 to 50 wt% of the carboxylic acid-containing bifunctional LC monomers, such as monomers of formulas (14) and (15). All of the foregoing amounts based on the total weight of the LC monomers.
  • a bifunctional chiral dopant such as an LC monomer of formulas (4a), (4b), (5), or (6)
  • the coating composition further comprises a Type II photoinitiator, which can be different from or the same as the Type II photoinitiator used in the
  • Type II photoinitiator is selected based on the type of LC monomers used, the irradiation parameters used, the desired degree of crosslinking, and like considerations.
  • the Type II photoinitiator is a benzophenone, a thioxanthone, a xanthone, or a quinone.
  • Benzophenones have the general structure of formula (i):
  • each W is independently C1 -12 alkyl, carboxyl, hydroxyl, or amino; and m and n are each independently integers from 0 to 2.
  • Thioxanthones and xanthones are compounds that contain a structure of formula
  • X is sulfur or oxygen.
  • the thioxanthone or xanthone can have substituents such as C1 -12 alkyl; halogen; or C1-12 alkoxy.
  • Exemplary thioxanthone Type II photoinitiators include thioxanthone; l-chloro-4-propoxythioxanthone; 2-chlorothioxanthone; 2,4- diethylthioxanthone; 2-isopropylthioxanthone; 4-isopropylthioxanthone; and 2- mercaptothioxanthone.
  • Quinones generally have a fully conjugated cyclic dione structure.
  • exemplary quinone Type II photoinitiators include anthraquinone; anthraquinone-2-sulfonic acid;
  • camphorquinone 2-ethylanthraquinone
  • phenanthrenequinone
  • the coating composition can comprise 1 to 5 wt% of the type II photoinitiator, based on the total weight of solids.
  • the coating compositions can accordingly comprise 90 to 100 wt%, or 90 to 100 wt% of LC monomers (by solids), and when present, 1 to 10 wt% of a second photoinitiator by solids).
  • Other components of the coating composition can be additives known in the art, for example 0.5 to 5 wt% of a surfactant (by solids).
  • An exemplary surfactant is 2-(N- ethylperfluorooctanesulfonamido) ethyl methacrylate.
  • the LC monomer composition is polymerized directly on a surface of a substrate.
  • the reaction takes place in the presence of a Type I photoinitiator that, under ultraviolet (UV) light, undergoes a homolytic bond cleavage, resulting in radicals that induce polymerization of the carbon-carbon double bond.
  • UV ultraviolet
  • the surface of the substrate does not take part in the polymerization, yielding a physisorbed film.
  • LCP films are often plagued by delamination (peeling), i.e., the premature detachment of the film from the substrate.
  • the accompanying loss of function reduces the lifespan of an article containing the film. This is particularly so for polymeric substrates.
  • a primer layer is present between the substrate and the LCP coating compositions when forming the LCP film, or more precisely, diffused into outer layers of the polymer substrate.
  • the primer layer is formed from a primer solution, which can be formed by dissolving an amount of the Type II photoinitiator as described above in a solvent.
  • the solvent dissolves the Type II photoinitiator but does not degrade the substrate.
  • the solvent an alcohol, such as methanol, ethanol, n-propanol, or i-propanol; or an alkane, such as hexane can be used.
  • the priming solution comprises 0.1 to 7 wt%, or 1 to 5 wt% of the Type II photoinitiator, based on the total weight of the priming solution.
  • benzophenone groups of the copolymer backbone remain, and provide a higher benzophenone density at the coating-substrate interface as well as entanglement, which is believed to improve adhesion.
  • the photoinitiator can be covalently linked to the copolymer as a polymer unit, i.e., as unit of a graft, or as a unit of the polymer main chain.
  • the type II photoinitiator can be incorporated into the copolymer by co-reaction of the type II photoinitiator (or a derivative thereof) during synthesis of the copolymer, or by grafting.
  • the other units of the copolymer are selected to have abstractable hydrogen atoms and to provide the desired substrate properties, such a flexibility, hardness, mechanical strength, and the like.
  • the other copolymer units are further selected to be sufficiently transmissive of the activating radiation to allow manufacture of the films as described in further detail below.
  • the other copolymer units can be selected to provide a substrate having one or more of a transparency of 80% or greater, as determined according to ASTM standard D- 1003 -00); a Young’s modulus of 1 GigaPascal (GPa) or greater, or 2 GPa or greater, each as determined according to ASTM D 882 (2012).
  • copolymer units that can be used include carbonate units, ester units, siloxane units, (meth)acrylate units and the like, or a combination thereof, for example a combination for carbonate and ester units, or a combination of carbonate units and siloxane (e.g., dimethylsiloxane) units.
  • Methods for the manufacture of copolycarbonates, copolyesters, copoly(carbonate-ester)s, and the like are known in the art.
  • a preferred copolymer for use as the copolymer substrate is a copolycarbonate, i.e., a polycarbonate copolymer comprising a Type II photoinitiator chemically bound to a polycarbonate main chain as a polymer unit.
  • the copolycarbonate comprises repeat structural carbonate units of formula (20)
  • each R 1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (21) or a bisphenol of formula (22).
  • each R h is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C 6 -io aryl, or a halogen-substituted C 6 -io aryl, and n is 0 to 4.
  • a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C 6 -io aryl, or a halogen-substituted C 6 -io aryl
  • n is 0 to 4.
  • R a and R b are each independently a halogen, C1-12 alkoxy, or Ci- 12 alkyl, and p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen.
  • p and q is each 0, or p and q is each 1
  • R a and R b are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
  • X a is a bridging group connecting the two hydroxy- substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group, for example, a single bond, -O-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-is organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • dihydroxy compounds that can be used are described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923.
  • Specific dihydroxy compounds include resorcinol, 2,2- bis(4-hydroxyphenyl) propane (“bisphenol A” or“BP A”), 3,3-bis(4-hydroxyphenyl)
  • phthalimidine 2 -phenyl-3, 3’ -bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol,“PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one),
  • copolycarbonates further comprise repeat structural carbonate units of formula (23) o
  • R 2 is not the same as R 1 , and R 2 is a type II photoinitiator moiety as described above.
  • the type II photoinitiator can be incorporated into the polycarbonate by co-reaction of its mono- or di-sub stituted hydroxy derivative during synthesis of the polycarbonate, as described, for example, in WO 2015/193862.
  • a specific photoinitiator is a benzophenone.
  • Mono- and dihydroxybenzophenones are known, for example 4-hydroxybenzophenone and 4,4’- dihydroxybenzophenone.
  • the benzophenone can be incorporated into the polycarbonate as a terminal group, in an amount, for example, of 0.5 to 15 mole percent (mol%).
  • a dihydroxy benzophenone is used, the benzophenone can be incorporated into the polycarbonate as a backbone unit, in an amount, for example, of 0.5 to 50 mol%.
  • a tether such as a (Cm alkylene) ether.
  • An example of the reactive group being linked by a tether is the group -0 ⁇ CH2-C00H.
  • Isomers can include structures wherein one or more of the Q are present on a different carbon atom of the ring system.
  • the copolycarbonate can be used by itself as the copolymer substrate, with optional additives as known in the art, for example a dye, mold release agent, heat stabilizer, ultraviolet light stabilizer, or the like, or a combination thereof.
  • an additional polymer compatible with the copolycarbonate is present.
  • another polycarbonate such as a homopolycarbonate can be present e.g., a bisphenol A homopolycarbonate. If an additional polymer is used, it can be present in an amount of 1 to 50 wt%, for example.
  • the copolymer substrate can be in the form of a molded article, a sheet, or a film.
  • the substrate can be formed by a variety of known processes, such as casting, profile extrusion, film or sheet extrusion, sheet-foam extrusion, injection molding, blow molding, thermoforming, and the like.
  • the substrate itself can be a component of an article, such that the article comprises a substrate to be coated with an LCP film.
  • a coating composition comprising the LC monomers is applied to the substrate to form a coating layer, and the coating layer is irradiated to photograft the monomers to form a film.
  • Photografting includes
  • the Type II photoinitiator produces radicals that induce a reaction with the surface of the substrate and with the LC monomers, forming a liquid crystalline polymer matrix that is chemically attached to the substrate.
  • the LC coating layers are thereby covalently bound (i.e., chemisorbed) to the surface of the substrate, and exhibit improved adhesion properties.
  • the process can further comprise forming a primer layer comprising a Type II photoinitiator directly to the substrate; followed by applying the coating composition directly onto the primer layer with no other intervening layers.
  • a coating composition is applied to an area of a first surface of the copolymer substrate.
  • the copolymer substrate can have at least a first surface and a second surface opposite the first surface, although the substrate can be provided in a variety of regular or irregular shapes and sizes.
  • the coating composition comprises at least one LC monomer, and optionally a Type II photoinitiator.
  • the Type II photoinitiator in the coating composition is generally the same as the Type II photoinitiator in the copolymer substrate.
  • the coating composition can be applied to one or more different surfaces of the substrate, or to only a portion of a surface of the substrate, depending on the desired area to be grafted with the LCP.
  • the coating composition can be applied directly to the substrate, with no intervening layers in between.
  • the coating composition can be applied while at room temperature, or at ambient pressure, or in open air, preferably all three. Generally, however, the coating composition is applied at a temperature that is lower than the nematic- isotropic phase transition temperature (TNI) of the coating composition and higher than the crystal-nematic phase transition temperature (TCN).
  • TTI nematic- isotropic phase transition temperature
  • TCN crystal-nematic phase transition temperature
  • the primer solution as described above is applied to an area of the substrate before the coating composition to form a primer solution layer.
  • the primer solution is preferably applied to the same area as where the coating
  • the primer solution comprises a Type II photoinitiator in a solvent.
  • the coating composition can be directly applied, or in an aspect the primer solution layer can be maintained on the surface of the substrate for a period of time to allow the solvent to partially or fully evaporate to form a primer layer, before applying any other layers. Depending on the solvent, this period of time may be 10 seconds to 1 hour or more, preferably 30 seconds to 30 minutes. Evaporation of the solvent can proceed at ambient conditions or with application of heat, for example in an oven.
  • the primer layer can be applied to one or more different surfaces of the substrate, or to only a portion of a surface of the substrate, depending on the desired area to be grafted with the LC coating composition.
  • the primer layer can be applied directly to the substrate, with no intervening layers in between.
  • the primer layer can be applied while at room temperature, or at ambient pressure, or in open air, preferably all three.
  • the coating layer (or, if present, the primer layer) directly contacts the surface of the copolymer substrate. If a primer layer is present, preferably the coating layer is applied directly on the primer layer with no intervening layers. Further, the methods described herein can be performed without pre-activating the surface of the substrate, treating the surface of the substrate with other substances prior to applying the primer layer or the coating layer (e.g. plasma treatment, or acid/base application, or coating with a thin layer of a hydrogen-rich material like polydopamine or polyphenols); or post-polymerization purification steps. In particular, the coating layer (or, if present, the primer layer) is applied without pre-treatment for LC alignment or without use of an alignment layer.
  • the coating layer or, if present, the primer layer
  • Alignment layers are commonly used in the industry, and include, for example, applying a polyimide (PI) layer to the substrate, which is subsequently rubbed with a soft fabric to scratch the PI layer, and subsequently applying the liquid crystalline composition to the PI layer.
  • the scratches act as a template for orientation of the liquid crystalline polymers in a particular direction.
  • the LC orientation of the coating layer can be induced by shear during their deposition upon the substrate (e.g. with a doctor blade, using a slot die, or other spreading mechanism, or by printing).
  • the coating layer and the primer layer are irradiated through the substrate to form an LCP film.
  • the layers can be irradiated by exposure to ultraviolet (UV) light at an appropriate wavelength and in an appropriate dosage that brings about the desired amount of photopolymerization and crosslinking of the LC monomers for the given application.
  • UV ultraviolet
  • the irradiation should reach the substrate-primer-coating interface, permitting the photoinitiator to cause the formation of covalent bonds between the substrate and the LCPs formed during the irradiation.
  • the coating layer and the primer layer are not directly exposed to UV light.
  • the substrate is transmissive or transparent to UV radiation, and a second surface of the substrate is exposed to the UV light, so that the coating layers are irradiated by UV light transmitted through the substrate.
  • the light transmitted through the substrate causes the photoinitiator in the copolycarbonate layer, the primer layer, and the coating layer to initiate polymerization of the LC monomers.
  • the polymer of the substrate is accordingly selected to be sufficiently transmissive to UV irradiation to allow initiation and photopolymerization at the selected dose and time of exposure.
  • a sample of the substrate having a thickness of 1 millimeter can transmit at least 50%, or at least 70%, or at least 90% of radiation in the UV range at a selected intensity.
  • the irradiation of the coated substrate is performed under a continuous nitrogen flow.
  • the level of irradiation and the exposure time of the coating layer to the photoactivating radiation depends on the LC monomers and photoinitiators used, the intended application, and the particular properties of the substrate (e.g. % UV transmittance). It has been found that lower levels of irradiation and longer times allow the formation of the pitch gradients.
  • the coating layer can be irradiated for 1 minute to 1 hour, or 2 to 20 minutes, depending on the irradiation system.
  • the irradiation can be accomplished by using a UV-emitting light source such as a mercury vapor, High-Intensity Discharge (HID), or various UV lamps, such as commercial UV lamps sold for UV curing from manufacturers such as Excelitas Technologies (for example, the OMNICURETM LX500 UVLED curing system), Heraeus Noblelight, and Fusion UV.
  • a UV-emitting light source such as a mercury vapor, High-Intensity Discharge (HID), or various UV lamps, such as commercial UV lamps sold for UV curing from manufacturers such as Excelitas Technologies (for example, the OMNICURETM LX500 UVLED curing system), Heraeus Noblelight, and Fusion UV.
  • Non limiting examples of UV-emitting light bulbs include mercury bulbs (H bulbs), or metal halide doped mercury bulbs (D bulbs, H+ bulbs, and V bulbs). Other combinations of metal halides to create a UV light source are also contemplated. Exemplary bulbs could also be produced by assembling the lamp out
  • UV light source where wavelengths that can cause polymer degradation or excessive yellowing are removed or are not present.
  • Equipment suppliers such as Excelitas, Heraeus Noblelight, and Fusion UV provide lamps with various spectral distributions.
  • the light can also be filtered to remove unwanted wavelengths of light, for example with optical filters that are used to selectively transmit or reject a wavelength or range of wavelengths. These filters are commercially available from a variety of companies such as Edmund Optics or Praezisions Glas & Optik GmbH.
  • Bandpass filters are designed to transmit a portion of the spectrum, while rejecting all other wavelengths.
  • Longpass edge filters are designed to transmit wavelengths greater than the cut-on wavelength of the filter.
  • Shortpass edge filters are used to transmit wavelengths shorter than the cut-off wavelength of the filter.
  • Various types of materials such as borosilicate glass, can be used as a long pass filter. Schott or
  • Praezisions Glas & Optik GmbH for example have the following long pass filters: WG225, WG280, WG295, WG305, WG320, which have cut-on wavelengths of 225, 280, 295, 305, and 320 nm, respectively. These filters can be used to screen out the harmful short wavelengths while transmitting the appropriate wavelengths for the crosslinking reaction.
  • An exemplary lamp is a high pressure 200-watt mercury vapor short arc used in combination with a light guide.
  • a filter and an adjustable spot collimating adapter for spreading the light beam over a large surface can also be used.
  • protective equipment to protect the user can also be used.
  • the coating layer is exposed to light that includes UVA light wavelengths with an intensity of 0.5 to 10 milliwatts per centimeter squared (mW/cm 2 ), or 1 to 5 mW/cm 2 .
  • UVA refers to wavelengths from 320 to 390 nm. This irradiation can be accomplished using a Collimated EXFO OMNICURETM S2000 lamp.
  • the carboxylic acid groups of the LCP film are converted to the salt form.
  • the layered article can be washed or soaked in an aqueous base solution such as sodium hydroxide or potassium hydroxide.
  • the resulting LCP films can have a broad reflection bandwidth, i.e., a broad reflection band, also referred to as a broadband reflective response, or simply a broadband response.
  • a“broad reflection bandwidth” or“broadband response” is all bands wider than Dl k ⁇ as determined by Eq. 1 :
  • Dl kA is the bandwidth
  • ne is the extraordinary refractive index
  • P is the pitch of the cholesteric alignment.
  • a tilting compensator can be used in a polarizing microscope, such as a“Tilting Compensator K” from Leitz Wetzlare.
  • a broadband response is a band wider than the corresponding narrow band according to Eq. 1 above wherein P is the smallest pitch.
  • a broadband response can be obtained from diffusion of the benzophenone.
  • the broadband response is located within a region of the spectrum from 10 nm (UV) to 1 millimeter (IR).
  • the broadband response can be located in the IR region of the light spectrum, for example in the region from 700 nm to 1 millimeter, or in the region of the spectrum from 800 to 1200 nm.
  • the broadband response can be located in the UV-visible light region of the spectrum, for example in the region from 10 nm to 700 nm.
  • the broadband response can also be located in overlapping regions of the spectrum, for example in a region that overlaps the visible and IR range, for example 600 to 1200 nm.
  • the location of the response can be adjusted by adjusting the characteristics of the LCP film as is known in the art, for example by modifying the concentration of a chiral dopant.
  • the particular shift of the broadband response (the magnitude of the shift in response to a temperature change) is selected based on the desired application of the LCP films, for example in a window.
  • the LCP films can have a broadband response shift (a shift along the spectrum) of 50 to 600 nm, or 50 to 400 nm, or 100 to 600 nm, or 100 to 400 nm, or 200 to 400 nm.
  • the response can be measured, for example, using a full width at half maximum (FWHM).
  • the resulting LCP films can have an isotropic to nematic phase transition temperature of, for example, 60 to l00°C, such as 70 to 90°C.
  • an isotropic phase i.e., liquid phase
  • the LCP film has no orientational order.
  • the LCP film can maintain a nematic phase at room temperature.
  • the LCPs can exhibit long- range orientational order (i.e., the long axes of the LC monomers tend to align along a preferred direction), although the locally preferred direction can vary throughout the LCP film.
  • the temperature range over which the films can show a response can be varied.
  • a suitable range is from -15 to 70°C, or from -10 to 70°C, from 0 to 70°C or from 2 to 70°C.
  • the resulting LCP film can have a thickness of 1 to 100 micrometers (pm), or 5 to 80 pm, or 10 to 50 pm, or 25 to 35 pm, although other thicknesses can be made.
  • the LCP films can have a broadband response shift of 50 to 600 nm, or 50 to 400 nm, or 100 to 600 nm, or 100 to 400 nm, or 200 to 400 nm at a relative humidity of 60% to 95%, over a temperature range of 2°C to 70°C.
  • the LCP films can have a broadband response shift of 100 to 400 nm, or 200 to 400 nm at a relative humidity of 60% to 90%, over a temperature range of 2°C to 70°C.
  • the LCP film can be formed from more than one layer. This can be done by sequentially applying another primer layer to a first LCP film layer to abstract hydrogen atoms from the first liquid crystalline layer. After the solvent has evaporated, a second coating layer is applied, and then irradiated to form a second LCP film crystalline layer. In this way, multiple liquid crystalline layers can be built up.
  • This disclosure also relates to a layered article comprising a substrate and an LCP film disposed on the substrate, where the film is made using the methods described herein.
  • the primer layer as described herein a combination of a solvent and a Type II photoinitiator
  • only a residue of the primer layer e.g., residual solvent molecules, unreacted photoinitiator, photoinitiator products, or a combination thereof would be present in the layered article.
  • the LCP film is disposed directly on the substrate, such that they are in contact and no intervening layers (except any residue of the primer layer) are present between the substrate and the LCP film.
  • no additional layers of any type i.e., additional to the substrate, any residue of the primer layer, and the LCP film
  • no alignment layer is present between the substrate and the LCP film. Elimination of an alignment layer saves time and cost during manufacture of the layered articles.
  • additional layers can be present in the layered article, provided that they are not located between the substrate layer and the LCP film.
  • an additional layer can be disposed on a side of the substrate layer opposite the LCP film, or an additional layer can be disposed on a side of the LCP film opposite the substrate.
  • a protective or abrasion-resistant layer can be disposed on the LCP film, an adhesive layer can be disposed on the substrate, or both. Any combination of the additional layers can be present to provide the desired functionality.
  • the multilayer films can be used disposed on a glass plate or between glass plates. However, in an advantageous aspect, the multilayer article is not sandwiched between two glass plates, which can provide a manufacturing and weight savings.
  • the window can be for a vehicle, such as a car, truck, boat, or ship, or for a building of any type, and can be used with or without a frame or other window component.
  • the windows are especially useful for buildings such greenhouses.
  • UV-VIS Ultraviolet- visible light
  • PbS lead sulfide
  • PMT photomultiplier tube
  • SEM Scanning electron microscope
  • Example 1 Narrowband films.
  • This example describes the preparation and properties of a narrowband, temperature-responsive film on a PC substrate using a 10% benzophenone primer layer.
  • a general procedure for preparation of the LC films on a polycarbonate (PC) substrate is as follows. To prepare the coating solution, an LC mixture was heated to its isotropic state and stirred for several minutes. Next, the LC mixture was applied to the substrate and heated again until the mixture was in its isotropic state (to ensure homogeneity) and then cooled to the cholesteric phase. This heating step can optionally be omitted. The coating was applied with a gap applicator having a gap height of 15 pm at 20°C. The coating was photopolymerized by exposure for 300 seconds to an unfiltered spectrum of a collimated EXFO OMNICURE S2000 lamp with an intensity of 30 mW/cm 2 in the range 320-390 nm.
  • the fully polymerized film was treated with a 1M potassium hydroxide solution for approximately 7 minutes. Afterwards, the film was washed with water and dried at 60°C for 10 minutes.
  • PC substrates (5x5 cm 2 ) were treated at 40°C with 0.25 ml of a benzophenone - ethanol solution containing 10 wt% benzophenone.
  • the ethanol solvent was allowed to evaporate for 15 minutes at 40°C on a heating plate, to provide substrates for coating with liquid crystal compositions.
  • the coating composition was applied to the pre-treated PC plate as described above. After coating, polymerization, and subsequent base treatment, the film was fully wetted with water. After the base treatment, the coating does not delaminate from the substrate.
  • Temperature responsiveness of the layered article was investigated at 75% RH at different temperatures. As seen in FIG. 2A, the film shows a red shift of the reflection band upon cooling. At temperatures below 40°C the coating absorbed water and therefore shifted to higher wavelengths. At temperatures above 40°C almost no shift of the reflection band was observed. At approximately 5°C the coating did not absorb more water and therefore the maximum shift of the reflection band was approximately 211 nm which was less than the maximum shift when the coating was fully wetted. This can be explained by when the coating is fully wetted with water, water lays on top of the coating. This water is most likely absorbed easier by the coating than when the water has to penetrate from the air into the coating which leads to less water absorption and therefore a smaller shift.
  • Temperature responsiveness was also investigated at 30%, 45%, and 60% RH.
  • FIG. 2C shows that above 60% RH, a proper temperature response is present.
  • the maximum shift of the reflection band increases with increasing RH.
  • the substrate (10 x 7 cm 2 ) was treated at 40°C with approximately 1 ml of a solution of benzophenone and ethanol. The ethanol was allowed to evaporate for 15 minutes at 40°C.
  • the liquid crystal composition shown in Table 3 was coated onto the substrate. Before the coating was applied, the liquid crystal composition was heated to its isotropic state and stirred for several minutes. Next, the heated composition was applied onto the substrate with a bar coat with a gap height of 60 pm at 70°C.
  • the coating was cured through the substrate at 70°C for 15-20 minutes using ETV light with an intensity of 3 mW/cm 2 in the range 320-390 nm, followed by a 5 minutes post-cure through the substrate at 70°C using ETV-light with an intensity of 30 mW/cm 2 in the range 320 to 390 nm.
  • the film was washed with water and dried at 60°C for approximately 10 minutes.
  • FIG. 3 is an SEM cross-sectional image of the LCP film thus prepared.
  • the PC layer was removed during sample preparation, indicating poor adhesion to the substrate.
  • At the bottom of the image the surface formerly in contact the PC substrate, a severely distorted LCP region with inconsistent thickness can be seen.
  • crystals have formed at the surface of the coating cholesteric lines are visible and only in the middle of the film.
  • This example describes the preparation and properties of a broadband, temperature-responsive film on a copolycarbonate (BPA-DHBP) substrate using a 0.5 wt% benzophenone primer solution. The procedure described above was followed.
  • FIG. 5 is an SEM cross-sectional image of the LCP film of Example 4. In this image, the PC substrate is still attached to the coating (bottom of image). The cholesteric pitch gradient can be very well seen. As with the other examples, an intermediate LCP region in which the LC are not aligned can be seen between the functional LCP film and the copolymer substrate. This region can lead to haze.
  • Example 1 is illustrative of a coating that does not delaminate, but that is narrowband. But when generating broadband multilayers, a too-high photoinitiator concentration (10 wt% in the primer) generates severe misalignment of the LCP as shown in Example 2, FIG. 3. When a too-low concentration of photoinitiator (0.5 wt% in ethanol) are used, alignment is improved as shown in Example 3, FIG. 4.
  • a layered article comprising a copolymer substrate comprising a covalently linked Type II photoinitiator; and a temperature-responsive, cholesteric LCP film chemisorbed to a surface of the copolymer substrate, wherein the LCP film has a broadband response at a relative humidity of 60% to 95%.
  • Aspect 2 The layered article of aspect 1, wherein the shift of the broadband response is 50 to 600 nanometers, or 50 to 400 nanometers, or 100 to 400 nanometers, or 200 to 400 nanometers.
  • Aspect 3 The layered article of aspect 1 or aspect 2, wherein the LCP film is disposed directly on the copolymer substrate.
  • Aspect 4 The layered article of any one of aspects 1 to 3, comprising no additional layer disposed on a side of the film opposite the copolymer substrate, or no additional layer disposed on a side of the film opposite the copolymer substrate, or both.
  • Aspect 5 The layered article of any one of aspects 1 to 3, comprising an additional layer disposed on a side of the LCP film opposite the copolymer substrate, or an additional layer disposed on a side of the copolymer substrate opposite the liquid crystal polymer, or both.
  • Aspect 6 The layered article of any one of aspects 1 to 5, wherein a cholesteric pitch of the liquid crystal film is present as a gradient effective to widen the photonic reflection band, preferably wherein the gradient decreases in pitch in a direction away from the substrate e.
  • Aspect 7 The layered article of any one of aspects 1 to 6, wherein the liquid crystal film has a thickness of 1 to 100 micrometers, preferably 10 to 50 micrometers.
  • Aspect 8 A method of forming the layered article of any one of aspects 1 to 7, the method comprising: providing a copolymer substrate having opposed first and second sides, and comprising a Type II photoinitiator covalently linked to the polymer of the substrate;
  • a primer composition comprising 0.1 to 7 weight percent, preferably 0.1 to 2 weight percent of a Type II photoinitiator onto a first surface area of the first side of the copolymer substrate to form a primer layer; applying a coating composition comprising a liquid crystal monomer composition onto at least a portion of the primer layer under shear to provide an aligned coating layer; irradiating the aligned coating layer on the second side of the copolymer substrate and through the substrate to form a liquid crystalline polymer film on the substrate; and treating the liquid crystalline film with an aqueous base.
  • Aspect 9 The method of aspect 8, wherein applying the primer layer comprises printing, slot die coating, spraying, or dip coating the substrate with the primer composition; and applying the coating composition comprises using a doctor blade, printing, or a slot die coating.
  • Aspect 10 The method of any one of aspects 8 to 9, wherein the copolymer substrate comprises a copolycarbonate, preferably wherein the copolycarbonate comprises bisphenol A units and benzophenone units.
  • Aspect 11 The method of any one of aspects 8 to 10, wherein the Type II photoinitiator of the primer layer comprises a benzophenone, a thioxanthone, a xanthone, a quinone, or a combination thereof, preferably wherein the Type II photoinitiator of the primer layer is the same as Type II photoinitiator of the copolymer substrate.
  • Aspect 12 The method of any one of aspects 8 to 11, wherein the crystalline monomer composition comprises a bifunctional chiral liquid crystal monomer, a polyfunctional crosslinking liquid crystal monomer, and a carboxylic acid-containing monomer capable of dimerizing to a liquid crystal monomer.
  • Aspect 13 An article comprising the layered article of any one of aspects 1 to 12, preferably wherein the article is a window.
  • a window comprising: a frame; and a sheet supported by the frame, wherein the sheet comprises the layered article of any one of aspects 1 to 12.
  • compositions or processes as“consisting of’ and“consisting essentially of’ the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom.
  • Numerical values in this application reflect average values for a composition that may contain individual polymers of different characteristics. Unless indicated to the contrary, the numerical values include numerical values that are the same when reduced to the same number of significant figures and numerical values that differ from the stated value by less than the experimental error of conventional measurement technique of the type described herein to determine the value, or a tolerance in manufacture. All ranges disclosed herein are inclusive of the recited endpoint and are independently combinable (e.g., the range of“from 2 to 10 g, preferably 3 to 7 g” is inclusive of the endpoints, 2 g, 7 g, and 10 g, the ranges such as 3 to 10 g, and all the
  • cyclohexyl.“Aromatic” means a group having a ring system containing a delocalized conjugated pi system with a number of pi-electrons that obeys HiickeTs Rule.
  • the ring system can include heteroatoms such as N, P, S, Se, Si, or O, or only C and H.
  • Exemplary aromatic groups include phenyl, pyridyl, furanyl, thienyl, naphthyl, and biphenyl.
  • alkyl means a wholly unsaturated aliphatic group (except for any substitutions), and can be linear, branched, or cyclic.
  • “Amino” means a radical of the formula - NR.2, where each R is alkyl.“Halogen” means fluorine, chlorine, bromine, and iodine.“Alkoxy” means an alkyl group attached to an oxygen atom, i.e. -OCiTEn+i .
  • nitrile means a radical of the formula -CN, wherein the carbon atom is covalently bonded to another carbon- containing group.
  • “Substituted” means at least one hydrogen atom on the named group is substituted with another functional group, such as halogen, -OH, -CN, or -NO2.
  • An exemplary substituted alkyl group is hydroxyethyl. The number of carbon atoms is exclusive of any substituents.

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Abstract

L'invention concerne un substrat polymère comprenant un photoamorceur de type II lié par liaison covalente au copolymère du substrat ; et un film polymère cristal liquide cholestérique sensible à la pression, chimisorbé par une surface du substrat polymère, le film polymère cristal liquide présentant une réponse à large bande, pour une humidité relative de 60 % à 95 %.
PCT/IB2019/059634 2018-11-09 2019-11-08 Film sensible à la température, à humidité élevée, et fenêtre autorégulatrice faisant intervenir celui-ci WO2020095275A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100178508A1 (en) * 2006-06-27 2010-07-15 Sicpa Holding S.A. Cholesteric Multi-Layers
WO2013175448A1 (fr) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Compositions thermoplastiques ignifugeantes, leurs procédés de fabrication et articles les contenant
WO2014072923A1 (fr) 2012-11-07 2014-05-15 Sabic Innovative Plastics Ip B.V. Procédé pour la production de compositions de polycarbonate
US20140295363A1 (en) 2011-10-08 2014-10-02 Sabic Innovative Plastics Ip B.V. Plastic flame housing and method of making the same
WO2015193862A1 (fr) 2014-06-20 2015-12-23 Sabic Global Technologies B.V. Résines de polycarbonate réticulables
US20160272890A1 (en) * 2013-11-08 2016-09-22 Sicpa Holding Sa Composite marking based on chiral liquid crystal precursors and modifying resins
US20170275534A1 (en) * 2014-09-30 2017-09-28 Transitions Optical, Inc. Ultraviolet light absorbers
WO2018122719A1 (fr) 2016-12-27 2018-07-05 Sabic Global Technologies B.V. Procédés de greffage de revêtements cristallins liquides sur des surfaces polymères

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100178508A1 (en) * 2006-06-27 2010-07-15 Sicpa Holding S.A. Cholesteric Multi-Layers
US20140295363A1 (en) 2011-10-08 2014-10-02 Sabic Innovative Plastics Ip B.V. Plastic flame housing and method of making the same
WO2013175448A1 (fr) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Compositions thermoplastiques ignifugeantes, leurs procédés de fabrication et articles les contenant
WO2014072923A1 (fr) 2012-11-07 2014-05-15 Sabic Innovative Plastics Ip B.V. Procédé pour la production de compositions de polycarbonate
US20160272890A1 (en) * 2013-11-08 2016-09-22 Sicpa Holding Sa Composite marking based on chiral liquid crystal precursors and modifying resins
WO2015193862A1 (fr) 2014-06-20 2015-12-23 Sabic Global Technologies B.V. Résines de polycarbonate réticulables
US20170275534A1 (en) * 2014-09-30 2017-09-28 Transitions Optical, Inc. Ultraviolet light absorbers
WO2018122719A1 (fr) 2016-12-27 2018-07-05 Sabic Global Technologies B.V. Procédés de greffage de revêtements cristallins liquides sur des surfaces polymères

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