WO2020002339A1 - Microlentilles ajustables - Google Patents

Microlentilles ajustables Download PDF

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Publication number
WO2020002339A1
WO2020002339A1 PCT/EP2019/066850 EP2019066850W WO2020002339A1 WO 2020002339 A1 WO2020002339 A1 WO 2020002339A1 EP 2019066850 W EP2019066850 W EP 2019066850W WO 2020002339 A1 WO2020002339 A1 WO 2020002339A1
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WO
WIPO (PCT)
Prior art keywords
group
chain
microlens
cfz
polymer
Prior art date
Application number
PCT/EP2019/066850
Other languages
English (en)
Inventor
Ugo De Patto
Rosaldo Picozzi
Original Assignee
Solvay Specialty Polymers Italy S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Specialty Polymers Italy S.P.A. filed Critical Solvay Specialty Polymers Italy S.P.A.
Publication of WO2020002339A1 publication Critical patent/WO2020002339A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/12—Fluid-filled or evacuated lenses
    • G02B3/14—Fluid-filled or evacuated lenses of variable focal length

Definitions

  • the present invention relates to the field of micro-optics. More specifically the invention relates to tunable, fluid-filled membrane microlenses.
  • micro-optical components have been developed that have opened the way to a number of important applications. Crucial for most of these applications is the tunability of the micro-optical components, that means a controlled variation in their optical characteristics. The more precise and reproducible is the tunability, the higher is the functionality of the micro-optic components.
  • tunable micro-optics one of the most promising technology is that of tunable microlenses, available as individual lenses or arranged in arrays and used in many applications where a very precise and efficient focus of the light is required, or other peculiar optical features such as in the 3D imaging systems.
  • Tunable microlenses are generally manufactured by using a distensible elastomer membrane leaning over a sealed, micromachined cavity filled with a liquid or fluid component.
  • the highly elastic membranes of poly(dimethylsiloxane) (PDMS) are widely used in these microlenses. These membranes define the surface shape of the lens, while the filled-in liquid does constitute the lens’ body and allows the optical properties of the lens, such as its focal length, to be tuned by variation in the pressure of the liquid through microfluidic channels, or by variation of other physical parameters in the liquid.
  • the filled-in liquid or fluid must have a refractive index as close as possible to that of the membrane’s material, in order to reduce scattering of light at their interface.
  • the liquid or fluid material has to be compatible with the membrane’s material too, and have for instance a low permeability through the membrane.
  • silicone oils cannot be used to fill a microlens with a PDMS membrane because they tend to leak from the surface of the lens through the membrane (see Friese C. et al., Transactions on electrical and electronic engineering, IEEJ Trans 2007; 2: 232-248).
  • EP 2465816 (Samsung Electronics Co., Ltd) discloses a varifocal lens structure including a frame having a fluid chamber filled with an optical fluid and formed of polymethylsiloxane (PDMS) containing a predetermined fluid; a transparent cover disposed on a top surface of the frame so as to cover the fluid chamber; a transparent elastic membrane disposed on a bottom surface of the frame so as to form a lower wall of the fluid chamber; and an actuator disposed on the elastic membrane.
  • PDMS polymethylsiloxane
  • US 2003/181633 discloses an energy curable composition
  • a compound having an aromatic or heteroaromatic moiety at least two fluorinated alkylenen, arylene or polyether moieties, at least one ethylenically unsaturated moiety.
  • EP 1057849 discloses the use of a composition for preparing by radical route polymeric films having refractive index lower than 1.400.
  • PFPEs Perfluoropolyethers
  • PFPEs are fluids with high transparency in the visible and UV regions of the light spectrum, also having an extremely high compatibility with all materials.
  • PFPEs have a low refractive index, which is lower than that of PDMS or of other possible materials used as elastic membrane in microlenses.
  • a high refraction index for an optical fluid of a microlens is also a desirable property in order to maximize the tuning range of the focal length of a microlens for a given ability to vary the lens radius of curvature. This also reduces the amount of spherical aberration for a given focal length.
  • the Applicant has now surprisingly found that by properly functionalizing the PFPEs with aromatic moieties as detailed below, the refractive index of PFPEs is increased, while maintaining a good compatibility with PDMS and other similar materials used as membranes for microlenses, also maintaining other beneficial optical properties of the PFPEs such as high transparency.
  • a subject of the present invention is therefore a microlens comprising an elastomer membrane filled with a (per)fluoropolyether polymer [polymer (PFPE)] comprising a (per)fluoropolyether backbone chain [chain (R f )], optionally comprising pendant groups, and comprising two chain ends, wherein at least one aromatic group [group (Ar F )] is comprised in the polymer (PFPE) in at least one chain end and/or in pendant groups of chain (R f ).
  • PFPE polymer
  • R f backbone chain
  • Ar F aromatic group
  • a further subject of the invention is a process for the manufacture of the microlens as defined above.
  • the invention relates to a microlenses array comprising a plurality of microlenses as defined above arranged on a supporting substrate.
  • microlenses means that they are able to be adjusted in their focal length by variation of one or more parameters.
  • PFPE “(per)fluoropolyether”, i.e. fully or partially fluorinated polyether, i.e. wherein all or only a part of the hydrogen atoms of the hydrocarbon structure have been replaced by fluorine atoms so that a higher proportion of fluorine atoms than hydrogen atoms is contained in the structure.
  • PFPEs “(per)fluoropolyether”
  • perfluorinated denotes herein a fully fluorinated straight or branched alkyl group.
  • parentheses before and after names of compounds, symbols or numbers identifying formulae or parts of formulae like, for example“group (Ar F )”,“chain (R f )”, etc..., has the mere purpose of better distinguishing those names, symbols or numbers from the rest of the text; thus, said parentheses could also be omitted.
  • the elastomer membrane component of the present microlenses can be selected from among silicon elastomer membranes, and preferably is a polydimethylsiloxane (PDMS) membrane.
  • PDMS polydimethylsiloxane
  • Other elastomer components having good compatibility with the polymer PFPE of this invention can be selected by any person of ordinary skills in the art.
  • the choice of the aromatic group [group (Ar F )], comprised in the polymer (PFPE), is not particularly limited, provided that this group is aromatic.
  • aromatic group is hereby intended to denote a cyclic substituent having a delocalized conjugated p system with a number of p delocalized electrons fulfilling the Hiickel's rule (number of p electrons equal to
  • the group (Ar F ) can be monocyclic or polycyclic. It can comprise one or more than one aromatic ring. Should it comprise more than one aromatic ring, these aromatic rings can be condensed or not condensed.
  • the group (Ar F ) can be a heteroaromatic compound, comprising one or more heteroatoms (e.g. O, S, N) in the ring. It can be substituted or not substituted. It may be fully or partially fluorinated or fully hydrogenated.
  • the group (Ar F ) is perfluorinated, that is to say, all its free valences are saturated with fluorine atoms.
  • group (Ar F ) which are suitable to the purposes of the invention are notably perfluorobenzene group, perfluorobiphenyl groups, perfluoronaphthalene groups, perfluoroanthracene groups, perfluoropyridine groups, perfluorotoluene groups and derivatives thereof comprising one or more perfluorinated substituent(s).
  • the group (Ar F ) is a perfluorobenzene group.
  • group (Ar F ) is an aromatic group substituted by one or more substituents comprising an aromatic moiety.
  • the (per)fluoropolyether chain [chain (R f )] of polymer (PFPE) is preferably a chain comprising a plurality of recurring units (Ri), said recurring units having general formula: -(CF 2 ) k -CFZ-0-, wherein k is an integer of from 0 to 3; Z is selected from a fluorine atom, a C1-C6 peril uoro(oxy)alkyl group or a group W-(Ar F ), wherein W is a divalent linking group that provides a link between the recurring unit (Ri) and the group (Ar F ).
  • the divalent linking group W may comprise a (per)fluoroalkylene chain, an ether group, a thioether group, an amide group, a carbonyl group, a carboxylic group, a phosphate group or combinations thereof.
  • the chain (R f ) of the polymer (PFPE) complies with formula:
  • Z is a fluorine atom.
  • the chain (R f ) is preferably selected so as to possess a number averaged molecular weight ranging from 400 to 2,000 Daltons.
  • the chain ends of polymer (PFPE), equal to or different from each other, are selected from:
  • Ci-C 6 peril uoroalkyl group optionally substituted with at least one halogen atom, -CFZ H2OH, -CFZ * COOR h and -CFZ * -CH 2 (OCH 2 CH 2 ) p -OH, wherein p is an integer ranging from 0 to 10; Z * is F or CF3; R h is a hydrocarbon chain; and
  • the divalent linking group Y may comprise a (per)fluoroalkylene chain, a a polyalkylene oxide chain, a carboxylic group an amide group, an alkylene group (Ak), a ether group, a thioether group or combinations thereof.
  • Suitable divalent linking groups Y are, notably, groups of formula: -CFZ FhO-, - CFZ H2OCH2CH2O-, -CFZ * CH 2 0C(0)0CH 2 -, -CFZ * C(0)NH- and CFZ * CH 2 0C(0)NH-, wherein Z * is as above defined.
  • the linking group Y is a group of formula -CFZ * -CH 2 (0CH 2 CH 2 ) k -0-, wherein k’ is an integer ranging from 0 to 10 and Z * is F or CF3.
  • PFPE present polymer
  • R f is a chain (R f ), as above detailed;
  • each of T and T equal to or different from each other, are chain ends as above defined,
  • R f , T and T bears a group (Ar F ).
  • T and T’ are -Y- (Ar F ) groups.
  • the polymer (PFPE) of this invention preferably complies with the following formula:
  • the polymer (PFPE) of this invention more preferably complies with the following formula:
  • - T and T’ are a group -Y-(Ar F ), wherein (Ar F ) is as above defined; Y is as above defined.
  • the Applicant has found that, in the polymer (PFPE) of this invention, the number of aromatic groups (Ar F ) as well as the length of the (per)fluoropolyether chain (R f ) influence the refractive index of the fluid, thus allowing tuning the refractive index parameter of the polymer according to specific needs of the microlenses applications by simply varying the number of aromatic moieties and the length of the PFPE chain. As shown in the following experimental part, the Applicant has found that it is possible to modulate the PFPEs with aromatic moieties of the invention by increasing this parameter from the 1.30 value of the non-derivatized PFPEs to 1.40 and above.
  • the present PFPEs with pendant and/or end aromatic groups show very good compatibility with elastomer membranes, such as PDMS membranes, commonly used for manufacturing microlenses.
  • elastomer membranes such as PDMS membranes
  • the microlenses of the present invention can be manufactured with the components as defined above, the elastomer membrane and the PFPE with aromatic moieties, by means of one of the known microfabrication technologies for this kind of optical components.
  • the present microlenses can be manufactured by using the elastomer membranes suspended over a sealed, micromachined microfluidic cavity, which is then filled with the PFPE fluid as defined above as the optical fluid. Once enclosed in the elastomer inner chamber formed by the membrane, the PFPE fluid will act as the lens body, while the membrane will provide the shape and the curvature to the lens.
  • the membrane of the present microlens may be structured on a silicon fluidic chip, mounted on a glass substrate, thus forming a fluidic cavity where the polymer PFPE is collected.
  • a tuning of the so-formed microlens and a variation of the lens’ curvature and thus of its focal length can be for instance achieved by varying the pressure of the liquid using the microfluidic channel, or by other known systems.
  • the present tunable microlenses filled with PFPEs having aromatic moieties can be used as individual lenses or they can be arranged in arrays.
  • Hexafluorobenzene (O Q R Q ), benzyl alcohol and isobutanol were purchased from Sigma-Aldrich and used as such.
  • Hexafluoroxylene (HFX) solvent was purchased from Miteni S.p.A. (Italy).
  • Measurement of refractive index the measurements were done using an ABBE B (Zeiss) instrument, at room temperature, following the standard procedure ASTM D 1747/62.
  • the compatibility tests were done using a cross-linked PDMS membrane with thickness of about 200 microns.
  • a weighed piece of material (about 100 mg) was immersed in about 50 ml of the present polymer PFPE and let stand at room temperature for 15 days. Afterwards, the material was removed from the fluid, gently dried on the surface with a piece of paper and weighed. The swelling data were expressed as weight % variation compared with the starting weight of the material.
  • Example 1 Synthesis of the a,w-di-pentafiuorophenyi derivative of the PFPE a,w-diol (!) identified above
  • 150 g (305 meq) of the PFPE diol (I) were loaded together with 62.5 g of O Q R Q (336 mmol) and 150 g of HFX solvent.
  • 22.1 g of KOH were added and the mixture was heated at 85°C for 5 hours; afterwards further 2.2 g of KOH were added and the mixture was heated for additional 5 hours at 80°C.
  • Example 2 Synthesis of the a,oj-di-(p-phenoxytetrafluorophenyl) derivative of the PFPE a,w-dioi (I) identified above
  • a swelling expressed as weight percentage variation lower than 1 % in the compatibility test described above does prove how the very good compatibility of the non-derivatized PFPEs with PDMS is maintained in the present PFPEs with aromatic moieties.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne une microlentille ajustable comprenant une membrane de silicone remplie de fluide, le fluide étant un (per) fluoropolyéther portant des fractions aromatiques.
PCT/EP2019/066850 2018-06-27 2019-06-25 Microlentilles ajustables WO2020002339A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18180049.1 2018-06-27
EP18180049 2018-06-27

Publications (1)

Publication Number Publication Date
WO2020002339A1 true WO2020002339A1 (fr) 2020-01-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/066850 WO2020002339A1 (fr) 2018-06-27 2019-06-25 Microlentilles ajustables

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TW (1) TW202012492A (fr)
WO (1) WO2020002339A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957994A (zh) * 2021-02-25 2022-08-30 奥普托图尼股份公司 用于可调光学装置的液体
WO2024035667A1 (fr) * 2022-08-12 2024-02-15 Corning Incorporated Dérivés polyfluoroaromatiques pour lentilles liquides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057849A2 (fr) 1999-06-03 2000-12-06 Ausimont S.p.A. Compositons pour films ayant un faible indice de réfraction
US20030181633A1 (en) 2002-02-04 2003-09-25 Robert Blomquist Halogenated optical polymer composition
US7256943B1 (en) 2006-08-24 2007-08-14 Teledyne Licensing, Llc Variable focus liquid-filled lens using polyphenyl ethers
EP2465816A1 (fr) 2010-12-16 2012-06-20 Samsung Electronics Co., Ltd Structure de lentille progressive et son procédé de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057849A2 (fr) 1999-06-03 2000-12-06 Ausimont S.p.A. Compositons pour films ayant un faible indice de réfraction
US20030181633A1 (en) 2002-02-04 2003-09-25 Robert Blomquist Halogenated optical polymer composition
US7256943B1 (en) 2006-08-24 2007-08-14 Teledyne Licensing, Llc Variable focus liquid-filled lens using polyphenyl ethers
EP2465816A1 (fr) 2010-12-16 2012-06-20 Samsung Electronics Co., Ltd Structure de lentille progressive et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FRIESE C. ET AL.: "Transactions on electrical and electronic engineering", /EEJ TRANS, vol. 2, 2007, pages 232 - 248

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957994A (zh) * 2021-02-25 2022-08-30 奥普托图尼股份公司 用于可调光学装置的液体
WO2024035667A1 (fr) * 2022-08-12 2024-02-15 Corning Incorporated Dérivés polyfluoroaromatiques pour lentilles liquides

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TW202012492A (zh) 2020-04-01

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