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WO1995000588A1 - Compositions de fluoropolymeres reticulables - Google Patents

Compositions de fluoropolymeres reticulables Download PDF

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Publication number
WO1995000588A1
WO1995000588A1 PCT/US1994/006783 US9406783W WO9500588A1 WO 1995000588 A1 WO1995000588 A1 WO 1995000588A1 US 9406783 W US9406783 W US 9406783W WO 9500588 A1 WO9500588 A1 WO 9500588A1
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WO
WIPO (PCT)
Prior art keywords
crosslinking
group
polymeric component
composition
acid
Prior art date
Application number
PCT/US1994/006783
Other languages
English (en)
Inventor
Shaul M. Aharoni
Original Assignee
Alliedsignal Inc.
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 Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to AU70614/94A priority Critical patent/AU7061494A/en
Publication of WO1995000588A1 publication Critical patent/WO1995000588A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • G02B1/105—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • This invention provides self-crosslinking fluoropolymer compositions suitable for making coatings such as protective coatings, release coatings, optical coatings; for use as an adjuvant for other polymeric compositions; and for encapsulating applications.
  • the present invention provides two-component (or multi- component) compositions of fluorinated polymers, which components each carry different active groups which are capable of forming crosslinks without use of crosslinking agents.
  • the individual components can be made under free-radical polymerization conditions. These components are mixed in desired proportions to obtain crosslinkable compositions, which can be cured, as by application of heat.
  • the cross-linked compositions are amorphous, optically clear, and have low refractive indexes.
  • novel crosslinkable fluoropolymer compositions comprising a first polymeric component A, and a second polymeric component B, each having the general formula
  • Y is a -(CH 2 ) q -R F group, wherein (a) -(CH 2 ) q - may be straight chain or branched, and q is an integer of from 1 to about 18; (b) -R f is a fluoroalkyl group, straight chain or branched, having from 1 to about 40 carbon atoms, and having at least one terminal -CF 2 X group wherein X is H or F; and
  • Z is a crosslinking group selected from the group consisting of -COOH, -COO-(CH 2 CH 2 -0) m -CH 2 -FM and -COO- (CH 2 ) m -F , wherein m is an integer of from 1 to about 18, and -COOH and FM are terminal functional moieties wherein FM is -NH 2# -NHR 3 or -CH—CH 2 , and wherein R* 3 has the meaning given below; (6) R 1 and R 2 are independently selected from the group consisting of (a) H;
  • R 1 when (t + v) is 0, R 1 must provide the crosslinking group Z;
  • the crosslinking group Z may only contain one type of terminal functional moiety -COOH, -NH 2 . -NHR 3 or -CH—CH 2 ;
  • first polymeric component A and second polymeric component B provide their respective terminal functional moiety -COOH, -NH 2 ,-NHR 3 or -CH—CH 2 in molar ratio of from about 1:2 to about 2:1.
  • the polymeric components of the compositions of this invention generally are copolymers.
  • copolymer is intended to refer to a polymer derived from at least two or more different monomer units.
  • monomer units which may be incorporated into these polymeric components; their number is limited only by the usual practical limitations imposed by polymerization process considerations, and the desire to obtain polymer products having useful properties.
  • the individual polymeric components can be prepared by polymerizing appropriate monomers, suitably in solution " in tetrahydrofuran ("THF") or glacial acetic acid, at elevated temperature with a free-radical generating initiator, using conventional procedures. They may also be polymerized in suspension or dispersion, such as an aqueous suspension or dispersion. The resultant polymer component can be recovered from the polymerization medium in conventional manner.
  • THF tetrahydrofuran
  • glacial acetic acid acetic acid
  • Blending may be accomplished in liquid media by mixing their solutions, suspensions or dispersions; by mixing their melts; or by dry-blending, typically in dry powder form.
  • the crosslinking fluoropolymer compositions are characterized in that they are mixtures of at least two polymeric components, each of which provides one type of active moiety for crosslinking, which, by reacting with each other, form desired crosslinks.
  • the active moieties are (a) carboxyl groups, (b) epoxy groups; and (c) amino groups. Each of these groups may react with each of the others, i.e. carboxyl groups react with amino groups; amino groups react with epoxy groups; and epoxy groups react with carboxyl groups. Each of these reactions provide desired crosslinks.
  • the polymeric components are stable. Mixed with each other, polymeric components carrying different active moieties will crosslink.
  • each of the individual components of the crosslinkable fluoropolymer compositions contain only one type of crosslinking group, i.e. either carboxyl, amino or epoxy groups. While two components each carrying a different type of crosslinking moieties are required for the compositions of this invention, it is also possible to mix and crosslink three components, the first providing carboxyl groups, the second providing amino groups, and third epoxy groups.
  • the appended claims are intended to cover such three-component compositions.
  • the present compositions can be crosslinked by heat treatment without the use of crosslinking agents.
  • Crosslinking proceeds readily at temperatures in the range of from about 75°C to about 180°C, within time periods of from about 5 minutes to about 4 hours. Degree of crosslinking can be varied and controlled by choice of crosslinking time and temperature. Ordinarily, crosslinking will be carried out after the fluoropolymer composition has been fabricated into desired form, such as a coating, a film, an encapsulation, and the like.
  • Heat-induced crosslinking has the advantage that no crosslinking agent is required, so that no impurities are introduced; the cured polymer is a single component without residual solvent, monomer or crosslinking agents.
  • Such crosslinking improves hardness, scratch resistance and adhesion of the polymer film, without change in refractive index, and without deleterious effect on any other desirable property. Of course, crosslinking drastically reduces solubility in solvents.
  • the crosslinking fluoropolymer compositions are soluble (before crosslinking) at concentrations of over 2 wt./vol.% in mixtures of from 1:2 to 2:1 of THF and 1,3-bis(trifluoromethyl)benzene (hexafluoroxylene - HFX) ; in 3M Company's Fluorinert FC-75 solvent; in trichlorotrifluoroethane (TCTFE); in mixtures of Fluorinert FC-75 with TCTFE; and in mixtures of TCTFE with HFX.
  • aqueous dispersions and suspension as may be obtained from polymerization in aqueous media, or from polymerization mixtures based on glacial acetic acid as polarization medium - coatings can be applied to any suitable substrate, and films can be cast. Following evaporation of the liquid medium, the fluoropolymer composition may be cured by crosslinking, as above described.
  • crosslinking fluoropolymer compositions are suitable for making coatings such as optical coatings, anti-static coatings, and release coatings; for encapsulation of electrical and optical devices and components; and for similar applications.
  • coatings such as optical coatings, anti-static coatings, and release coatings; for encapsulation of electrical and optical devices and components; and for similar applications.
  • they can be compression molded at temperature in the order of 75°C to about 110°C before crosslinking sets in, and then crosslinked at higher temperatures in the order of above about 120°C, say between about 125°C to about 180°C. Selection of appropriate molding and curing (crosslinking) temperatures is within the ordinary skill of the art.
  • the starting materials (monomers) for making the individual polymeric components (polymeric component A and polymeric component B) for the fluoropolymer compositions of the present invention are known compounds. Some are commercially available; the others can be made using conventional procedures.
  • fluorine-containing units (the units bearing the Y group) wherein r is 0 are based on the corresponding fluorine-containing acrylate or methacrylate monomers; when r is 1, the fluorine containing units are based on the monoesters and/or the diesters of itaconic acid; and when v is greater than 0, the composition will contain fluorine-containing units based on monoesters and/or diesters of fumaric acid and/or maleic acid.
  • fluorine-containing acrylates or methacrylates are commercially available, as mixtures of homologues having perfluoroalkyl groups of varying chain length. Out of these, one could separate individual compounds of defined perfluoroalkyl chain length, if desired for any reason, but this is ordinarily not necessary.
  • fluorinated monomers include products sold by DuPont under its "Zonyl” trademark, e.g. Zonyl TM (methacrylate) and Zonyl TA-N (acrylate) , and sold by Hoechst-Celanese under its "NUVA-HF” and "Fluowet MAE” trademarks.
  • Zonyl e.g. Zonyl TM (methacrylate) and Zonyl TA-N (acrylate)
  • Hoechst-Celanese under its "NUVA-HF” and "Fluowet MAE” trademarks.
  • Such specific examples include mixed perfluroalkylethylene acrylates and methacrylates wherein n is predominantly an even number, and in particular wherein the perfluoroalkyl group is represented by a mixture of C 4 through C 2 o groups, particularly C ⁇ , C 8 , Cio and C i2 groups.
  • non-fluorinated monomers for the polymeric components are derived from acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid, and their esters (including the diesters of itaconic, fumaric and maleic acid), or mixtures thereof. All of these are either commercially available, or readily prepared by those skilled in the art using known procedures.
  • Polymerization of the monomers to make the individual polymeric components for the crosslinking fluoropolymer compositions proceeds readily in solution in THF or glacial acetic acid, at elevated temperature within the range of from about 35°C to the boiling point of the polymerization mixture, more desirably within the range of from about 45°C to the atmospheric pressure boiling point of the solvent, about 65°C for THF and about 110°C for glacial acetic acid, under autogenous pressure, typically atmospheric pressure, using a free radical generating initiator, such as 2,2 '-azobis (2-methylpropanenitrile) (CAS #78-67-1) available from DuPont under the designation VAZO 64 ("AIBN”) .
  • a free radical generating initiator such as 2,2 '-azobis (2-methylpropanenitrile) (CAS #78-67-1) available from DuPont under the designation VAZO 64 ("AIBN") .
  • Suitable initiators include dimethyl-2,2'azobis (isobutyrate) PMAIB") , 2,2'-azobis(2,4-dimethylpentanenitrile) (CAS # 4419-11-8) and 2,2 '-azobis (2-methylbutanenitrile) (CAS # 13472-08-7) .
  • the AIBN and MAIB are preferred.
  • the catalyst is employed in amount of from about 0.15 to about 0.4 wt.%, based on the combined weight of all the monomers to be polymerized. Desirably, polymerization is conducted under agitation. Typical polymerization times range from about 4 hours to about 8 hours.
  • the monomer concentration in the reaction medium typically ranges from about 35 to about 70 percent by weight, based on the combined weight of reaction medium (THF or glacial acetic acid) and the monomers.
  • the polymer product is readily recovered from the reaction mixture, as by evaporation of the solvent and/or cooling the mixture to precipitate the polymer product, followed by separation of liquid and solid phases, as by filtration, and washing of the polymer product to remove residual unreacted monomers using any suitable solvent, if desired. These operation are conventional.
  • Example 1 Preparation of fluorinated mono-itaconate: Perfluoroalkylethanol mixture (DuPont' s Zonyl BA TM) was dissolved in tetrahydrofuran (THF) with slight warming. To this, a solution of itaconyl chloride (Aldrich, CAS # 1931-60-8) was added to reach equimolarity. followed by. dropwise addition of pyridine. Under constant stirring the reaction was permitted to proceed at temperature below about 60°C for time period of up to 24 hours. The solvent was then stripped by evaporation, and the residue was washed with water to remove the pyridine.HC1 by-product, and to hydrolyze any unreacted acid chloride. The monomer was then washed with methanol remove as much as possible of the unreacted perfluoroalkylethanol. The resultant desired itaconic acid monoester was dried in vacua at room temperature.
  • fluorinated monofumarate is carried out in analogous fashion, starting with fumaryl chloride (Aldrich, CAS # 627-63-4) .
  • the preparation of fluorinated monomalonate is carried out using maleic anhydride in perfluoroalkylethanol in the presence of catalytic amounts of strong inorganic acid. All of these involve conventional reaction mechanisms.
  • Unfluorinated itaconic acid monoesters can be prepared in similar fashion from appropriate alcohols following the procedure of Cowie et al., Brit. Polymer J. 9, 241 (1977). Monoesters of fumaric acid are commercially available; the monoesters of maleic acid are conveniently made reacting maleic anhydride with the desired alcohol. Epoxy terminated itaconates can be prepared under basic conditions from glycidol and itaconyl chloride, in the manner shown in Example 1. In similar fashion, epoxy terminated fumarates and maleates can be prepared by the reaction of glycidol with fumaryl chloride or maleic anhydride, respectively.
  • Amine-terminated itaconates, fumarates, maleates, acrylates or methacrylates may be prepared in three steps from the corresponding acid chloride and an appropriate aliphatic ⁇ , ⁇ -hydroxy acid.
  • the unsaturated acid chloride is reacted in solution in the presence of pyridine with an excess of the hydroxy acid (Schotten-Baumann reaction) , at room temperature or below.
  • the acid chloride reacts with the hydroxy group to form an ester of the unsaturated acid in which the substituent carries a terminal carboxylic acid group.
  • the terminal carboxylic acid group is converted to the acid chloride by treatment with thionyl chloride, in known manner.
  • the acid chloride group is then converted into the amine group via Curtius rearrangement using first sodium azide (c.f., e.g. Macromolecules 12, 94 (1979) and references there cited) , followed by thermal rearrangement and treatment with water to convert the isocyanate intermediate to the desired amine product.
  • first sodium azide c.f., e.g. Macromolecules 12, 94 (1979) and references there cited
  • Sterically hindered secondary amines (those providing the -NHR 3 group) whose reactivity is sufficient to react with epoxy groups but not with carboxy groups, are easier to prepare.
  • the acid chloride derivatives of acrylic, metharcylic, itaconic, maleic or fumaric acid are reacted in a solvent containing excess pyridine under Schotten-Baumann conditions with an appropriate secondary-amino alcohol, for example 2 (tert-butylamino)ethanol. Under these conditions, the hydroxy group reacts with the acid cloride group to form the desired ester of the secondary amine.
  • the amine-terminated esters of the unsaturated acid are copolymerized into the copolymer chain of the polymer component via free radical initiated addition polymerization of the unsaturated double bonds provided by the initial unsaturated acid.
  • Polymerization of the mono- and di-esters of itaconic, fumaric or maleic acid to obtain the polymeric components based thereon also employs conventional methods.
  • the polymerization may be carried out in glacial acetic acid or in THF.
  • the preferred solvent for the reaction is glacial acetic acid (occasionally trichlorotrifluoro ethane can be used instead) .
  • THF is the solvent of choice.
  • the monomer to solvent ratio is approximately in the range of 1:4 weight/volume to 2:1 weight/volume, depending on the viscosity of the system.
  • a free radical generating initiator such as AIBN or MAIB, is added, and the polymerization is carried out over a period of time, generally up to about 12 hours, at temperatures in the order of about 60°C to 65°C (for THF solvent) or 80°C to 85°C (for glacial acetic acid) . Work-up is as above described.
  • Example 7 Preparation of terpolymer with t>0 and v>0: Eighty wt .% of perfluoroalkylethylene methacrylate (Zonyl- TM) is mixed with 10 wt.% glycidylmethacrylate from which the inhibitor has been removed, and 10 wt . % diethylfumarate in 1:1 vol./wt. amount of THF.
  • Zonyl- TM perfluoroalkylethylene methacrylate
  • the mixture With constant stirring, the mixture is heated to dissolve reactants and purged with nitrogen for about 2 hours at temperatures below about 50°C, followed by addition of 0.3 wt.% MAIB free radical initiator. Under continued nitrogen purge, the temperature is raised to 60°C - 65°C and the polymerization is permitted to continue for about 8 hours. Thereafter, the THF is removed by evaporation, solids are washed, first with water, then with water/methanol, and the washed solids are dried under dynamic vacuum at temperature lower than about 50°C.
  • Polymeric component B was a copolymer of 90 wt.% of DuPont's Zonyl TM and 10 wt.% of methacrylic acid. Solutions of components A and B in 1:1 THF/hexafluoroxylene (THF/HFX) were mixed in about 1:1 molar ratio. The mixture was allowed to dry, and the dried mixture was heated. After 90 min. at 120°C some crosslinking occurred. A separate sample was heated at 150°C, and more crosslinking occurred. The crosslinked system swelled in boiling 1:1 THF/HFX, but did not dissolve. The material strongly adhered to an aluminum surface. In general, the THF/HFX mixture is a good solvent for the crosslinkable fluoropolymer compositions.
  • solvents and solvent mixtures can be employed, so long as both polymeric components are soluble in the solvent. Often, this means that, for any given pair of polymeric components, the ratio of fluorinated to non-fluorinated groups should be close, more or less.
  • polymers based on less than about 5 wt.% of non-fluorinated monomers dissolve very well in Fluorinert FC-75 alone, in TCTFE alone, or in mixtures thereof.
  • Polymeric components based on about 8 or more wt.% of non-fluorinated monomers are generally very soluble in THF/HFX mixtures.
  • the optimum ratio of THF:HFX is a function of the composition of the polymeric components: the higher the weight fraction of non-fluorinated monomer, the higher the amount of THF.
  • Useful proportions in general range about 1:2 THF/HFX to about 2:1 THF/HFX.
  • TCTFE/HFX is an excellent solvent mixture.
  • the fluoropolymer compositions can also be crosslinked employing conventional crosslinking agents, such as, for example, diisocyanates, carbodiimides, diacid chlorides, diepoxides and the like.
  • conventional crosslinking agents such as, for example, diisocyanates, carbodiimides, diacid chlorides, diepoxides and the like.
  • specific effective crosslinking agents include hexamethylenediisocyanate, methylene di-p-phenyldiisocyanate, 1,3-dicyclohexyl carbodiimide, dodecanedioyl dichloride, adipoyl chloride and diglycidyl of bisphenol A.
  • the crosslinking agents are used in amounts conventionally employed to obtain desired crosslinking of the polymer which, by use of such agents, can take place at ambient temperatures.
  • the Y units are preferably straight chain; the q in the Y units preferably is an integer of from 1 - 12, more preferably from 1 - 8, and most preferably from 1 - 2.
  • the R F in the Y units preferably contains from 1 - 36, more preferably from 2 - 24, and most preferably from 4 - 20 carbon atoms. If the composition is to be used for optical purposes, then R F preferably represents a mixture of units of straight and branched chains, to decrease the refractive index and to increase amorphicity.
  • the terminal -CF 2 X group in R F is peferably a -CF 3 group.
  • crossslinking Z groups the epoxy- amine combination is most preferred, followed by the epoxy- carboxyl combination and the carboxyl-amine combination, in that order.
  • mixtures of three polymeric components, each providing a different type of crosslinking group Z, are crosslinkable in accordance with the present invention and are intended to be covered by the appended claims.
  • m is preferably an integer of from 1 - 8, more preferably from 1 - 4, and most preferably from 1 - 2.
  • the molar ratio of terminal functional moieties in first and second polymeric components A and B is ideally 1:1, may range from about 1:2 to about 2:1; is preferably from about 1:1.5 to about 1.5:1; and more preferably yet within the range of from about 1.2:1 to about 1:1.2.
  • the R3 units are preferably linear alkyl groups.
  • the preferred carbon content of the R 3 groups ranges from 1 to about 12, more preferably from 1 to about 8, and most preferred from 1 to about 4.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention se rapporte à des compositions de fluoropolymères à deux composants réticulables, dans lesquelles chaque composant produit un groupe réactif capable de se réticuler avec un groupe réactif différent de l'autre composant. Ces compositions sont appropriées à la fabrication de revêtements, films, encapsulages et analogues, qui peuvent être durcis par réticulation induite par de la chaleur.
PCT/US1994/006783 1993-06-21 1994-06-15 Compositions de fluoropolymeres reticulables WO1995000588A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU70614/94A AU7061494A (en) 1993-06-21 1994-06-15 Crosslinking fluoropolymer compositions

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US7888893A 1993-06-21 1993-06-21
US08/078,888 1993-06-21

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WO1995000588A1 true WO1995000588A1 (fr) 1995-01-05

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855977A (en) * 1996-08-26 1999-01-05 Minnesota Mining And Manufacturing Company Multi-layer compositions comprising a fluoropolymer
EP0962789A3 (fr) * 1998-06-05 2003-07-23 Fuji Photo Film Co., Ltd. Couche antiréfléchissante et dispositif d'affichage avec cette couche
WO2003054042A3 (fr) * 2001-12-20 2003-10-09 Lumenon Innovative Lightwave T Matieres de guide d'ondes optique polymere a faible perte

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4925906A (en) * 1989-01-03 1990-05-15 Allied-Signal Inc. Stain-resistant polymers derived from the itaconic acid useful as coatings for fibers
US5061769A (en) * 1990-12-17 1991-10-29 Allied-Signal Inc. Fluoropolymers and fluoropolymer coatings
WO1993024569A1 (fr) * 1992-06-01 1993-12-09 Allied-Signal Inc. Compositions de fluoropolymeres reticulables

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4925906A (en) * 1989-01-03 1990-05-15 Allied-Signal Inc. Stain-resistant polymers derived from the itaconic acid useful as coatings for fibers
US5061769A (en) * 1990-12-17 1991-10-29 Allied-Signal Inc. Fluoropolymers and fluoropolymer coatings
WO1993024569A1 (fr) * 1992-06-01 1993-12-09 Allied-Signal Inc. Compositions de fluoropolymeres reticulables

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855977A (en) * 1996-08-26 1999-01-05 Minnesota Mining And Manufacturing Company Multi-layer compositions comprising a fluoropolymer
EP0962789A3 (fr) * 1998-06-05 2003-07-23 Fuji Photo Film Co., Ltd. Couche antiréfléchissante et dispositif d'affichage avec cette couche
WO2003054042A3 (fr) * 2001-12-20 2003-10-09 Lumenon Innovative Lightwave T Matieres de guide d'ondes optique polymere a faible perte

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