Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/28—Interference filters
  • G02B5/285—Interference filters comprising deposited thin solid films
  • G02B5/287—Interference filters comprising deposited thin solid films comprising at least one layer of organic material
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
  • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
  • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the current application relates to polyester copolymers for use in optical films.
• Polymeric films are used in a wide variety of applications.
• One particular use of polymeric films is in optical films to control light.
• optical film that control light include mirrors and reflective polarizers that reflect light of a given polarization or wavelength range.
• Such reflective films are used, for example, in conjunction with backlights in liquid crystal displays to enhance brightness.
• a reflective polarizing film may be placed between the user and the backlight to recycle the polarization state that becomes an image, thereby increasing brightness.
• a mirror film may be placed behind the backlight to reflect light towards the user; thereby enhancing brightness.
• Another use of polarizing films is in articles, such as sunglasses, to reduce light intensity and glare.
• polyester-based polarizer includes a stack of polyester layers of differing composition.
• One configuration of this stack of layers includes a first set of birefringent layers and a second set of layers with an isotropic index of refraction. The second set of layers alternates with the birefringent layers to form a series of interfaces for reflecting light.
• the current application relates to polyester copolymers for use in optical films.
• the copolyester polymeric material comprise 40 to 51 mol% substituted naphthalate units, 10 to 40 mol% ethylene units, and 10 to 40 mol% hexane units.
• the substituted naphthalate units comprise dimethyl -2, 6-naphthalene dicarboxylate .
• the polyester copolymers can be used to prepare multi-layer optical films by coextrusion and/or co-stretching.
• FIG. 1 is a cross-sectional view of a multi-layer optical film of this disclosure.
• FIG. 2 is a cross-sectional view of an optical stack article of this disclosure.
• FIG. 3 is graph showing the correlation of Tg to mol% hexanediol in copolymers of this disclosure.
• FIG. 4 is graph showing the correlation of in plane birefringence to % hexanediol in copolymers of this disclosure.
• Polymeric films are used in a wide variety of optical applications. Among uses of polymeric films is in mirrors and reflective polarizers that reflect light of a given polarization or wavelength range. Such reflective films are used, for example, in conjunction with backlights in liquid crystal displays to enhance brightness. A reflective polarizing film may be placed between the user and the backlight to recycle the polarization state that becomes an image, thereby increasing brightness. A mirror film may be placed behind the backlight to reflect light towards the user; thereby enhancing brightness. Another use of polarizing films is in articles, such as sunglasses, to reduce light intensity and glare.
• polyester-based polarizer includes a stack of polyester layers of differing composition.
• One configuration of this stack of layers includes a first set of birefringent layers and a second set of layers with an isotropic index of refraction. The second set of layers alternates with the birefringent layers to form a series of interfaces for reflecting light.
• the multi-layer reflective polarizer films it is often desirable for the multi-layer reflective polarizer films to include relatively thick and rigid outer layers to serve to increase the rigidity and handleability of these films, especially since the individual layers of the multi-layer reflective polarizer films are so thin (typically, 55 to 130 nanometers) and in some instances there are relatively few layers.
• relatively thick and rigid outer layers are laminated to the multi-layer reflective polarizer films.
• Lamination is an extra step in the formation of the film article, and thus can add cost and manufacturing time to the preparation of the film articles. Also, lamination can add defects to film articles.
• the outer layers are prepared from polymeric materials such as polycarbonates or polyesters that tend to add expense to the film articles. As mentioned above, the outer layers are relatively thick to provide the desired rigidity to the formed articles, and therefore the outer layers comprise a substantial portion of the mass of the formed article.
• polyester materials have issues.
• PET Polyethylene Terephthalate
• RP Reflective Polarizers
• HIO high index optics
• PEN polytheylene naphthalate
• CoPEN Co-polyethylene naphthalate
• NDC naphthalene dicarboxylate
• Multi-layer reflective polarizers typically use an HIO composed of PEN or CoPENs that are composed of 90 mole % or more of NDC. For colder temperatures the HIO will break or be hazy. Typical one-dimensional orientation temperatures for PET are 95°C (see US Patent No. 9,664,834). Thus, there is clearly no overlap in the orientation temperatures between that used for HIOs that demonstrate the high birefringence required for RPs and PET which has low cost and good mechanical properties for rigid films. Thus, the use of PET in the films of this disclosure is unexpected.
• polyester materials suitable for these optical uses where the polyester materials are copolyester polymeric material comprising substituted naphthalate units, ehtylene units, and hexane units.
• Tg glass transition temperature
• the optical film comprises an optically active portion comprising a plurality of alternating polymeric first and second interference layers, where the number of layers is greater than 25, where the optically active portion is disposed between, and integrally formed with, first and second skin layers.
• the optical films may also contain additional layers as is described in detail below.
• the multi-layered polymer films of this disclosure may be used, for example, as an optical reflective polarizer or mirror.
• the film includes optical layers comprising alternating layers of first interference layers and second interference layers, as well as non-optical layers such as skin layers.
• the non-optical layers typically provide protection and rigidity to the film articles.
• the first interference layers are generally birefringent polymer layers which are uniaxially- or biaxially-oriented.
• the second interference layers may also be polymer layers which are birefringent and uniaxially- or biaxially- oriented. More typically, however, the second interference layers have an isotropic index of refraction which is different from at least one of the indices of refraction of the first interference layers after orientation.
• the methods of manufacture and use, as well as design considerations for the multi-layered polymer fdms are described, for example, in U.S. 5,882,774 and U.S. 2001/0011779A1.
• the materials used in the multi-layer optical fdm constructions of this disclosure include polyester materials.
• Polyesters include carboxylate and glycol subunits and are generated by reactions of carboxylate monomer molecules with glycol monomer molecules.
• Each carboxylate monomer molecule has two or more carboxylic acid or ester functional groups and each glycol monomer molecule has two or more hydroxy functional groups.
• the carboxylate monomer molecules may all be the same or there may be two or more different types of molecules. The same applies to the glycol monomer molecules.
• Suitable carboxylate monomer molecules for use in forming the carboxylate subunits of the polyester layers include, for example, 2,6-naphthalene dicarboxylic acid and isomers thereof; terephthalic acid; isophthalic acid; phthalic acid; azelaic acid; adipic acid; sebacic acid; norbomene dicarboxylic acid; bi-cyclooctane dicarboxylic acid; 1,6-cyclohexane dicarboxylic acid and isomers thereof; t-butyl isophthalic acid, tri-mellitic acid, sodium sulfonated isophthalic acid; 4,4-biphenyl dicarboxylic acid and isomers thereof; and lower alkyl esters of these acids, such as methyl or ethyl esters.
• lower alkyl refers, in this context, to Ci-Cio straight-chained or branched alkyl groups.
• polyester also included within the term “polyester” are polycarbonates which are derived from the reaction of glycol monomer molecules with esters of carbonic acid, and blends of polycarbonates with copolyesters made from the above comonomers.
• Suitable glycol monomer molecules for use in forming glycol subunits of the polyester layers include ethylene glycol; propylene glycol; 1,4-butanediol and isomers thereof; 1,6-hexanediol; neopentyl glycol; polyethylene glycol; diethylene glycol; tricyclodecanediol; 1,4-cyclohexanedimethanol and isomers thereof; 2-butyl -2-ethyl- 1,3 -propane diol; 2, 2, 4-triethyl- 1,3-pentane diol; norbomanediol; bicyclo-octanediol; trimethylol propane; pentaerythritol; 1,4-benzenedimethanol and isomers thereof; bisphenol A; 1,8-dihydroxy biphenyl and isomers thereof; and l,3-bis(2-hydroxyethoxy)benzene.
• 1,4-cyclohexane dimethanol also has been found useful for some exemplary embodiments of the present disclosure due to the inverse effect it has on the polymer properties of glass transition temperature and refractive index.
• Increasing the mol portion of chdm can increase the glass transition temperature of the copolymer while at the same time decrease its refractive index.
• co polyesters containing both tbia and chdm were found to have relatively high glass transition temperatures for their respective refractive indices.
• hexanediol-containing polyester copolymers are hexanediol-containing polyester copolymers. These polyester copolymers have been found to have the proper combination of melt processability and optical properties to be particularly useful in the current optical film constructions.
• the hexanediol-containing polyester copolymers are copolymers of substituted naphthalene dicarboxylate moieties, ethylene glycol moities, and hexanediol moities. These polymers may be viewed as modified versions of PEN (polyethylene naphthalate) where some of the ethylene moieties are replaced by hexane moieties. PEN has been found to be very useful in multi-layer optical fdms.
• the copolymers are prepared in reaction mixtures that also contain at least one metal catalyst to facilitate the formation of the copolymers.
• the hexanediol-containing polyester copolymers are prepared from a reaction mixture comprising 55-62 parts by weight of a substituted naphthalene dicarboxylate, 5-24 parts by weight of hexanediol, 20-35 parts by weight of ethylene glycol, and less than 0.3 parts by weight of a metal catalyst.
• the substituted naphthalene dicarboxylate comprises dimethyl -2, 6-naphthalene dicarboxylate (NDC).
• polyester copolymers are described by the mol% of the units within the copolymer that are linked by ester linkages.
• particularly suitable hexanediol-containing polyester copolymers are ones comprising 40-51 mol% substituted naphthalate units, 10-40 mol% ehtylene units, and 10-40 mol % hexane units.
• the substituted naphthalene dicarboxylate comprises dimethyl-2, 6-naphthalene dicarboxylate (NDC).
• Figure 1 shows a cross-sectional view of a first multi-layer optical film construction of this disclosure.
• Optical film 100 comprises a plurality of alternating polymeric first interference layers 10 and second interference layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating polymeric first interference layers 10 and second interference layers 20, are disposed between, and integrally formed with, first skin layer 30 and second skin layer 40.
• the optical film For substantially normally incident light 50 and for each wavelength in a predetermined wavelength range 60 extending at least from about 430 nanometers (nm) to about 600 nm, the optical film has an optical reflectance of at least 40% for a first polarization state (Px).
• the predetermined wavelength range extends at least from about 400 nm to about 650 nm, or at least from about 430 nm to about 650 nm, or from about 400 to about 600 nm.
• the optical film has an optical reflectance of at least 50%, at least 60% or even at least 70% for a first polarization state (Px).
• Each of the first and second interference layers has an average thickness less than about 250 nm.
• the adjacent first and second interference layers have respective in plane indices of refraction nix and n2x along the first polarization state (Px), nly and n2y along an orthogonal second polarization state (Py), and nlz and n2z along a z-axis orthogonal to the first and second polarization states.
• nix is greater than each of nly and nlz by at least 0.18.
• the difference between nly and nlz is less than about 0.10.
• the maximum difference between n2x, n2y and n2z is less than about 0.01, and the difference between nix and n2x is greater than about 0.18.
• the first interference layer 10 comprises a hexanediol-containing polyester copolymer
• the first skin layer 30 comprises polyester
• the second skin layer 40 comprises at least 70% by weight of polyethylene terephthalate (PET) and the second skin layer has an average thickness greater than about 0.5 micrometers.
• PET polyethylene terephthalate
• the first interference layer comprises a hexanediol-containing polyester copolymer.
• the first interference layer comprises a copolymer of sustituted naphthalene dicarboxylate moities, ethylene glycol moities, and hexanediol moities.
• more than about 95% of the first interference layer is a copolymer of sustituted naphthalene dicarboxylate moities, ethylene glycol moities, and hexanediol moities.
• the polyester copolymer in some embodiments comprises between about 5% to about 90% by weight of one or more diol moieties.
• the diol moieties in the first interference layer are hexanediol, with the remaining diol moities being ethylene glycol moities. In some embodiments, at least about 40% of the diol moieties or at least 70% of the diol moities in the first interference layer are hexanediol. In some embodiments, the Tg of the first interference layer is between about 60 to about 110°C.
• the first interference layer can have a wide range of thicknesses. Typically, the first interference layer and the second interference layer have the same thickness, having an average thickness of less than aobut 200 nm, less than about 150 nm, or between 40 and 150 nm.
• the first skin layer also comprises a polyester layer.
• the first skin layer and the first interference layer may be same composition, or they may be different compositions.
• the first skin layer comprises polyethylene terephthalate (PET) or copolymers of PET.
• PET polyethylene terephthalate
• Copolymers of PET typically are prepared by replacing some of the 1,4-terephthalate units with 1,2- or 1,3-units. This can disrupt the crystallinity of the polymer and reduce the melting temperature.
• Such polymers are often referred to as co-PET.
• Other modified PET polymers are modified by replacing some of the ethylene glycol with a different glycol. These polymers are often referred to as glycol-modified PET of PETg.
• An example of PETg is EASTAR COPOLYESTER GN071 from Eastman Chemical Company.
• the first skin layer comprises at least about 50% by weight PET, at least about 60% by weight PET, or at least about 70% by weight PET.
• the first skin layer comprises co-PET.
• the amount of co-PET can vary widely.
• the first skin layer comprises at least about 10% by weight co-PET, at least about 20% by weight co-PET, or at least about 30% by weight co-PET.
• the first skin layer comprises PETg.
• the amount of PETg can vary widely.
• the first skin layer comprises at least about 10% by weight PETg, at least about 20% by weight PETg, or at least about 30% by weight PETg.
• the first skin layer comprises a polyester copolymer that comprises hexanediol, ethylene glycol, or a combination thereof.
• the second interference layer can also have a wide range of compositions and thicknesses.
• the composition of the second interference is different from the composition of the first interference so as to give the desired optical effect.
• the second interference layer comprises a majority of a polyester or copolyester material, in other embodiments the second interference layer comprises a majority of one or more (meth)acrylate materials. Examples of suitable polyester and copolyester materials are described above.
• the copolyester comprises a copolyester ether such as NEOSTAR ELASTOMER FN007 commercially available from Eastman Chemical Company are also suitable.
• the term “(meth)acrylate” as used herein refers to both acrylate and methacrylate materials.
• the second interference layer comprises a majority of polyester materials. Particularly suitable materials are PET and copolyester such as a copolyester ether. In some embodiments, the second interference layer comprises at least 80% by weight of PET, at least 90% by weight of PET, or even at least 95% by weight of PET. In other embodiments, the second interference layer comprises at least 80% by weight of a copolyester, least 90% by weight of a copolyester, or at least 95% by weight of a copolyester.
• the second interference layer comprises at least 50% by weight of at least one (meth)acrylate. In other embodiments, second interference layer comprises at least 60% by weight of at least one (meth)acrylate, at least 70% by weight of at least one (meth)acrylate, at least 80% by weight of at least one (meth)acrylate, at least 90% by weight of at least one (meth)acrylate, or at least 95% by weight of at least one (meth)acrylate. In some embodiments, the (meth)acrylate comprises a coPMMA. In these embodiments, the second interference layer comprises at least 50% by weight of a coPMMA.
• the second skin layer 40 can comprise a wide range of materials and a wide range of thicknesses.
• the second skin layer 40 comprises at least 70% by weight of polyethylene terephthalate (PET) and has an average thickness greater than about 0.5 micrometers.
• PET polyethylene terephthalate
• the average thickness of the second skin layer is greater than about 1 micrometer, greater than 10 micrometers, greater than 100 micrometers, greater than 150 micrometers, or even greater than 200 micrometers.
• the average thickness of the second skin layer is less than about 400 micrometers, less than about 300 micrometers, less than about 200 micrometers, less than about 100 micrometers, less than about 50 micrometers, or even less than about 30 micrometers.
• the second skin layer comprises at least 80% by weight PET, at least 85% by weight of PET, or about 90% by weight of PET. In some embodiments, the second skin layer further comprises at least about 5% by weight of PETg. In some embodiments, the second interference layer has the same composition as the first skin layer described above.
• the multi-layer film articles of this disclosure may also comprise a variety of optional layers, as shown in Figure 1.
• the multi-layer article further comprises a first protective layer 70 disposed between the plurality of alternating polymeric first and second interference layers and the second skin layer 40
• the first protective layer may have a wide range of material compositions.
• the first protective layer and the first interference layers have substantially the same composition.
• the first protective layer may have a wide range of thicknesses.
• the first protective layer has an average thickness between about 0.5 micrometers and about 20 micrometers.
• the particles comprise a (meth)acrylate or (meth)acrylate copolymer.
• the particles comprise a polystyrene or polystyrene copolymer.
• the particles comprise an inorganic material, such as glass.
• the average size of the particles is between about 1 micrometer to about 20 micrometers. In some embodiments, at least some of the particles in the plurality of particles protrude from a top surface of the light diffusing layer.
• the first skin and the first and second interference layers comprise polyester, where the first interference layer comprises a copolyester polymeric material comprising hexane diol moieties, and where the second skin layer comprises at least 70% by weight of polyethylene terephthalate (PET).
• PET polyethylene terephthalate
• the first and second skin layers, in combination, comprise at least 70% by volume of polyester.
• the multi-layer optical film has an optical reflectance of at least 50% for a first polarization state (Px).
• the optical film has an optical reflectance of at least 60% for a first polarization state (Px), or even an optical reflectance of at least 70% for a first polarization state (Px).
• the first and second skin layers, in combination comprise at least 80% by volume of polyester.
• the multi-layer optical articles have a flexural modulus of greater than about 1500 MPa, as measured according to the ASTM D790 test method.
• the multi-layer optical film 100 comprises a plurality of alternating polymeric first 10 and second 20 polymeric layers numbering greater than 25 and disposed between, and integrally formed with, first 30 and second 40 skin layers, where the first skin and the first and second interference layers are polyester compositions, wherein at least the first interference layer comprises a copolyester polymeric material comprising hexanediol moities.
• the second skin layer comprises at least 70% by weight of polyethylene terephthalate (PET).
• the optical film For substantially normally incident light 50 and for each wavelength in a predetermined wavelength range 60 extending at least from about 400 nm to at least about 600 nm, the optical film has an optical reflectance of at least 50% for a first polarization state (Px), and the optical film has a flexural modulus of greater than about 1500 MPa, as measured according to the ASTM D790 standard test method.
• Px first polarization state
• the multi-layer optical film 100 has mirror-like properties, having an optical reflectance of at least 50% for the second polarization state (Py). In some embodiments, the optical reflectance is at least 60% or even 70% for the second polarization state (Py).
• the film 100 comprises a plurality of alternating polymeric first 10 and second 20 interference layers numbering greater than 100 and disposed between, and integrally formed with, first 30 and second 40 skin layers, where each of the first and second interference layers has an average thickness less than about 250 nm, and the first skin and the interference layers having respective first and second compositions comprising polyester.
• the second skin layer comprises at least 70% by weight of polyethylene terephthalate (PET) and had an average thickness of greater than about 100 micrometers.
• nix is greater than each of nly and nlz by at least 0.20, by at least 0.21, by at least 0.22, by at least 0.23, by at least 0.24, or even by at least 0.25; the difference between nly and nlz is less than about 0.08, or even less than 0.07, in some embodiments, the difference between nly and nlz is not greater than 0.06; the maximum difference between n2x, n2y and n2z is less than about 0.01; and the difference between nix and n2x is greater than about 0.14.
• the multi-layer optical film 100 is a reflective polarizer, having optical transmittance of at least 60% for the second polarization state (Py). In some embodiments, the optical transmittance is at least 70% or even 80% for the second polarization state (Py).
• the multi-layer optical films of the present disclosure can be prepared in a variety of different ways. As was mentioned above, an advantage of the present disclosure is the simple and straightforward techniques that can be used to prepare the article. One particularly suitable technique for forming the articles is co-extrusion. Co-extrusion techniques are well understood by one of skill in the art.
• the plurality of alternating polymeric first and second interference layers and the first and second skin layers are co-extruded. In some embodiments, the first and second interference layers and the first and second skin layers are co-extruded the at a temperature between about 460 and 550°F, in some embodiments at a temperature of about 500°F. In some embodiments, the plurality of alternating polymeric first and second interference layers and the first and second skin layers are further co-stretched at a temperature between about 190 and 220°F.
• the multi-layer optical film is formed by co-extruding the plurality of alternating polymeric first and second interference layers and the first and second skin layers, and in some embodiments, the optical film is further formed by co-stretching the plurality of alternating polymeric first and second interference layers and the first and second skin layers at a temperature between about 190 and 220°F.
• optical stack 200 comprises a structured film 110 comprising a plurality of structures 111, each structure comprising opposing facets 112, and 113 meeting at a peak 114 with the multi-layered optical film article 100 disposed on the peaks of the structures.
• a first adhesive layer 120 bonds the optical film 100 to the peaks 114 of the structures 111.
• the optical stack has a flexural modulus of greater than about 1500 MPa, as measured according to the ASTM D790 test method.
• the plurality of structures 111 are embedded in the first adhesive layer 120 as shown in Figure 2.
• the structured film 110 further comprises a first substrate 115, where the plurality of structures 111 are disposed on a major surface 116 of the first substrate 115.
• the optical stack article can contain a variety of additional layers and features.
• the optical stack further comprises a second substrate 130 disposed between the optical film and the first adhesive layer, and a second adhesive layer 140 bonding the second substrate to the multi-layer optical film article 100.
• a wide range of optically clear adhesives are suitable for use as the adhesive layers 120 and 140.
• the adhesive layers may be the same or different.
• Figure 1 also shows a cross-sectional view of a second multi-layer optical film mirror construction of this disclosure.
• Optical film 100 comprises a plurality of alternating polymeric first interference layers 10 and second interference layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating polymeric first interference layers 10 and second interference layers 20 each have a thickness of less than 250 nm and are disposed between, and integrally formed with, first skin layer 30 and second skin layer 40.
• the optical film For substantially normally incident light 50 and for each wavelength in a predetermined wavelength range 60 extending at least from about 400 nm to at least about 600 nm, the optical film having an optical reflectance of at least 50% for each of orthogonal first (Px) and second (Py) polarization states.
• Adjacent first and second interference layers have respective in plane indices of refraction: nix and n2x along the first polarization state; nly and n2y along the second polarization state; and nlz and n2z along a z-axis orthogonal to the first and second polarization states.
• each of nix and nly is greater than nlz by at least 0.18; a maximum difference between n2x, n2y and n2z is less than about 0.01; and a difference between nix and n2x is greater than about 0.18.
• Figure 1 also shows a cross-sectional view of a fourth multi-layer optical film construction of this disclosure.
• Optical film 100 comprises a plurality of alternating first polymeric layers 10 and second polymeric layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating first polymeric layers 10 and second polymeric layers 20 are disposed between, and integrally formed with, first skin layer 30 and second skin layer 40.
• the first skin layer comprises a polyester
• the first polymeric layers comprise a copolyester polymeric material with hexanediol moieties
• the second skin layer comprises at least 70% by weight PET.
• the optical film For substantially normal incident light 50 and for each wavelength in a predetermined wavelength range 60 extending at least from 400 nm to at least about 600 nm, the optical film has an optical reflectance of at least 50% for a first polarization sate (Px).
• the first and second skin layers, in combination, comprise at least 70% polyester by volume.
• Figure 1 also shows a cross-sectional view of a fifth multi-layer optical film construction of this disclosure.
• Optical film 100 comprises a plurality of alternating first polymeric layers 10 and second polymeric layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating first polymeric layers 10 and second polymeric layers 20 are disposed between, and integrally formed with, first skin layer 30 and second skin layer 40 and are co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F with first 30 and second 40 skin layers.
• first and second polymeric layers have an average thickness less than about 250 nm
• the first polymeric layers comprise a polyester copolymer with hexanediol and ethylene glycol moieties.
• the first and the second polymeric layers have respective in-plane birefringences greater than about 0.21 and less than about 0.01.
• Figure 1 also shows a cross-sectional view of a sixth multi-layer optical film construction of this disclosure.
• Optical film 100 comprises a plurality of alternating first polymeric layers 10 and second polymeric layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating first polymeric layers 10 and second polymeric layers 20 are disposed between, and co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F with, first skin layer 30 and second skin layer 40.
• Each of the first and second polymeric layers have an average thickness less than about 250 nm.
• the first and second polymeric layers and the first and second skin layers have glass transition temperatures less than about 95°C, the first polymeric layers have in-plane birefringences greater than about 0.21.
• the optical film For substantially normally incident light 50 and for at least one wavelength between about 400 nm to about 1500 nm, the optical film reflects at least 20% of the incident light having a first polarization state.
• Figure 1 also shows a cross-sectional view of a seventh multi-layer optical film construction of this disclosure.
• Optical film 100 comprises a plurality of alternating first polymeric layers 10 and second polymeric layers 20, where the number of layers is greater than 25. In some embodiments, the number of layers is greater than 35, or even greater than 100.
• the alternating first polymeric layers 10 and second polymeric layers 20 are disposed between, and co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F with, first skin layer 30 and second skin layer 40.
• Each of the first and second polymeric layers have an average thickness less than about 250 nm.
• the first and second polymeric layers and the first and second skin layers have glass transition temperatures within about 5°C of each other, and the first polymeric layers have in-plane birefringences greater than about 0.21.
• the optical film For substantially normally incident light 50 and for at least one wavelength between about 400 nm to about 1500 nm, the optical film reflects at least 20% of the incident light having a first polarization state.
• Embodiment 1 includes an optical fdm (100) comprising a plurality of alternating polymeric first (10) and second (20) interference layers numbering greater than 25 in total and disposed between, and integrally formed with, first (30) and second (40) skin layers, each of the first and second interference layers having an average thickness less than about 250 nm, the first interference layer comprising a hexanediol-containing polyester copolymer, the first skin layer comprising polyester, the second skin layer comprising at least 70% by weight of polyethylene terephthalate (PET) and having an average thickness greater than about 0.5 micrometers, for substantially normally incident light (50) and for each wavelength in a predetermined wavelength range (60) extending at least from about 430 nm to at least about 600 nm, the optical film having an optical reflectance of at least 40% for a first polarization state (Px), adjacent first and second interference layers having respective in plane indices
• Px first polarization state
• Embodiment 3 is the optical film of embodiment 1 or 2, wherein the plurality of alternating polymeric first and second interference layers number greater than 100.
• Embodiment 4 is the optical film of any of embodiments 1-3, wherein each of the first and second interference layers has an average thickness less than about 200 nm.
• Embodiment 5 is the optical film of any of embodiments 1-4, wherein each of the first and second interference layers has an average thickness less than about 150 nm.
• Embodiment 6 is the optical film of any of embodiments 1-5, wherein each of the first and second interference layers has an average thickness between about 40 nm and 150 nm.
• Embodiment 7 is the optical film of any of embodiments 1-6, wherein the first interference layer comprises a copolymer of substituted naphthalene dicarboxylate moieties, ethylene glycol moieties, and hexanediol moieties.
• Embodiment 8 is the optical film of any of embodiments 1-7, wherein more than about 95 weight% of the first interference layer comprises a copolymer of substituted naphthalene dicarboxylate moieties, ethylene glycol moieties, and hexanediol moieties.
• Embodiment 9 is the optical film of any of embodiments 1-8, wherein between about 5% to about 90% of diol moieties in the first interference layer are hexanediol.
• Embodiment 10 is the optical film of any of embodiments 1-9, wherein at least about 40% of diol moieties in the first interference layer are hexanediol.
• Embodiment 11 is the optical film of any of embodiments 1-10, wherein at least about 70% of diol moieties in the first interference layer are hexanediol.
• Embodiment 12 is the optical film of any of embodiments 1-11, wherein between about 30% to about 80% of diol moieties in the first interference layer are hexanediol.
• Embodiment 13 is the optical film of embodiment 12, wherein remaining diol moieties in the first interference layer are ethylene glycol.
• Embodiment 14 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 80% by weight of a copolyester.
• Embodiment 15 is the optical film of any of embodiments 1-14, wherein the second interference layer comprises at least 90% by weight of a copolyester.
• Embodiment 16 is the optical film of any of embodiments 1-15,
• Embodiment 17 is the optical film of any of embodiments 1-16, wherein the second interference layer comprises at least 95% by weight of a copolyester.
• Embodiment 18 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 80% by weight of PETg.
• Embodiment 19 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 90% by weight of PETg.
• Embodiment 20 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 95% by weight of PETg.
• Embodiment 21 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 50% by weight of an acrylate.
• Embodiment 22 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 60% by weight of an acrylate.
• Embodiment 23 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 70% by weight of an acrylate.
• Embodiment 24 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 80% by weight of an acrylate.
• Embodiment 25 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 90% by weight of an acrylate.
• Embodiment 26 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 95% by weight of an acrylate.
• Embodiment 27 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 50% by weight of a coPMMA.
• Embodiment 28 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 60% by weight of a coPMMA.
• Embodiment 29 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 70% by weight of a coPMMA.
• Embodiment 30 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 80% by weight of a coPMMA.
• Embodiment 31 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 90% by weight of a coPMMA.
• Embodiment 32 is the optical film of any of embodiments 1-13, wherein the second interference layer comprises at least 95% by weight of a coPMMA.
• Embodiment 35 is the optical film of any of embodiments 1-34, wherein at least one of the first skin and the first interference layers has a glass transition temperature between about 60°C and 110°C.
• Embodiment 36 is the optical film of any of embodiments 1-35, wherein the glass transition temperatures of the first skin and the first interference layers are within 5°C of each other.
• Embodiment 37 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises PET.
• Embodiment 38 is the optical film of any of embodiments 1-37, wherein the first skin layer comprises PET at least about 50% by weight.
• Embodiment 39 is the optical film of any of embodiments 1-38, wherein the first skin layer comprises PET at least about 60% by weight.
• Embodiment 40 is the optical film of any of embodiments 1-39, wherein the first skin layer comprises PET at least about 70% by weight.
• Embodiment 41 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises a co-PET.
• Embodiment 42 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises a co-PET at least about 10% by weight.
• Embodiment 43 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises a co-PET at least about 20% by weight.
• Embodiment 44 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises a co-PET at least about 30% by weight.
• Embodiment 45 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises PETg.
• Embodiment 46 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises PETg at least about 10% by weight.
• Embodiment 47 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises PETg at least about 20% by weight.
• Embodiment 48 is the optical film of any of embodiments 1-36, wherein the first skin layer comprises PETg at least about 30% by weight.
• Embodiment 50 is the optical film of any of embodiments 1-49, wherein the first skin layer comprises ethylene glycol moieties.
• Embodiment 52 is the optical film of any of embodiments 1-51, wherein the first skin layer has an average thickness greater than about 2 micrometers.
• Embodiment 54 is the optical film of any of embodiments 1-53, wherein the second skin layer comprises at least 80% by weight of polyethylene terephthalate (PET).
• PET polyethylene terephthalate
• Embodiment 55 is the optical film of any of embodiments 1-54, wherein the second skin layer comprises at least 85% by weight of PET.
• Embodiment 56 is the optical film of any of embodiments 1-55, wherein the second skin layer comprises about 90% by weight of PET.
• Embodiment 58 is the optical film of any of embodiments 1-57, wherein the average thickness of the second skin layer is greater than about 1 micrometer.
• Embodiment 59 is the optical film of any of embodiments 1-58, wherein the average thickness of the second skin layer is greater than about 10 micrometers.
• Embodiment 60 is the optical film of any of embodiments 1-59, wherein the average thickness of the second skin layer is less than about 400 micrometers.
• Embodiment 62 is the optical film of any of embodiments 1-61, wherein the average thickness of the second skin layer is less than about 200 micrometers.
• Embodiment 63 is the optical film of any of embodiments 1-62, wherein the average thickness of the second skin layer is less than about 100 micrometers.
• Embodiment 64 is the optical film of any of embodiments 1-62, wherein the average thickness of the second skin layer is less than about 50 micrometers.
• Embodiment 65 is the optical film of any of embodiments 1-63, wherein the average thickness of the second skin layer is less than about 30 micrometers.
• Embodiment 66 is the optical film of any of embodiments 1-58, wherein the average thickness of the second skin layer is greater than about 100 micrometers.
• Embodiment 67 is the optical film of any of embodiments 1-58, wherein the average thickness of the second skin layer is greater than about 150 micrometers.
• Embodiment 68 is the optical film of any of embodiments 1-58, wherein the average thickness of the second skin layer is greater than about 200 micrometers.
• Embodiment 69 is the optical film of any of embodiments 1-68, wherein the first and second skin layers, in combination, comprise at least 80% by volume of polyester.
• Embodiment 71 is the optical film of any of embodiments 1-69, wherein the difference between nly and nlz is not greater than about 0.06.
• Embodiment 72 is the optical film of any of embodiments 1-69, wherein the difference between nly and nlz is less than about 0.07.
• Embodiment 73 is the optical film of any of embodiments 1-72, wherein nix is greater than each of nly and nlz by at least 0 2
• Embodiment 74 is the optical film of any of embodiments 1-73, wherein nix is greater than each of nly and nlz by at least 0.21.
• Embodiment 75 is the optical film of any of embodiments 1-74, wherein nix is greater than each of nly and nlz by at least 0.22.
• Embodiment 76 is the optical film of any of embodiments 1-75, wherein nix is greater than each of nly and nlz by at least 0.23.
• Embodiment 77 is the optical film of any of embodiments 1-76, wherein nix is greater than each of nly and nlz by at least 0.24.
• Embodiment 78 is the optical film of any of embodiments 1-77, wherein nix is greater than each of nly and nlz by at least 0.25.
• Embodiment 79 is the optical film of any of embodiments 1-78, having an optical reflectance of at least 50% for the first polarization state (Px).
• Embodiment 80 is the optical film of any of embodiments 1-79, having an optical reflectance of at least 60% for a first polarization state (Px).
• Embodiment 81 is the optical film of any of embodiments 1-80, having an optical reflectance of at least 70% for a first polarization state (Px).
• Embodiment 83 is the optical film of any of embodiments 1-81, wherein the predetermined wavelength range extends from about 400 nm to about 650 nm.
• Embodiment 84 is the optical film of any of embodiments 1-83, having an optical reflectance of at least 50% for the second polarization state.
• Embodiment 85 is the optical film of any of embodiments 1-84, having an optical reflectance of at least 60% for the second polarization state.
• Embodiment 86 is the optical film of any of embodiments 1-85, having an optical reflectance of at least 70% for the second polarization state.
• Embodiment 87 is the optical film of any of embodiments 1-83, having an optical transmittance of at least 60% for the second polarization state.
• Embodiment 88 is the optical film of any of embodiments 1-83, having an optical transmittance of at least 70% for the second polarization state.
• Embodiment 89 is the optical film of any of embodiments 1-83 having an optical transmittance of at least 80% for the second polarization state.
• Embodiment 90 is the optical film of any of embodiments 1-89, formed integrally and having an average thickness greater than about 200 micrometers.
• Embodiment 91 is the optical film of any of embodiments 1-89, formed integrally and having an average thickness greater than about 250 micrometers.
• Embodiment 92 is the optical film of any of embodiments 1-89, formed integrally and having an average thickness greater than about 50 micrometers.
• Embodiment 93 is the optical film of embodiment 92, wherein the plurality of alternating polymeric first and second interference layers and the first and second skin layers are further co-stretched at a temperature between about 190 and 220°F.
• Embodiment 94 is the optical film of any of embodiments 1-91 formed by co-extruding the plurality of alternating polymeric first and second interference layers and the first and second skin layers.
• Embodiment 96 is the optical film of any of embodiments 1-95, having a flexural modulus of greater than about 1500 MPa, as measured according to ASTM D790 standard.
• Embodiment 97 is the optical film of any of embodiments 1-96, further comprising a first protective layer 70 disposed between the plurality of alternating polymeric first and second interference layers and the second skin layer.
• Embodiment 98 is the optical film of embodiment 97, wherein the first protective layer and the first interference layers have substantially the same composition.
• Embodiment 99 is the optical film of embodiment 97 or 98, wherein the first protective layer has an average thickness between about 0.5 micrometers and about 20 micrometers.
• Embodiment 100 is the optical film of any of embodiments 1-99, further comprising a light diffusing layer (80) disposed on the first skin layer opposite the plurality of alternating polymeric first and second interference layers.
• Embodiment 101 is the optical film of embodiment 100, wherein light diffusing layer is co extruded with the plurality of alternating polymeric first and second interference layers and the first and second skin layers.
• Embodiment 102 is the optical film of embodiment 100, wherein light diffusing layer is coated on the plurality of alternating polymeric first and second interference layers.
• Embodiment 103 is the optical film of any of embodiments 100-102, wherein the light diffusing layer comprises a plurality of particles (81) dispersed in a material (82).
• Embodiment 104 is the optical film of embodiment 103, wherein the material comprises polyester and an acrylate.
• Embodiment 106 is the optical film of embodiment 103 or 104, wherein the particles comprise an inorganic material.
• Embodiment 107 is the optical film of embodiment 106, wherein the inorganic material comprises glass.
• Embodiment 108 is the optical film of embodiment 103 or 104, wherein the particles comprise a polystyrene.
• Embodiment 109 is the optical film of any of embodiments 103-108, wherein the particles have a volume percentage of a total volume of the light diffusing layer between about 40% to about 65%.
• Embodiment 110 is the optical film of any of embodiments 103-109, wherein an average size of the particles is between about 1 micrometer to about 20 micrometers.
• Embodiment 111 is the optical film of any of embodiments 103-110, wherein at least some of the particles in the plurality of particles protrude from a top surface of the light diffusing layer.
• Embodiment 112 is the optical film of any of embodiments 100-111, wherein the light diffusing layer has an average thickness between about 0.5 to about 12 micrometers.
• Embodiment 113 is an optical film (100) comprising a plurality of alternating polymeric first (10) and second (20) interference layers numbering greater than 25 in total and disposed between, and integrally formed with, first (30) and second (40) skin layers, each of the first and second interference layers having an average thickness less than about 250 nm, the first skin layer comprising polyester, the first interference layers comprising a hexanediol-containing polyester copolymer, wherein at least 30% by weight of diol moieties in the first interference layer is hexanediol, the second skin layer having an average thickness greater than about 100 micrometers and comprising polyethylene terephthalate (PET), and, for substantially normally incident light (50) and for each wavelength in a predetermined wavelength range (60) extending at least from about 400 nm to at least about 600 nm, the optical film having an optical reflectance of at least 50% for each of orthogonal first (Px) and second (Py) polarization states, adjacent first and
• Embodiment 114 is an optical film (100) comprising a plurality of alternating first (10) and second (20) polymeric layers numbering greater than 25 and disposed between, and integrally formed with, first (30) and second (40) skin layers, the first skin layer comprising polyester, the first polymeric layers comprising a hexanediol-containing polyester copolymer, the second skin layer comprising at least 70% by weight of polyethylene terephthalate (PET), for substantially normally incident light (50) and for each wavelength in a predetermined wavelength range (60) extending at least from about 400 nm to at least about 600 nm, the optical film having an optical reflectance of at least 50% for a first polarization state (Px), the optical film having a flexural modulus of greater than about 1500 MPa, as measured according to ASTM D790 standard.
• PTT polyethylene terephthalate
• Embodiment 115 is an optical film (100) comprising a plurality of alternating first (10) and second (20) polymeric layers numbering greater than 25 and disposed between, and integrally formed with, first (30) and second (40) skin layers, the first skin layer comprising polyester, the first polymeric layers comprising a hexanediol-containing polyester copolymer, the second skin layer comprising at least 70% by weight of polyethylene terephthalate (PET), for substantially normally incident light (50) and for each wavelength in a predetermined wavelength range (60) extending at least from about 400 nm to about 600 nm, the optical film having an optical reflectance of at least 50% for a first polarization state (Px), wherein the first and second skin layers, in combination, comprise at least 70% polyester by volume.
• PET polyethylene terephthalate
• Embodiment 116 is an optical film (100) comprising a plurality of alternating first (10) and second (20) polymeric layers numbering greater than 25 in total and disposed between, and co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F, with first (30) and second (40) skin layers, each of the first and second polymeric layers having an average thickness less than about 250 nm, the first polymeric layers comprising a polyester, hexanediol and ethylenediol copolymer, wherein the first and the second polymeric layers have repsective in-plane birefringences greater than about 0.21 and less than about 0.1.
• Embodiment 117 is an optical film (100) comprising a plurality of alternating first (10) and second (20) polymeric layers numbering greater than 25 in total and disposed between, and co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F, with first (30) and second (40) skin layers, each of the first and second polymeric layers having an average thickness less than about 250 nm, the first and second polymeric layers and the first and second skin layers having glass transition temperatures less than about 95°C, the first polymeric layers having in-plane birefringences greater than about 0.21, wherein for substantially normally incident light and for at least one wavelength between about 400 nm to about 1500 nm, the optical film reflects at least 20% of the incident light having a first polarization state.
• Embodiment 118 is an optical film (100) comprising a plurality of alternating first (10) and second (20) polymeric layers numbering greater than 25 in total and disposed between, and co-extruded and then co-stretched at one or more temperatures between about 190°F to about 220°F, with first (30) and second (40) skin layers, each of the first and second polymeric layers having an average thickness less than about 250 nm, the first and second polymeric layers and the first and second skin layers having glass transition temperatures within about 5°C of each other, the first polymeric layers having in-plane birefringences greater than about 0.21, wherein for substantially normally incident light and for at least one wavelength between about 400 nm to about 1500 nm, the optical film reflects at least 20% of the incident light having a first polarization state.
• Embodiment 119 is an optical stack (200) comprising: a structured film (110) comprising a plurality of structures (111), each structure comprising opposing facets (112, 113) meeting at a peak (114); the optical film of any of embodiments 1-118 disposed on the peaks of the structures; and a first adhesive layer (120) bonding the optical film to the peaks of the structures, the optical stack having a flexural modulus of greater than about 1500 MPa, as measured according to ASTM D790 standard.
• Embodiment 120 is the optical stack of embodiment 119, wherein the peaks of at least some of the structures in the plurality of structures are embedded in the first adhesive layer.
• Embodiment 121 is the optical stack of embodiment 119 or 120, wherein the structured film further comprises a first substrate (115), the plurality of structures disposed on a major surface (116) of the first substrate.
• Embodiment 123 is a copolyester polymeric material comprising: the reaction product of a reaction mixture comprising:
• Embodiment 125 is a copolyester polymeric material comprising:
• the materials were tested using DSC (Q2000 commercially available from TA Instruments, New Castle, Del.). A sample of about 5-10 mg was used for each composition.
• the test involved a 3-stage heating -cooling -heating temperature ramp at a temperature range of 30-290°C. The sample was held at 290°C for 3 min after the first heat. The ramp rate was 20°C./min for both heating and cooling. Both the first heating scan and the second heating scan were analyzed.
• the refractive indices of the various samples were measured using a Metricon Prism coupler (Metricon Corporation, Pennington, N.J.) in the MD, TD, and TM directions.
• MD and TD are in-plane directions and TM is normal to the film surface.
• the refractive indices of MD, TD and TM are labeled as: N x , N y , and N z , respectively.
• a series of polyhexylethylene naphthalate copolymers were produced using the following procedure using the components listed in Table 1: To a room temperature stainless steel 10-gallon reactor equipped with hot oil temperature control, an overhead separation column and a vacuum pump. The materials were heated and mixed at 125 rpm under 20 psig (138 kPa) of N2. The transesterification reaction was driven over the course of ⁇ 2 hours to a temp of 495°F (257°C). Methanol was driven off through the separation column and collected in a receiver. The pressure in the kettle was slowly bled down to atmospheric and vacuum was applied to the kettle and increased as batch viscosity allowed. Excess ethylene glycol was driven off.
• Figure 3 shows a graph of the Tg values for the copolymers of Examples 1-8 as well as for PEN (0 mol% HD).
• a series of films were produced using these resins of Examples 1-8 above in the following fashion: A twin-screw extruder w/vacuum was connected to melt train consisting of a gear pump, and neck tube which fed to a feed block and die. The extruder and melt train utilized a progressive temp profile with the bulk of the melt train at 500°F (260°C). The resins were extruded at 15 lb/hr and cast on to a 100°F (37°C) chill roll producing 12 mil (305 micrometer) thick cast web films.
• Figure 4 graphically shows the in-plane birefringence values (N x -N y ) for the copolymers of Examples 1-8.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Polarising Elements (AREA)
• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
• Polyesters Or Polycarbonates (AREA)
• Eyeglasses (AREA)
• Optical Elements Other Than Lenses (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=76130073

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (4)

Family Cites Families (8)

• 2020
  • 2020-11-23 JP JP2022530646A patent/JP2023503342A/ja active Pending
  • 2020-11-23 CN CN202080077147.4A patent/CN115038585B/zh active Active
  • 2020-11-23 WO PCT/IB2020/061041 patent/WO2021105852A1/en not_active Ceased
  • 2020-11-23 US US17/772,546 patent/US20220381964A1/en active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events