EP2925521A1 - Non-iridescent film with polymeric particles in primer layer - Google Patents
Non-iridescent film with polymeric particles in primer layerInfo
- Publication number
- EP2925521A1 EP2925521A1 EP13858125.1A EP13858125A EP2925521A1 EP 2925521 A1 EP2925521 A1 EP 2925521A1 EP 13858125 A EP13858125 A EP 13858125A EP 2925521 A1 EP2925521 A1 EP 2925521A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- particles
- film
- composite
- primer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims description 128
- 239000010410 layer Substances 0.000 claims abstract description 225
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 71
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 58
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 58
- 229920000728 polyester Polymers 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000012792 core layer Substances 0.000 claims abstract description 18
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 16
- 239000011241 protective layer Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000010954 inorganic particle Substances 0.000 claims abstract description 7
- 229920002635 polyurethane Polymers 0.000 claims description 54
- 239000004814 polyurethane Substances 0.000 claims description 54
- 229920006267 polyester film Polymers 0.000 claims description 50
- 239000003431 cross linking reagent Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 239000004645 polyester resin Substances 0.000 claims 1
- 229920001225 polyester resin Polymers 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 27
- 238000004132 cross linking Methods 0.000 abstract description 8
- 239000013538 functional additive Substances 0.000 abstract description 3
- 239000011146 organic particle Substances 0.000 abstract description 3
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 239000002987 primer (paints) Substances 0.000 description 106
- 239000010408 film Substances 0.000 description 98
- 230000003287 optical effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 23
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- 239000000243 solution Substances 0.000 description 13
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- PHBCDAHASFSLMJ-UHFFFAOYSA-N 2-hydroxybenzotriazole Chemical class C1=CC=CC2=NN(O)N=C21 PHBCDAHASFSLMJ-UHFFFAOYSA-N 0.000 description 2
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 230000032798 delamination Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920003009 polyurethane dispersion Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
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- 238000010292 electrical insulation Methods 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
Definitions
- the invention relates to optically clear biaxially oriented polyester film with at least one primer layer, having excellent adhesive properties to acrylic coating material over the primer layer even under harsh conditions, such as a high moisture environment.
- the polyester film coated with an acrylic hard coat has reduced iridescence due to dispersion of particles of certain polyurethane or polymethylmethacrylate within a primer layer between the polyester and the acrylic hard coat.
- the polyester film may have UV blocking and weatherable properties and may be preferably used for window film, display film, outside clear label, outside signage and photo voltaic applications.
- biaxially oriented polyester films can serve as a component of many articles such as food packaging, printing media, electrical insulation, optical and the other industrial uses.
- the thermal stability, dimensional stability, chemical resistance, relative high surface energy, optical clarity as well as cost effectiveness of biaxially oriented polyester films are beneficial for typical end use applications.
- biaxially oriented polyster films can be used for instance as a substrate of optical products such as window films, display parts, touch screen, eyewear, including visors, goggles, and spectacles, lenses, sunscreens, labels and photovoltaic materials.
- applications will involve placing optically clear acrylic coating material onto the biaxially oriented polyester films.
- the composite film of biaxially oriented polyester film coated with acrylic materal can have adverse optical properties.
- the film can exhibit excessive iridescence.
- the refractive index ("RI") of an acrylic coating material can be different from the RI of a biaxially oriented polyester film, e.g. polyethylene terephthalate (PET) film that is about 1.66.
- PET polyethylene terephthalate
- the difference between these refractive indices causes optical interference of light rays reflected from the surface between the acrylic layer and the polyester layer. This interference produces a rippled iridescent appearance through the spectral reflectance of the acrylic material-coated polyester film. Iridescence on the acrylic material coated polyester film is very evident under spectral light of fluorescent lamps because such light has a sharp distribution of luminescence that interferes with the rippled spectral reflectance of the acrylic material coated polyester film.
- polyester-coated polyester films Another problem with the acrylic material-coated polyester films is adhesion between layers of acrylic material and the polyester layer.
- biaxially oriented polyester film has a highly crystallized surface that makes the polyester difficult to adhere to an acrylic material coating layer.
- a primer layer is sometimes used between polyester and acrylic polymer layers to improve adhesion.
- Japanese Patent Publication Number JP 2004-299101 of YOKOTA SUNAO et al, entitled “Transparent Laminated Film for Surface Protection” is directed to a transparent composite film with a 10-250 ⁇ thick base layer of biaxially stretched polyester and a 3-20 ⁇ thick hard coat layer of acrylic polymer providing at least 90% light transmission.
- the film is for laminating to a surface of an article, such as a flat panel display member, a nameplate, a window and the like, to protect the article from scratching or other damage.
- US patent application 2008/0038539 of Yokota et al. discloses a composite film having a core layer sandwiched between outer layers to form a base polyester layer.
- a coating layer containing anti-iridescent material covers one side of the base polyester layer and an acrylic coating is disposed over the anti-iridescent coating layer.
- US '539 discloses the effect achieving anti-iridescence by optimizing RI and the coating layer thickness to minimize infringement of reflection light which causes ripples of the spectral reflectance.
- this invention relates to a highly optically clear, composite film having a predominantly thermoplastic polyester base layer and a primer layer of a polyester and polyurethane blend composition.
- the base layer preferably has an A/B/C layered structure with a substantially particle-free core layer B of polyester and outer layers A and C of polyester containing non-polyester, organic and or inorganic particles.
- the primer layer is preferably applied to the base layer from solution that is organic solvent-free and is crosslinked using a carbodiimide crosslinking agent.
- the primer layer and base layer composite can be laminated with a protective layer of primarily acrylic polymer, for example to obtain a solar control film.
- Various layers of the composite and solar control films can contain effective amounts of functional additives, such as UV light blockers.
- Polyurethane in the primer especially in combination with crosslinking by the carbodiimide, provides the acrylic coated polyester base solar control film with notably reduced iridescence and durable adhesion between polyester and acrylic layers in moist and warm service conditions.
- PMMA polymethylmethacrylate
- Fig. 1 is an elevation cross section view of a composite film according to an embodiment of this invention.
- Fig. 2 is an elevation cross section view of a solar control film including the composite film of Fig. 1 and a protective layer according to another embodiment of this invention.
- Fig. 3 is a graphical plot showing hemispherical reflectance (%R) vs wavelength (nm), for a comparative example and for selected operative examples described in greater detail, below.
- FIG. 1 showing a cross section of novel composite film 10.
- This composite film includes a base layer 5 and a primer layer 2.
- the base layer is preferably formed of three sublayers, namely core layer 6, and outer layers 4 and 8.
- Each of the core and outer layers is predominantly polyester and can include other components, such as "UV" (ultraviolet light) blocking additives and particles.
- a solar film 20 includes a protective layer 9 primarily of preferably an acrylic polymer. The protective layer 9 is positioned on the composite film in contact with the primer layer 2.
- the primer layer contains polymeric binder as a major component of the primer layer.
- the polymeric binder may be selected from, but not limited to, polyester, acrylic, polyurethane or the mixture thereof. It is preferred to select a polyester binder because its RI is similar to that of the polyester base layer and thus is helpful to reduce iridescence in the manner as described in US 2008/0038539. Also the polyester binder is very compatible with the base polyester layer to provide preferred adhesion, in general.
- a preferred raw material for the polyester binder is a 30 % solids dispersion, in 2% propanol, aqueous solution commercially available under the name Eastek® 1200 (Eastman Chemicals Company, Kingsport, TN). This polyester has inherent viscosity of 0.34-0.42, glass transition temperature (Tg) of 63 °C and softening point 65°C.
- a traditional approach to reducing iridescence in composite film utilizes refractive index matching techniques.
- the refractive indices of the acrylic material layer and the base biaxially oriented polyester film layer are distinctly different.
- the refractive index difference generates iridescence, as mentioned above. Selecting a primer composition having a RI that matches and complements those of the two layers could reduce iridescence by canceling the effect of disparate refractive indices.
- low iridescence from the polyurethane according to this invention is caused by a light scattering phenomenon (without increasing haze) rather than or in combination with refractive index matching. This is remarkable because the polyurethane can be utilized at a particle size and concentration low enough to allow excellent optical clarity of the overall film yet provide good anti-iridescence performance.
- the implications of this theory include that a polyurethane fine particle dispersion in a primer layer can be utilized to reduce iridescence in a wide variety combinations of base layer and the over coating layer materials.
- low iridescence can be obtained without constraining the primer layer to have a particular refractive index that complements the refractive indices of the other composite film layers, although the combination of the refractive index matching may be preferred.
- the preferred iridescence-reducing component polyurethane particle is an inversely synthesized aliphatic polyurethane.
- inversely synthesized aliphatic polyurethane means that the polyurethane is formed by a process in which (i) non-aromatic organic polyisocyanate and non-aromatic organic polyol are reacted to form a polyurethane polymer, (ii) a neutralizing agent, such as a tertiary amine, is added to water to form an aqueous solution, and then (iii) the polyurethane polymer is added to and dispersed in the aqueous neutralizing agent solution.
- a neutralizing agent such as a tertiary amine
- Neorez RIO 10 DSM NeoResins B.V., Waalwijk, Netherlands.
- inversely synthesized aliphatic polyurethane particles interrelates successfully with several important performance parameter ⁇ of optically clear and solar control films. In addition to exhibiting little or no iridescence, these films are called upon to have high cohesive strength for durability and to be highly transparent with controlled refractive indices. All of these properties can be achieved by these polyurethane particles employed in a primer layer together with polymeric binder and a carbodiimide crosslinking agent in proper proportions.
- the polymeric binder provides structural integrity and serves as a matrix for the dispersed phase of polyurethane particles.
- the crosslinking agent transforms the binder to a rigid network. If too little binder or crosslinking agent is present, the primer will be too weak to durably hold the protective layer to the base layer, Delamination can occur. The polyurethane particles cancel undesirable iridescence. If too little inversely synthesized aliphatic polyurethane particles are present, iridescence can occur. Conversely, if there is too much of binder, polyurethane or crosslinking agent, or the primer layer is too thick, the film can become excessively hazy and thus unsuitable for optical or solar control film utilities.
- the desired particle size of the polyurethane particles within the primer layer is about 1 ⁇ to about 100 ⁇ , preferably about 1 ⁇ to about 60 ⁇ and more preferably about 1 ⁇ to about 25 ⁇ . If the particle size is larger than 100 ⁇ , the coated film surface can develop a grainy appearance. Additionally, the haze value can exceed the less than 3 % desired limit for the coated polyester film (i.e., the base layer/primer/acrylic polymer layer composite), thereby reducing the optical clarity. If the particle size is smaller than 1 ⁇ , the anti-iridescing properties may not be achieved.
- the content of the polyurethane particles in the primer layer can be at least about 0.2 wt% preferably at least about 0.25 wt%, and more preferably about 0.3 wt%. If the content is less than about 0.2 wt% there may not be enough particles to effectively reduce or eliminate iridescence. There can be at most about 2.5 wt% polyurethane particles in the primer layer, preferably at most about 2 wt%, and more preferably at most about 1.5 wt%. If the content is more than about 2.5 wt%, the coated film surface may exceed a less than 3 % haze value, thereby reducing optical clarity.
- the urethane particles are preferably uniformly dispersed within the primer layer.
- the primer layer should be of a consistent dry coating weight and thickness with adequate unagglomerated dispersed particles to sufficiently provide an optically clear coating with a haze value.
- Primer layer-coated base layer (i.e., without an acrylic polymer hard coat layer) of this invention has a haze value of less than 4%.
- the preferred thickness of the primer layer is about 0.03 to 0.15 ⁇ , more preferably, 0.07 to 0.12 ⁇ . If the thickness is less than 0.03 ⁇ , the desired adhesiveness and ant ridescence effect may not be achieved. If the thickness is more than 0.15 ⁇ , then presence of the primer can detract from overall optical clarity and the desired anti-iridescence effect may not be achieved.
- crosslinking strengthens the primer layer by forming the polymeric binder component of the primer layer into a permanent, rigid, network structure. It also produces chemical links between the polymeric binder and the polyester base layer. Crosslinking can be accomplished during and/or after drying solvent from the wet primer layer. Typically a crosslinking agent is added to the primer composition to catalyze the reaction. Many conventional crosslinking agents for reacting polyurethane and polyester may be used, such as carbodiimide, melamine, aziridine, glyoxal, oxazoline and mixtures thereof.
- a preferred carbodiimide crosslinking agent is Solucote® XLl (DSM NeoResins B.V., Waalwijk, Netherlands).
- the crosslinking agent is added to the primer coating liquid and mixed to uniform concentration.
- the preferred content of the crosslinking agent in the primer layer is about 1 wt% to 5 wt%, more preferably, about 2 to 3 wt%. If the content is less than 1 wt%, the organic solvent resistance properties, the inorganic solvent resistance properties and the required adhesive strength of the primer layer will not be achieved. If the content is more than 5 wt%, excessive crosslinking can produce haze value of the base layer/primer layer film greater than 4 %, thereby reducing optical clarity.
- Inversely synthesized aliphatic polyurethane dispersion and the crosslinking agent are mixed with the polymeric binder dispersion in appropriate preselected ratios to form a primer coating liquid.
- the coating liquid can be applied to a surface of the base layer by
- the primer coating liquid is dried by heating and low humidity ventilation to remove liquid dispersing medium (mainly water), and leave a solid content of the primer layer on the base polyester layer.
- Such coating processes can be done after the biaxially oriented polyester film is made, or continuously (i.e., in line) with the biaxially oriented polyester film fabrication. The in line method is preferred to reduce the number of steps and cost of coating.
- polyester suitable to form the base of the biaxially oriented polyester film are, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene isophthalate (IPET) and blends or co-polymers thereof.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- IPET polyethylene isophthalate
- a preferred polyester is PET because of its good balance of cost and performance.
- the base layer of biaxially oriented polyester film may have a mono layer structure or a multi layer structure such as A/B, A/B/A or A/B/C.
- A/B/A or A/B/C structures are preferred in which wherein the core layer B is a polymer layer substantially free of particles and layers A and C each independently can contain organic and/or inorganic particles.
- Core layer B should contain no particles to achieve the preferred optical clarity of at most about 3 % haze value and more preferably at most 2%.
- the outer layers A and C may have desired slip agents such as organic and/or inorganic particles, as disclosed in US patent application 2008/0038539 hereby incorporated herein.
- the biaxially oriented polyester film generally has a thickness of from 1 to 500 ⁇ , preferably from 5 to 350 ⁇ .
- a film thickness of 10 to 50 ⁇ may be preferred for some applications, such as for solar window film use.
- the biaxially oriented polyester film can be produced by any conventional method, such as sequential stretching or simultaneous stretching.
- raw material polyester pellets and additives are fed to a melt processor, such as a mixing extruder.
- the molten material, including the additives, is extruded through a slot die and quenched on a chill roll, in the form of a substantively amorphous film.
- the film may then be reheated and stretched longitudinally and transversely or transversely and
- the longitudinal stretching ratio is from 2 to 6, more preferably from 3 to 4.5.
- the transverse stretching ratio is from 2 to 5, more preferably from 3 to 4.5.
- any second longitudinal or transverse stretching is carried out at a ratio of from 1.1 to 5.
- the first longitudinal stretching may also be carried out at the same time as the transverse stretching (simultaneous stretching).
- Heat setting of the film may follow at an oven temperature of about 180 to 260°C, preferably about 220°C to 250°C. The film may then be cooled and wound up.
- the biaxially oriented polyester film may contain other additives such as, but not limited to, UV stabilizer, hydrolysis resistant agent, optical brightener, frame retardant agent, anti-oxidation agent.
- UV stabilizer to protect the film itself and/or protect article behind the film from UV light.
- UV light blocker "UV blocking additive”, “UV stabilizer”, “UV absorber”, “UV agent” and the like used herein are to be construed interchangeably as referring to components included in the base layer to control the effect of ultraviolet light incident thereon.
- Preferred UV absorbers include 2-hydroxybenzotriazoles, benzoxazinones and the triazines.
- a more preferred UV absorber is 2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethyl- hexyloxy)phenyl]-l,3,5-triazine in terms of the weatherability and UV resistance
- the content of UV absorber may be 0.1 to 2 wt.%. Less than 0.1 wt.% is not enough to be effective, more than 2 wt.% may increase haze, yellow color, affect the mechanical properties of the film, and may create processing issues such as generating undesirable gaseous byproducts and causing migration to the surface (i.e., "blooming") of the UV absorber.
- the polyester film includes 0.1 to 2 wt.% UV absorber; more preferably in the range of 0.5 to 1.5%.
- the biaxially oriented polyester film with primer of this invention can be used as a substrate on which is deposited a coating of acrylic polymer as mentioned above and seen in Fig. 2.
- the acrylic polymer layer is preferred to be optically clear and primarily to provide a hard, strong, impact resistant barrier against physical and chemical attack from environmental conditions to which the desired application of this invention can be exposed in service. That is, such protective layer reduces damage to the film from scratching, denting, moisture, atmospheric-borne contaminants, dirt and permits wash-and-wipe cleaning of the exposed film surface.
- the preferred thickness of the acrylic polymer layer is 2 to 5 ⁇ . Coating layer thickness exceeding 5 ⁇ can adversely affect the refractive index and cause iridescence.
- Acrylic polymers for the protective layer of this invention have repeat units that are derivatives of acrylic acid or substituted acrylic acid. That is, the acrylic polymer is a polymer comprising polymerized units of the following formula (I)
- X H
- R is an alkyl group, a glycidyl group or a hydroxyalkyl group.
- Representative acrylic polymers include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyglycidyl methacrylate, polyhydroxyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyglycidyl acrylate, polyhydroxyethyl acrylate and mixtures of these.
- a protective layer of predominantly acrylic polymer typically has a refractive index of at most about 1.54, and frequently about 1.48 to about 1.54.
- the acrylic polymer layer can include functional additives for specific purposes. Typical additives include antioxidants, impact resistance modifiers, surfactants, light blocking additives and the like. Preferably, the acrylic layer for the desired application such as solar control films contain light blocking additives, particularly UV light blocking materials. The additives are usually present in minor quantities to avoid degrading optical clarity of the acrylic polymer layer. Typically the acrylic polymer layer contains a total of less than about 1 wt% of additives.
- UV light blocking is a significant utility for coated polyester base solar control films.
- PET which is a most desired polyester, alone does not resist transmission of ultraviolet ("UV") light very well.
- UV light blocking is typically improved by placing a coat of an effective UV light blocking material on a PET core layer of a composite film.
- An example of such a material is a polymeric coating, for example, a hard coat such as an acrylic polymer that contains a uniformly dispersed UV light blocking composition.
- the hard coat also physically protects the PET base layer with enhanced impact resistance, abrasion resistance and like properties that lower the risk of damage from denting, scratching and similar other environmental assaults.
- the acrylic polymer layer includes UV light blocking materials.
- the acrylic polymer layer generally comprises greater than about 60 wt.%, preferably greater than about 80 wt.%, more preferably, greater than about 95 wt.%, and most preferably greater than about 98 wt.% of an acrylic polymer and 0 to about 2 wt.% preferably about 0.05 - 1 wt.%, more preferably about 0.1 - 0.5 wt.%, and most preferably about 0.2 - 0.4 wt.% of ultraviolet light blocking component.
- the acrylic polymer can be applied to the primer layer from a solution of the acrylic polymer dissolved in organic solvent. Although the organic solvent is substantially completely removed from the acrylic polymer after lamination, trace amounts of solvent can remain in the acrylic polymer layer.
- trace amounts is meant a minute amount very much less than 1 wt%, and barely detectible by rudimentary chemical analytical methods.
- the compositions in the primer layer are soluble in organic me * dia. Over time, the very slight but finite residual solvent in adjacent acrylic polymer layer can weaken the primer layer. After exposure to heat and moisture under environmental service conditions, cracking and flaking off of the weakened acrylic polymer layer can occur.
- a system for adhering acrylic polymer layer applied from organic solvent media onto optically clear solar control films is much needed in the industry. Therefore, superior organic solvent resistance of the primer layer is also desired and is achieved by crosslinking agent mentioned above.
- the acrylic polymer layer can be laminated to the biaxially oriented polyester film by various known methods.
- laminate is used herein to mean the generic permanent joining of layers to form a composite structure and is not limited to any specific method.
- the acrylic polymer layer can be preformed as a sheet and laminated onto the primer layer using heat and pressure.
- Acrylic polymer can also be extruded onto the primer layer.
- the acrylic polymer can be deposited onto the primer layer from a solution.
- a preferred material for making the acrylic polymer layer of this invention is an acrylic polymer with a UV cure initiator solution in methyl ethyl ketone and isopropyl alcohol solvent.
- the cure initiator is one which can be activated by exposure to UV radiation.
- the solvent is removed to leave a dry, e.g. hard coat of the acrylic polymer for the solar control film or display film such as touch screen.
- a dry acrylic polymer layer e.g. hard coat of the acrylic polymer for the solar control film or display film such as touch screen.
- the primer according to this invention can withstand the solubilizing effect of the presence of such trace residual solvent. It is thus able to create a durable and strong bond between the acrylic polymer layer and the polyester base layer. Consequently, the acrylic polymer layer will resist cracking, chipping, flaking and peeling from the base layer for extended duration.
- Optically clear biaxially oriented polyester film comprising an anti-iridescent primer layer comprising, (A) polymeric binder as a major component of the primer layer, (B) 0.1 - 1.5 wt.% of inversely synthesized aliphatic polyurethane particle as iridescent reducing component, and (C) at least one crosslinking agent, wherein, the haze of the polyester film is 4 % or less.
- optically clear biaxially oriented polyester film of contemplated embodiment 1. which further comprises at least one ultraviolet light absorber.
- optically clear biaxially oriented polyester film of contemplated embodiment 1. for a window film, optical, display, label or photo voltaic application.
- polymethyl methacrylate particles can be dispersed within the primer layer in place of polyurethane particles.
- Polyester film having PMMA particles in the primer layer has been found to have generally equivalent or better film quality and typically superior iridescence-reducing performance than that of film with polyurethane particles.
- PMMA particles Preference is given to using spherical PMMA particles. Particle diameters that are suitable in this invention are in the micron range and are sometimes referred to herein as "microspheres". Hollow microspheres can be used, however, solid PMMA microspheres are preferred.
- the nominal particle size of the PMMA is generally diameter of about 1 ⁇ - 10 ⁇ , preferably about 2 ⁇ - 8 ⁇ , and more preferably about 2 ⁇ - 5 ⁇ .
- the particle size distribution of the PMMA is preferably narrow. Typically greater than 50 wt. % and preferably greater than 80 wt.
- Preferred PMMA particles are commercially available under the name Techpolymer SSX (Sekisui Plastics Co.,Tokyo, Japan). This material is understood to be a cross-linked polymethylmethacrylate in spherical particle form with small particle size distributions. This characteristic makes them well-suited for applications having uniform coating thickness and surface coverage specifications.
- inversely produced polyurethane particles suitable for use in this invention as described above can have slightly more variable particle size distribution. Particle size variability over the area of the primer layer can produce subtle iridescent effects.
- Use of PMMA particles allows greater control over uniformity of particle size within the primer layer. While polyurethane particles as set out above can achieve good quality optical films with reduced iridescence, PMMA particles in the primer layer provide more consistent iridescence reduction.
- the PMMA particles preferred for use in this invention provide a smaller particle size than the preferred polyurethane particles in the range of at most about 60 ⁇ nominal particle size. Smaller particle size coupled with precise particle size distribution of PMMA particles contributes to lower haze across the primer coated PET web.
- low iridescence from the PMMA according to this invention is caused by a light scattering phenomenon (without increasing haze) rather than or in combination with refractive index matching. This is remarkable because the PMMA can be utilized at a particle size and concentration low enough to allow excellent optical clarity of the overall film yet provide good anti-iridescence performance.
- the implications of this theory includes that a PMMA particle dispersion in a primer layer can be utilized to reduce iridescence in a wide variety combinations of base layer and the over coating layer materials.
- low iridescence can be obtained without constraining the primer layer to have a particular refractive index that complements the refractive indices of the other composite film layers, although the combination of the refractive index matching may be employed.
- PMMA particles also influences several important performance parameters of optically clear and solar control films in addition to exhibiting little or no iridescence.
- Optically clear, solar control films are called upon to have high cohesive strength for durability and to be highly transparent with controlled refractive indices. All of these properties can be achieved by these PMMA particles employed in a primer layer together with polymeric binder and a carbodiimide crosslinking agent in proper proportions.
- the polymeric binder provides structural integrity and serves as a matrix for the dispersed PMMA particles.
- the crosslinking agent transforms the binder to a rigid network. If too little binder or crosslinking agent is present, the primer will be too weak to durably hold the protective layer to the base layer. Delamination can occur.
- the description and examples of this disclosure provide guidance for selecting relative amounts of the primer components for successful practice of this invention. The artisan of ordinary skill will be able to adjust proportions of primer components and primer layer thickness according to the principles set forth herein to effectively apply the invention without undue experimentation.
- the content of the PMMA particles in the primer layer can be at least about 0.2 wt% preferably at least about 0.25 wt%, and more preferably about 0.3 wt%. If the content is less than about 0.2 wt% there may not be enough particles to effectively reduce or eliminate iridescence. There can be at most about 2.5 wt% polyurethane particles in the primer layer, preferably at most about 2 wt%, and more preferably at most about 1.5 wt%. If the content is more than about 2.5 wt%, the coated film surface may exceed a less than 3 % haze value, thereby reducing optical clarity.
- the PMMA particles are preferably uniformly dispersed within the primer layer.
- Optically clear biaxially oriented polyester film comprising an anti-iridescent primer layer comprising, (A) polymeric binder as a major component of the primer layer, (B) 0.1 - 1.5 wt.% of PMMA particles (C)
- Haze of films was measured according to ASTM D1003 that determines the percent of transmitted light scattered at more than 2.5° from the incident light.
- a suitable instrument to measure haze is GARDNER HAZE-GARD PLUS No. 4725 hazemeter (BYK- Gardner USA).
- a haze value of 3 % or less is considered acceptable, and 2% or less is preferred.
- Iridescent appearance test Samples of primer layer-coated base layer composite films were coated with an acrylic polymer layer. A solution of acrylic polymer composition with an ultraviolet light cure initiator in methyl ethyl ketone was drawn onto the composite film sample with a No. 2.5 mayer coating rod. The solution coated composite film was passed at a rate of 0.25 ni/s (50 ft min.) through a field of ultraviolet light radiation of 620,000 Watts/m 2 (400 Watts per square inch) to cure and thereby solidify the acrylic polymer composition. The coated film was taped to a black & white lanetta card (9 A). Then the surface of the hard coating was visually inspected under fluorescent lamp illumination and rated according to the scale below.
- Acrylic polymer layer (hard coat) adhesion test (Spray Test): A 12.7 cm x 25.4 cm sample of composite film coated with an acrylic polymer layer as described in the Anti- Iridescent Appearance test method, above, was rolled up in a cylinder of approximately 2.5 cm diameter and secured with a paper clip. The rolled up film was exposed to temperature of 66°C (150°F) for 5 minutes. Thereafter the cylinder was unrolled and the surface of the film was visually inspected and rated according to the scale below.
- Acrylic polymer layer (hard coat) adhesion test (Boil Test): A 12.7cm x 25.4 cm sample of composite film was coated with an acrylic polymer layer as described in the Anti- Iridescent Appearance test method, above. The acrylic polymer layer-coated sample was submerged in boiling water (100°C) for 5 minutes. Thereafter the surface of the film was visually inspected and rated according to the same scale as in the Spray Test for Acrylic polymer layer adhesion.
- a 12.7cm x 25.4 cm sample of composite film was coated with an acrylic polymer layer as described in the Anti-Iridescent Appearance test method, above.
- the acrylic polymer layer surface of the sample was pressed against Scotch Brand 810 adhesive tape to adhere the sample to the tape.
- the tape was peeled away rapidly from the tape in directions,
- the sample and tape were visually inspected for transfer of hard coat acrylic polymer layer to the tape.
- the sample failed the test if any of the acrylic polymer layer transferred to the tape.
- MB- A through MB-D of additives were prepared by individually blending additive components with polyethylene terephthalate in the proportions shown in Table 1.
- MB-A, MB-B and MB-C were produced by adding the additive components to the reaction mass during polymerization of the PET. After synthesis, the PET with additive masterbatch compositions were pelletized.
- MB-D was made by charging the additive with PET pellets (0.65 inherent viscosity) to a twin screw extruder in which the masterbatch composition was melt blended and then pelletized.
- An outer layer composition for a polyester base layer film was made by mixing the masterbatch pellets with PET pellets of inherent viscosity 0.6 in the proportions shown in Table 2. The combination of pellets was dried to less than 100 ppm moisture content then melt-blended in an extruder.
- a core layer was formed by mixing 4 wt. % of MB-D pellets and 96 wt.% PET (inherent viscosity 0.65) pellets, drying the mixture to less than 100 ppm moisture content, then melt-blending the dried pellet mixture in an extruder.
- the outer layer and core layer melt streams were then continuously co-extruded at a temperature of 285 °C through a rectangular joining zone to form an A/B/A multi-layered melt structure.
- the multi-layered melt curtain was quenched on a casting drum at 20°C to form a base layer film.
- the film was oriented in the machine direction by stretching to 3.3 times original length at 95 °C with a roller stretcher.
- a liquid primer composition was formed by combining and blending to uniform composition 19.3 parts weight per hundred ("pph") of a polyester binder dispersion, 0.04 pph of a leveling surfactant, 0.08 pph of an antifoam/leveling surfactant, 0.14 pph of an aqueous silica particle dispersion, and 2.62 pph of an aqueous crosslinking agent dispersion with 76.7 pph deionized water.
- the polyester binder dispersion was a 30 wt % solids polyester particle dispersion in 2% propanol, aqueous solution (Eastek® 1200, Eastman Chemicals Company, Kingsport, TN).
- the leveling surfactant was an ethoxylated acetylenic diol (Surfonyl 440), and the antifoam/leveling surfactant was an ethoxylated acetylenic diol (Surfonyl 420).
- the silica particle dispersion was a 20 wt% aqueous dispersion of synthetic amorphcas silica particles (Grace 703A, W. R. Grace Co. ).
- the crosslinking agent was a 45 wt% aqueous dispersion of polycarbodiimide (Solucote XL1, (DSM NeoResins B.V., Waalwijk,
- the liquid primer composition was coated with a Mayer rod coater onto one side of the base layer film.
- the primer solution was deposited at a rate of about 1.4 g/m 2 of base layer area that was calculated as effective to produce a primer layer of basis weight of 0.10 g/m , 0.1 ⁇ thickness and 97.9 wt.% crosslinked polyester after drying.
- the wet coated film was transported through an oven, preheated at 110°C, and oriented in the transverse direction to 4.0 times original width at 110°C.
- the composite film was heat-set at 236°C and relaxed (5%) using a chain driven stretcher.
- the completed film was then wound up.
- the biaxially oriented polyester film had an A/B/A thickness of 1.5/47/1.5 ⁇ .
- the film was aged seven days at ambient temperature for full crosslinking to occur.
- a methyl ethyl ketone (MEK) based, acrylic hard coat containing a UV cure initiator was drawn onto the primed surface of the substrate polyester composite film above with a size No. 2.5 Mayer coating rod.
- the solution coated composite film was passed at a rate of
- the radiation exposure caused the crosslinking agent to crosslink the polyester binder while volatizing the MEK from the solution to produce an acrylic polymer coated polyester film (having a dry hard coat of acrylic polymer laminated onto the base polyester film above).
- Comparative Example 1 The procedure of Comparative Example 1 was repeated except that the liquid mixture composition for the primer layer consisted of 19.267 pph polyester primer dispersion, 0.04 pph of leveling surfactant, 0.081 pph of antifoam/leveling surfactant, 0.144 pph of aqueous silica particle dispersion, 2.615 pph of aqueous crosslinking agent dispersion and 0.329 pph aqueous polyurethane particle dispersion combined with 76.455 pph deionized water.
- the aqueous polyurethane dispersion was a 32 wt% solids dispersion of particles less than about 100 ⁇ size of inversely synthesized aliphatic polyurethane (Neorez R1010, DSM
- NeoResins B.V., Waalwijk, Netherlands The primer layer drying conditions were same as in Comparative Example 1.
- the dry primer layer basis weight was again about 0.10 g/m 2 and dry primer layer thickness was about 0.1 ⁇ .
- Composition of the dry primer layer was about 96.5 wt% crosslinked polyester and about 1.5 wt% of the inversely synthesized aliphatic polyurethane particles dispersed therein.
- Example 2 The procedure of Example 2 was repeated except that primer solution was deposited onto the base layer at about 2.8 g/m 2 rate such that the primer thickness after drying was 0.2 ⁇ . Analytical results shown in Table 3 indicate that excessive thickness of the primer layer adversely affects optical clarity although iridescence was canceled.,
- Example 2 For Comp. Ex. 6, the procedure of Example 2 was repeated except that a glyoxal crosslinking agent (Freechem® 40DL from Emerald Performance Materials) was substituted for the carbodiimide crosslinking agent.
- Freechem 40DL is an aqueous solution of ethanedial which containing less than 0.2% residual acid.
- melamine formaldehyde resin crosslinking agent Freechem® 40DL from Emerald Performance Materials
- SSX- 102 particles had a nominal diameter of 2 ⁇ . Mean diameter was 2.51 ⁇ , median diameter was 2.46 ⁇ , standard deviation of diameter was 0.25 ⁇ and 97.6 % of the particles had diameter between 2.00 and 3.17 ⁇ .
- SSX-104 particles had a nominal diameter of 4 ⁇ . Mean diameter was 4.298 ⁇ , median diameter was 4.239 ⁇ , standard deviation of diameter was 0.504 ⁇ and 89.4 % of the particles had diameter between 4.00 and 5.04 ⁇ .
- the PMMA particles were Techpolymer SSX-103DXE and had a nominal diameter of 3 ⁇ , however these were hollow microspheres. .
- Example 11 the same aqueous polyurethane dispersion was Used again to essentially repeat Ex. 2 within the range of experimental accuracy. Resulting samples were tested together with samples of Comp. Ex. 1 for adhesion, haze and iridescence, as above. Additional iridescence testing was performed. Analytical methods are described and results are presented in Table 4 below.
- a 2.5 cm x 2.5 cm (1 inch x 1 inch) square hole was cut out near the center of an opaque 21.6 x 27.9 cm (8.5 inch x 11 inch) cardboard sheet to form a mask.
- the mask was laid over the three sample sheets at four observation positions along a corner-to-corner diagonal line of the sheets.
- the diagonal line was oriented with the same orientation for all the sheets (i.e., top left corner to bottom right corner).
- the line was divided into five equal length segments and the four observation positions, OP1-OP4 were located at the interior junctions of the segments.
- Iridescence assessments and haze measurements were obtained at each observation point of the three sheets. Results are shown in Table 4. The average value of iridescence and haze and the standard deviation of the haze from average were calculated. Results show that the iridescence canceling with both PMMA (Exs.8-10) and polyurethane (Ex. 11) in the primer layer was better than when neither of these materials was present (Comp. Ex. 1). Iridescence canceling performance was very good for the polyurethane sample and even better for Ex. 8 with nominal 2 ⁇ and 4 ⁇ particle size, solid PMMA microspheres. Iridescence performance of the larger solid microspheres of Ex. 10 was less effective but acceptable. Ex.
- the instrument was set up in total hemispherical reflectance geometry (8 t) using a high technology 60 mm integrating sphere accessory with the measurement beam focused at the center of the sphere.
- the reflectance factor measurements were relative to barium sulfate instrument calibration standard material E259-98 and CIE 15.2 at ambient temperature (22° ⁇ 1 °C).
- the calibration of the sample was performed at 1.0 nm intervals over the wavelength range from 250nm to 900 nm for 8° hemispherical geometry. In the 250-320 nm wavelength range a deuterium source was used. A tungsten-halogen source was used in the 340-900 nm wavelength range.
- a photomultiplier detector in the UV-Vis (ultraviolet- visual wavelength range) and a lead sulfide detector in the NIR (near infrared wavelength range) were also used.
- Other settings for these analyses were: integrating sphere 60 mm diameter, data mode % reflectance (R), scan speed 300 nm/min., delay 0 second, cycle time 0 min., auto zero before each run off, PMT voltage auto, slit width 4 nm, lamp change mode auto, base line correction userl, high resolution off, D2 lamp on, WI lamp on and R/S on.
- Spectral scans were obtained with each sample in 0° and 90° (mutually orthogonal) orientations and the arithmetical average of the two analyses were used for plots of results.
- Fig. 3 shows that for Comp. Ex. 1, %R fluctuates significantly in the visible wavelength range and thus iridescence is significant.
- Ex. 11 utilized particles of inversely synthesized polyurethane as the iridescence reducing agent in the primer. The reflectance plot shows much less variability of reflectance in the visual range. This indicates that the polyurethane particles were very effective at reducing iridescence.
- the plot for Ex. 8 that used PMMA particles in the primer was extremely constant in the visible range. This performance demonstates the superior ability of PMMA particles to cancel iridescence.
- IriIriIriIri ⁇ Iridescence Haze descence Haze descence Haze descence Haze descence Haze rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%) rating (%)
- A/OP1 2 1.18 1 1,49 3 1.45 ,3 1.64 1 2.57
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US13/688,181 US20130089721A1 (en) | 2011-08-02 | 2012-11-28 | Non-iridescent film with polymeric particles in primer layer |
PCT/US2013/070769 WO2014085139A1 (en) | 2012-11-28 | 2013-11-19 | Non-iridescent film with polymeric particles in primer layer |
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CN114071918A (zh) * | 2021-11-12 | 2022-02-18 | Oppo广东移动通信有限公司 | 壳体、其制备方法及电子设备 |
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JP3790571B2 (ja) * | 1995-11-06 | 2006-06-28 | 株式会社きもと | 光拡散性シートおよびそれを用いた液晶ディスプレイ用バックライトユニット |
US7048823B2 (en) * | 2002-05-20 | 2006-05-23 | Eastman Kodak Company | Acrylic films prepared by coating methods |
CN101300294B (zh) * | 2005-09-12 | 2011-09-07 | 东丽株式会社 | 层合薄膜 |
US20080038539A1 (en) * | 2006-08-08 | 2008-02-14 | Toray Plastics (America), Inc. Lumirror Divison | Anti-iridescent easy handling ultraclear thermoplastic film |
US9109138B2 (en) * | 2011-08-02 | 2015-08-18 | Toray Plastics (America), Inc. | Optically clear biaxially oriented polyester film with anti-iridescent primer layer |
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- 2013-11-19 WO PCT/US2013/070769 patent/WO2014085139A1/en active Application Filing
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CN114071918B (zh) * | 2021-11-12 | 2023-08-22 | Oppo广东移动通信有限公司 | 壳体、其制备方法及电子设备 |
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