US20060019113A1 - Plastic sheet product offering matte appearance and method of preparation - Google Patents
Plastic sheet product offering matte appearance and method of preparation Download PDFInfo
- Publication number
- US20060019113A1 US20060019113A1 US11/194,061 US19406105A US2006019113A1 US 20060019113 A1 US20060019113 A1 US 20060019113A1 US 19406105 A US19406105 A US 19406105A US 2006019113 A1 US2006019113 A1 US 2006019113A1
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- United States
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- plastic sheet
- sheet product
- thermoplastic polymer
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- microns
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- 239000002985 plastic film Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 4
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 87
- 239000010410 layer Substances 0.000 claims abstract description 85
- 239000002245 particle Substances 0.000 claims abstract description 69
- 239000012792 core layer Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 239000011324 bead Substances 0.000 claims description 45
- 238000009792 diffusion process Methods 0.000 claims description 19
- 238000005299 abrasion Methods 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 10
- -1 polyethylenes Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000010998 test method Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 33
- 238000011068 loading method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920006353 Acrylite® Polymers 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
Images
Classifications
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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
- B32B27/06—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
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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
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood 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
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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
-
- 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
-
- 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
- B32B2250/02—2 layers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/408—Matt, dull surface
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
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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
- B32B2307/554—Wear resistance
-
- 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
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the invention relates to a plastic sheet product exhibiting a matte appearance which comprises a core layer and at least one layer of a capstock composition which overlies and is bonded to at least one face of the core layer, where the capstock composition contains particulate inclusions that yield the desired appearance and that emulates frosted glass.
- plastic sheets with a matte finish can be manufactured using textured or embossing calendar rolls.
- Such technology has several disadvantages such as frequent replacement of the rolls, limited predictability and consequent uniformity of the textural designs of the sheets produced, loss of the texture if the sheet is thermoformed, and the like.
- a translucent screen comprising a dispersion of a transparent material in a matrix material in which the refractive index of the transparent material differs slightly from that of the matrix material—see U.S. Pat. No. 2,287,556 and published European Patent Application 0 464 499 A2. It is additionally known to coextrude a matrix layer and one or two layers of a capstock composition containing miscible particles of an impact modifier—see U.S. Pat. No. 5,318,737.
- the sheet materials presently available offer inconsistencies in appearance and difficulty in preparation, as there are often unacceptable variations in the thickness of the matte layer. Also, in the instance where the finish is achieved by surface texturization, the products are more difficult to maintain and clean.
- FIGS. 1A and 1B are pictures of an acrylic sheet with a textured cap layer ( FIG. 1B ) and a textured acrylic sheet produced from a standard manufacturing process ( FIG. 1A ) after four years of natural weathering in Florida in accordance with ASTM G 7 “Standard Practice for Atmospheric Environmental Exposure Testing of Nonmetallic Materials”.
- the pictures demonstrate that an acrylic sheet with a textured cap layer contains less dirt and algae than the standard textured acrylic sheet.
- These pictures demonstrate that acrylic sheets with a textured cap layer are less porous and require less cleaning maintenance than standard textured acrylic sheets.
- the capstock composition comprises a thermoplastic polymer which may be the same or different from the thermoplastic polymer employed for the core layer and will contain a plurality of discrete particles immiscible with, and dispersed in, the capstock thermoplastic polymer. The refractive index of the particles will differ from that of the capstock thermoplastic polymer.
- the sheets of the invention may be prepared with one or more capping layers, and can be prepared by co-extrusion, with a particular technique employing extrusion through a feed block system.
- Such parameters as the size and loading of immiscible particles in the capping layer, and the thickness of all layers, may vary within the ranges recited herein as within the scope of the invention, to achieve particular effects in the final manufactured products.
- the products of the present invention exhibit a combination of improved properties, among them durability and cleanability, and are useful in a variety of applications where a matte or frosted appearance is desirable, among them, for light diffusers and lighting fixtures, privacy panels such as shower doors, retail displays, and projection screens.
- the core layer may consist of a transparent (which is preferred), translucent or opaque first thermoplastic polymer.
- first thermoplastic polymer include polyethylenes, polypropylenes, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methylmethacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, polyvinyl chloride, acrylonitrile-styrene copolymers, polystyrenes, styrene-methylmethacrylate copolymers, polyethyl acrylates, polymethyl-methacrylates, methylmethacrylate-methylacrylate copolymers, polyethylene terephthalates, polyamides, polycarbonates, polyurethanes, silicone resins and the like.
- the polymer is an organic polymer
- the first thermoplastic polymer comprises a methyl methacrylate-methyl acrylate copolymer wherein the methyl methacrylate is present in the amount of about 80 to about 98 wt. %, preferably 93 to 97 wt. %, and even more preferably 94 to 96 wt. %.
- the methyl acrylate is present in the amount of about 2 to about 20 wt. %, preferably 3 to 7 wt. %, and even more preferable about 4 to about 6%.
- the methyl methacrylate-methyl acrylate copolymer may have a melt index of about 1.5 to 5, or 2.0 to 4.0, or even 2.1 to 2.5.
- At least one capstock layer may be included with the core layer and will overly and will be bonded to at least one face of the core layer.
- the plastic sheet product of the invention may have one capstock layer overlying and bonded to one face of the core layer or it may have two capstock layers with each layer overlying and bonded to each face of the core layer.
- the capstock layer composition comprises a second thermoplastic polymer containing a plurality of discrete particles immiscible with, and dispersed in, the polymer.
- the refractive index of the particles will differ from the refractive index of the second thermoplastic polymer.
- the second thermoplastic polymer may be any of the thermoplastic polymers listed above in respect to the first thermoplastic polymer.
- the second thermoplastic polymer may be different from the first thermoplastic polymer. In the latter case, the choices of the first and second thermoplastic polymer should be such that they are sufficiently compatible with one another such that the capstock layer will bond to the face of the core layer, and in one embodiment, is able to so bond when the layers are processed by feedblock coextrusion.
- the second thermoplastic polymer is the same as the first thermoplastic polymer.
- the core layer will have a thickness of about 2 to 13 mm, more particularly, a thickness of from about 3 to about 10 mm, and even more preferably about 3 to about 8 mm.
- the capstock layer(s) may have a thickness of from about 10 to about 400 microns, and more particularly, from about 50 to about 300 microns, and even more particularly, from about 100 to about 275 microns.
- the particles may be immiscible in the second thermoplastic polymer and will typically be present in the amount of about 4 to about 30 wt. %, or for instance 10 to 30 wt. %, preferably about 18 to about 28 wt. %, and even more preferably 22 to 26 wt. %.
- the particles may typically have particle size diameters in the range of about 1 micron to about 60 microns, and preferably be from about 20 to about 80 microns, more preferably about 30 to about 50 microns, and even more preferably be from about 35 to about 45 microns, for instance about 40 microns.
- the particles may comprise a polymer or a pigment.
- polymers include crosslinked polymethylmethacrylate, crosslinked polymethylmethacrylate modified with an acrylate or methacrylate monomer, crosslinked copolymers of methylmethacrylate and styrene, silicone resins and polyallyl methacrylates.
- pigments include barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.
- the second thermoplastic polymer and the particles will typically have refractive indices in the range of about 1.40 to about 1.65, preferably 1.49 to 1.55.
- the difference in the refractive index values of the particles and the second thermoplastic polymer will typically be in the range of about 0.001 to about 0.050, preferably 0.005 to 0.040, and even more preferably about 0.015 to about 0.035.
- the plastic sheet according to the present invention may demonstrate particular Half Angles as measured in degrees and particular Diffusion Factors.
- the Half Angle is a measure of the angle at which the light intensity is halved. It therefore provides a measurement of how the light is diffusing in the sheet.
- the Half Angle is from about 5° to about 10°, preferably from about 7° to about 9°.
- the Diffusion Factor may range from about 2 to about 10, preferably about 3 to about 9, and more preferably from about 4 to about 7 (Diffusion Factor determined by ASTM E167).
- the plastic sheet according to the present invention may demonstrate particular transmission and haze characteristics.
- sheets tested in accordance with the ASTM D 1003 “Test Method for Haze and Luminous Transmittance of Transparent Plastics” using a GretagMacBeth Color Eye-7000A spectrophotometer using Illuminant C and a 2° observer normally demonstrate Transmission of light of at least about 92%, preferably at least about 92.3%, and more preferably, at least about 92.5%.
- sheets measured in accordance with ASTM D 523 “Test Method for Specular Gloss” using BYK-Gardner micro-TRI-gloss (20°, 60° and 85°) with a black felt backing may demonstrate gloss at 20 20 of about 0.5 to 1.0, preferably about 0.6, 0.7 or 0.8.
- the sheets may demonstrate gloss at 60° of about 5 to about 7, preferably, about 5.2 to about 6.6.
- the sheets may also demonstrate gloss at 85° of about 1 to about 6, preferably about 2 to about 5.
- thermoplastic polymer used for the core layer and the second thermoplastic polymer used for the capstock layer were the same: a copolymer of about 94 wt. % methyl methacrylate and about 6 wt. % methyl acrylate having a melt index of 2.1, a weight average molecular weight of 150,000 and a refractive index of 1.490.
- the amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymer for the capstock layer was such that, after feedblock coextrusion of the two layers, the core layer had a thickness of 5.75 mm and the capstock layer had a thickness of 250 microns.
- Particles comprising beads of a crosslinked polymethyl methacrylate with a refractive index of 1.52 and average particle diameters of about 40 microns were combined with the second thermoplastic polymer in an amount of 25 wt. % of the beads.
- the equipment used to coextrude streams of the core layer composition and the capstock layer composition was a conventional extruder equipped with means to melt and pump the two streams.
- a conventional combining feedblock combined the streams in molten form as they exited the extruders and thereafter the streams were fed into a conventional single-manifold sheet die and then exited onto conventional multi-roll polishing units cooling racks and pull rolls.
- only one capstock layer was bonded to one face of the core layer and therefore, the flow channel on one side of the feedblock was closed off so that the capstock layer could flow to only one side of the core layer.
- the equipment was heated to provide a melt temperature of 255° C. and the extrusion process is started. Once the flow is established through the die. the sheet line is strung up in the typical manner with speeds gradually increased to the desired production rate which typically is in the range of 200 to 5,000 pounds per hour.
- Example 1 was repeated so as to prepare a plastic sheet product with capstock layers on both faces of the core layer and a total thickness of about 6 mm. Accordingly, the composition of the core layer and the capstock layer were the same as those of Example 1, and the general manufacturing procedure was also the same, with the exception that the flow channels on both sides of the feed block were opened so that the capstock layer composition could flow to both faces of the core layer.
- the amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymers for each capstock layer was such that, after feedblock coextrusion of the three layers was complete, the core layer had a thickness of 5.5 mm and each capstock layer had a thickness of 250 microns.
- plastic sheet products containing one capstock layer bonded to the core layer were prepared.
- the first thermoplastic polymer used for the core layer and the second thermoplastic polymer used for the capstock layer were the same: a copolymer of about 94 wt. % methyl methacrylate and about 6 wt. % methyl acrylate having a melt index of 2.1, a weight average molecular weight of 150,000 and a refractive index of 1.490.
- the amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymer for the capstock layer was such that, after feedblock coextrusion of the two layers, the core layer had a thickness of of between about 2 and about 9 mm as reflected in Table 1, and the capstock layer had a thickness of between about 125 and 195 microns as reflected in Table 1.
- Particles comprising beads of a crosslinked polymethyl methacrylate with a refractive index of about 1.52 and average particle diameters of about 40 microns may be combined with the second thermoplastic polymer in an amount of about 25 wt. % of the beads.
- the equipment used to coextrude streams of the core layer composition and the capstock layer composition was a conventional extruder equipped with means to melt and pump the two streams.
- a conventional combining feedblock combined the streams in molten form as they exited the extruders and thereafter the streams were fed into a conventional single-manifold sheet die and then exited onto conventional multi-roll polishing units cooling racks and pull rolls.
- only one capstock layer was bonded to one face of the core layer and therefore, the flow channel on one side of the feedblock was closed off so that the capstock layer could flow to only one side of the core layer.
- the equipment was heated to provide a melt temperature of 255° C. and the extrusion process is started. Once the flow is established through the die. the sheet line is strung up in the typical manner with speeds gradually increased to the desired production rate which typically is in the range of 200 to 5,000 pounds per hour.
- Example 1 a comparison was made as to gloss, haze and transmission as between a sheet product having a cap layer with a bead loading of 12% and that of a product having a bead loading of 25%. Accordingly, Example 1 was repeated so as to prepare a plastic sheet product with a capstock on only one side, but with the capstock containing only 12% of the crosslinked PMMA bead particles. The composition and size of the beads was the same as in Example 1. This example produced a sheet product with higher gloss values (6.6% versus 0.7% at 20°), lower haze (43% versus 86.5%), but similar light transmission values (91.7% versus 92.5%) to the product in Example 1. The product in this example visually had a less consistent surface appearance than the material in Example 1.
- Table 2 summarizes the abrasion resistance. The results show that acrylic sheets with a textured cap layer having 12% and 25% weight percent particles produce a lower change in haze and gloss. These results indicate that acrylic sheets with a textured cap layer provide better abrasion resistance than polished and textured acrylic sheets manufactured through standard processes.
- abrasion resistance was determined in relation to capstock layer thickness.
- the thickness of the capstock layer also affects the abrasion resistant properties of the sheet.
- Samples with various capstock layer thicknesses of 40 micron diameter beads were measured for abrasion resistance in accordance with CYRO's steel wool rotary test. The test consisted of rotating “0000” fine steel wool on a sample under a weight of 37 lbs for 100 revolutions. Samples were measured for haze before and after steel wool abrasion. The results are reported as a change in haze. A higher change in haze value indicates lower abrasion resistance.
- Table 4 summarizes the abrasion resistance of the ACRYLITE FF Crystal Ice acrylic sheet.
- Haze and Gloss were calculated for various capstock layers made according to Example 2 and described in Table 6.
- the capstock layers contained 5 micron diameter beads having a refractive index of 1.54.
- a BYK-Gardner TCS-35 Spectrophotometer was used for light transmission and to measure Haze.
- a BYK-Gardner Micro-Tri-Gloss Gloss Meter was used for Gloss measurements. The results are set forth in Table 6.
- Diffusion Factor and Half Angle measurements are important for lighting fixtures, light diffusers and projection screens.
- Diffusion Factor and Half Angle measurements were calculated for various sheets made according to Example 2 and described in Table 1.
- the total sheet thickness ranged from about 3 mm to about 6 mm
- the capstock layer thickness ranged from about 102 to about 330 microns as set forth in Table 7.
- the capstock layers contained either 5 or 40 micron diameter beads having a refractive index of 1.54 or 1.52 respectively.
- Diffusion Factor and Half angle measurements were performed with a device made at Cyro Industries. Commercial equipment is available, but the Cyro device is a simplified version built in house.
- the Cyro device consists of a variable power light source (Dolan-Jenner, Fiber-Lite PL900 Illuminator), fiber optic light guide, light meter ( Minolta LS100 Luminance Meter ) and optical element bars, mounting hardware and protractor rotating base to mount the various parts on.
- the equipment is arranged such that the angle of the light source can easily be adjusted, and the sample with respect to the light meter may be adjusted to measure light intensities at the surface of the sample to be measured at various angles. The results are set forth in Table 7.
- the Half Angle is a measure of the angle at which the light intensity is halved. It therefore provides a measurement of how the light is diffusing in the sheet.
- the Diffusion Factor is obtained by measuring light intensity at three different angles, namely 5°, 20° and 70°.
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Abstract
A plastic sheet product having a matte finish comprises a core layer of a thermoplastic polymer and at least one layer of a capstock composition which overlies, and is bonded to, at least one face of the core layer. The capstock composition comprises the same or different thermoplastic polymer and contains a plurality of discrete particles immiscible with and dispersed in the thermoplastic polymer of the capstock composition. The sheet product may be prepared by the co-extrusion of the thermoplastic polymer and the capstock composition, and in a particular embodiment, such co-extrusion may be conducted by means of a feedblock. In a particular embodiment, the thermoplastic polymer of the core layer and that of the capstock composition may be the same, such as in the instance of a methylmethacrylate-methylacrylate copolymer. Sheet products prepared in accordance with the invention exhibit improved post-processability and ease of surface maintenance, and may be fabricated into a variety of products including light diffusers, projection screens, and the like.
Description
- The present application is a continuation-in-part of co-pending non-provisional application Ser. No. 09/817,788, filed Mar. 26, 2001, which, in turn, is based upon Provisional Application Ser. No. 60/192,057 filed on Mar. 24, 2000. Applicants claim the benefits of 35 U.S.C. § 120 as to the said non-provisional application, and 35 U.S.C. § 119(e) as to the said provisional application, and the disclosures of both of said applications are incorporated herein in their entireties.
- 1. Field of the Invention
- The invention relates to a plastic sheet product exhibiting a matte appearance which comprises a core layer and at least one layer of a capstock composition which overlies and is bonded to at least one face of the core layer, where the capstock composition contains particulate inclusions that yield the desired appearance and that emulates frosted glass.
- 2. Description of Related Art
- It is well known that plastic sheets with a matte finish can be manufactured using textured or embossing calendar rolls. However, such technology has several disadvantages such as frequent replacement of the rolls, limited predictability and consequent uniformity of the textural designs of the sheets produced, loss of the texture if the sheet is thermoformed, and the like.
- It is also known to prepare a translucent screen comprising a dispersion of a transparent material in a matrix material in which the refractive index of the transparent material differs slightly from that of the matrix material—see U.S. Pat. No. 2,287,556 and published European Patent Application 0 464 499 A2. It is additionally known to coextrude a matrix layer and one or two layers of a capstock composition containing miscible particles of an impact modifier—see U.S. Pat. No. 5,318,737.
- Among the shortcomings of the prior art, the sheet materials presently available offer inconsistencies in appearance and difficulty in preparation, as there are often unacceptable variations in the thickness of the matte layer. Also, in the instance where the finish is achieved by surface texturization, the products are more difficult to maintain and clean.
- None of the known technology effectively addresses the shortcomings of the prior art with respect to the preparation and resultant quality of the matte appearance plastic sheeting, and it is toward the preparation of products that do not suffer from these shortcomings that the present invention is directed.
-
FIGS. 1A and 1B are pictures of an acrylic sheet with a textured cap layer (FIG. 1B ) and a textured acrylic sheet produced from a standard manufacturing process (FIG. 1A ) after four years of natural weathering in Florida in accordance with ASTM G 7 “Standard Practice for Atmospheric Environmental Exposure Testing of Nonmetallic Materials”. The pictures demonstrate that an acrylic sheet with a textured cap layer contains less dirt and algae than the standard textured acrylic sheet. These pictures demonstrate that acrylic sheets with a textured cap layer are less porous and require less cleaning maintenance than standard textured acrylic sheets. - It has now been found that it is possible to inexpensively prepare a plastic sheet product that offers a matte appearance without the aforementioned drawbacks, which sheet product comprises a core layer of a thermoplastic polymer and at least one layer of a capstock composition which provides the matte appearance to the sheet product, and that overlies and is bonded to at least one face of the core layer. The capstock composition comprises a thermoplastic polymer which may be the same or different from the thermoplastic polymer employed for the core layer and will contain a plurality of discrete particles immiscible with, and dispersed in, the capstock thermoplastic polymer. The refractive index of the particles will differ from that of the capstock thermoplastic polymer.
- Accordingly, in a first aspect of the invention, the sheets of the invention may be prepared with one or more capping layers, and can be prepared by co-extrusion, with a particular technique employing extrusion through a feed block system. Such parameters as the size and loading of immiscible particles in the capping layer, and the thickness of all layers, may vary within the ranges recited herein as within the scope of the invention, to achieve particular effects in the final manufactured products.
- The products of the present invention exhibit a combination of improved properties, among them durability and cleanability, and are useful in a variety of applications where a matte or frosted appearance is desirable, among them, for light diffusers and lighting fixtures, privacy panels such as shower doors, retail displays, and projection screens.
- For the purposes of the present invention the core layer may consist of a transparent (which is preferred), translucent or opaque first thermoplastic polymer. Suitable examples of the first thermoplastic polymer include polyethylenes, polypropylenes, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methylmethacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, polyvinyl chloride, acrylonitrile-styrene copolymers, polystyrenes, styrene-methylmethacrylate copolymers, polyethyl acrylates, polymethyl-methacrylates, methylmethacrylate-methylacrylate copolymers, polyethylene terephthalates, polyamides, polycarbonates, polyurethanes, silicone resins and the like. In the instance where the polymer is an acrylic, the first thermoplastic polymer will typically have a weight average molecular weight of about 100,000 to about 175,000, preferably 125,000 to 150,000.
- Preferably, the first thermoplastic polymer comprises a methyl methacrylate-methyl acrylate copolymer wherein the methyl methacrylate is present in the amount of about 80 to about 98 wt. %, preferably 93 to 97 wt. %, and even more preferably 94 to 96 wt. %. The methyl acrylate is present in the amount of about 2 to about 20 wt. %, preferably 3 to 7 wt. %, and even more preferable about 4 to about 6%. The methyl methacrylate-methyl acrylate copolymer may have a melt index of about 1.5 to 5, or 2.0 to 4.0, or even 2.1 to 2.5.
- At least one capstock layer may be included with the core layer and will overly and will be bonded to at least one face of the core layer. Thus, the plastic sheet product of the invention may have one capstock layer overlying and bonded to one face of the core layer or it may have two capstock layers with each layer overlying and bonded to each face of the core layer.
- The capstock layer composition comprises a second thermoplastic polymer containing a plurality of discrete particles immiscible with, and dispersed in, the polymer. The refractive index of the particles will differ from the refractive index of the second thermoplastic polymer. The second thermoplastic polymer may be any of the thermoplastic polymers listed above in respect to the first thermoplastic polymer. The second thermoplastic polymer may be different from the first thermoplastic polymer. In the latter case, the choices of the first and second thermoplastic polymer should be such that they are sufficiently compatible with one another such that the capstock layer will bond to the face of the core layer, and in one embodiment, is able to so bond when the layers are processed by feedblock coextrusion. In a particular embodiment, the second thermoplastic polymer is the same as the first thermoplastic polymer.
- Typically, the core layer will have a thickness of about 2 to 13 mm, more particularly, a thickness of from about 3 to about 10 mm, and even more preferably about 3 to about 8 mm. The capstock layer(s) may have a thickness of from about 10 to about 400 microns, and more particularly, from about 50 to about 300 microns, and even more particularly, from about 100 to about 275 microns.
- The particles may be immiscible in the second thermoplastic polymer and will typically be present in the amount of about 4 to about 30 wt. %, or for instance 10 to 30 wt. %, preferably about 18 to about 28 wt. %, and even more preferably 22 to 26 wt. %. The particles may typically have particle size diameters in the range of about 1 micron to about 60 microns, and preferably be from about 20 to about 80 microns, more preferably about 30 to about 50 microns, and even more preferably be from about 35 to about 45 microns, for instance about 40 microns. In some embodiments at least about half of the particles will be greater than about 30 microns and at least about half of the particles will be less than about 50 microns in diameter. In other embodiments, at least about two thirds of the particles will be greater than about 25 microns in diameter. The particles may comprise a polymer or a pigment. Useful examples of such polymers include crosslinked polymethylmethacrylate, crosslinked polymethylmethacrylate modified with an acrylate or methacrylate monomer, crosslinked copolymers of methylmethacrylate and styrene, silicone resins and polyallyl methacrylates. Useful non-limiting examples of such pigments include barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.
- The second thermoplastic polymer and the particles will typically have refractive indices in the range of about 1.40 to about 1.65, preferably 1.49 to 1.55. The difference in the refractive index values of the particles and the second thermoplastic polymer will typically be in the range of about 0.001 to about 0.050, preferably 0.005 to 0.040, and even more preferably about 0.015 to about 0.035.
- The plastic sheet according to the present invention may demonstrate particular Half Angles as measured in degrees and particular Diffusion Factors. The Half Angle is a measure of the angle at which the light intensity is halved. It therefore provides a measurement of how the light is diffusing in the sheet. The Diffusion Factor is obtained by measuring light intensity at three different angles, namely 5°, 20° and 70°. The values are then related by the following formula:
light intensity at 70°+light intensity at 20°×100=Diffusion Factor 2×(light intensity at 520 )
In particular embodiments, the Half Angle is from about 5° to about 10°, preferably from about 7° to about 9°. Additionally the Diffusion Factor may range from about 2 to about 10, preferably about 3 to about 9, and more preferably from about 4 to about 7 (Diffusion Factor determined by ASTM E167). - The plastic sheet according to the present invention may demonstrate particular transmission and haze characteristics. In some embodiments, sheets tested in accordance with the ASTM D 1003 “Test Method for Haze and Luminous Transmittance of Transparent Plastics” using a GretagMacBeth Color Eye-7000A spectrophotometer using Illuminant C and a 2° observer normally demonstrate Transmission of light of at least about 92%, preferably at least about 92.3%, and more preferably, at least about 92.5%. In some embodiments, sheets measured in accordance with ASTM D 523 “Test Method for Specular Gloss” using BYK-Gardner micro-TRI-gloss (20°, 60° and 85°) with a black felt backing may demonstrate gloss at 2020 of about 0.5 to 1.0, preferably about 0.6, 0.7 or 0.8. The sheets may demonstrate gloss at 60° of about 5 to about 7, preferably, about 5.2 to about 6.6. The sheets may also demonstrate gloss at 85° of about 1 to about 6, preferably about 2 to about 5.
- The following nonlimiting examples are illustrative of the invention. Unless otherwise indicated, all amounts and percentages are on a weight basis.
- In this example, a plastic sheet product containing one capstock layer bonded to the core layer was prepared. The first thermoplastic polymer used for the core layer and the second thermoplastic polymer used for the capstock layer were the same: a copolymer of about 94 wt. % methyl methacrylate and about 6 wt. % methyl acrylate having a melt index of 2.1, a weight average molecular weight of 150,000 and a refractive index of 1.490. The amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymer for the capstock layer was such that, after feedblock coextrusion of the two layers, the core layer had a thickness of 5.75 mm and the capstock layer had a thickness of 250 microns. Particles comprising beads of a crosslinked polymethyl methacrylate with a refractive index of 1.52 and average particle diameters of about 40 microns were combined with the second thermoplastic polymer in an amount of 25 wt. % of the beads.
- The equipment used to coextrude streams of the core layer composition and the capstock layer composition was a conventional extruder equipped with means to melt and pump the two streams. A conventional combining feedblock combined the streams in molten form as they exited the extruders and thereafter the streams were fed into a conventional single-manifold sheet die and then exited onto conventional multi-roll polishing units cooling racks and pull rolls. In this example, only one capstock layer was bonded to one face of the core layer and therefore, the flow channel on one side of the feedblock was closed off so that the capstock layer could flow to only one side of the core layer.
- The equipment was heated to provide a melt temperature of 255° C. and the extrusion process is started. Once the flow is established through the die. the sheet line is strung up in the typical manner with speeds gradually increased to the desired production rate which typically is in the range of 200 to 5,000 pounds per hour.
- Example 1 was repeated so as to prepare a plastic sheet product with capstock layers on both faces of the core layer and a total thickness of about 6 mm. Accordingly, the composition of the core layer and the capstock layer were the same as those of Example 1, and the general manufacturing procedure was also the same, with the exception that the flow channels on both sides of the feed block were opened so that the capstock layer composition could flow to both faces of the core layer. The amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymers for each capstock layer was such that, after feedblock coextrusion of the three layers was complete, the core layer had a thickness of 5.5 mm and each capstock layer had a thickness of 250 microns.
- In this example, as in Example 1, plastic sheet products containing one capstock layer bonded to the core layer were prepared. The first thermoplastic polymer used for the core layer and the second thermoplastic polymer used for the capstock layer were the same: a copolymer of about 94 wt. % methyl methacrylate and about 6 wt. % methyl acrylate having a melt index of 2.1, a weight average molecular weight of 150,000 and a refractive index of 1.490. The amount of the first thermoplastic composition for the core layer in relation to the second thermoplastic polymer for the capstock layer was such that, after feedblock coextrusion of the two layers, the core layer had a thickness of of between about 2 and about 9 mm as reflected in Table 1, and the capstock layer had a thickness of between about 125 and 195 microns as reflected in Table 1. Particles comprising beads of a crosslinked polymethyl methacrylate with a refractive index of about 1.52 and average particle diameters of about 40 microns may be combined with the second thermoplastic polymer in an amount of about 25 wt. % of the beads.
- The equipment used to coextrude streams of the core layer composition and the capstock layer composition was a conventional extruder equipped with means to melt and pump the two streams. A conventional combining feedblock combined the streams in molten form as they exited the extruders and thereafter the streams were fed into a conventional single-manifold sheet die and then exited onto conventional multi-roll polishing units cooling racks and pull rolls. In this example, only one capstock layer was bonded to one face of the core layer and therefore, the flow channel on one side of the feedblock was closed off so that the capstock layer could flow to only one side of the core layer.
- The equipment was heated to provide a melt temperature of 255° C. and the extrusion process is started. Once the flow is established through the die. the sheet line is strung up in the typical manner with speeds gradually increased to the desired production rate which typically is in the range of 200 to 5,000 pounds per hour.
TABLE 1 Thickness 3 3 6 6 6 6 6 9 9 9 9 (mm) 0917- 0917- 0917- 0917- 0917- 0917- 0917- 0917- 0917- 5169- 5169- Color 9 9 9 9 9 9 9 9 9 8 8 Skid 1298 1299 1307 1308 1309 1310 1311 1316 1324 1325 1326 Cap thickness 175 175 314 255 295 286 263 376 341 370 390 (microns) across sheet 190 166 260 287 320 290 261 355 325 354 435 195 172 270 240 339 287 289 312 308 317 422 185 159 235 231 315 237 251 323 269 286 390 171 165 224 220 282 216 230 260 263 280 371 155 137 210 214 299 205 213 263 245 238 323 145 138 218 208 250 218 219 231 266 239 293 139 148 242 205 245 232 220 268 231 234 288 140 130 211 195 207 212 206 249 240 251 291 125 132 201 198 198 179 208 240 255 224 262 145 123 233 196 200 192 204 233 228 205 265 125 112 201 168 170 177 195 255 234 215 238 122 135 212 184 158 181 201 240 223 243 233 140 144 199 205 177 190 215 246 264 247 231 131 127 224 215 193 210 236 267 265 253 222 130 130 242 220 184 212 230 293 269 272 240 135 124 235 245 205 225 241 281 307 293 235 131 127 268 263 212 223 247 305 317 293 256 129 122 280 282 190 237 278 336 338 317 232 133 121 285 292 220 265 274 348 349 375 239 147 157 310 299 250 301 311 395 390 375 276 146 158 336 297 248 314 306 390 402 428 325 149 160 333 302 256 298 331 429 386 407 345 145 146 298 291 301 290 312 416 408 373 335 Average 147.0 142.0 251.7 238.0 238.1 236.5 247.5 304.6 296.8 295.4 297.4 (microns) St. Dev 20.67 17.79 42.02 40.95 51.87 42.60 39.30 61.00 57.63 64.03 64.35 Maximum 195 175 336 302 339 314 331 429 408 428 435 Minimum 122 112 199 168 158 177 195 231 223 205 222 Range 73 63 137 134 181 137 136 198 185 223 213 Total thickness 2.85 2.85 5.85 5.85 5.85 5.85 5.85 8.85 8.85 8.85 (mm) Cap (mm) 0.147 0.142 0.252 0.238 0.238 0.237 0.248 0.305 0.297 0.295 - In this example, a comparison was made as to gloss, haze and transmission as between a sheet product having a cap layer with a bead loading of 12% and that of a product having a bead loading of 25%. Accordingly, Example 1 was repeated so as to prepare a plastic sheet product with a capstock on only one side, but with the capstock containing only 12% of the crosslinked PMMA bead particles. The composition and size of the beads was the same as in Example 1. This example produced a sheet product with higher gloss values (6.6% versus 0.7% at 20°), lower haze (43% versus 86.5%), but similar light transmission values (91.7% versus 92.5%) to the product in Example 1. The product in this example visually had a less consistent surface appearance than the material in Example 1.
- In this experiment abrasion resistance was compared between standard polished acrylic sheets and standard texture acrylic sheet and acrylic sheet with a textured capstock layer. Acrylic sheets with a textured cap layer provide better abrasion resistance than acrylic sheets, polished and textured, which are produced from standard manufacturing processes. Samples of standard polished acrylic sheet, standard texture acrylic sheet and acrylic sheet with a textured cap layer with various loadings of beads approximately 40 microns in diameter were tested in accordance with DIN 52 348 “Resistance to Falling Sand”. The test measures the change in haze and gloss at 60° after the samples have been subjected to 3000 g of falling sand in diameters 0.5-0.7 mm. A lower change in haze and gloss value indicates better abrasion resistance properties. Table 2 summarizes the abrasion resistance. The results show that acrylic sheets with a textured cap layer having 12% and 25% weight percent particles produce a lower change in haze and gloss. These results indicate that acrylic sheets with a textured cap layer provide better abrasion resistance than polished and textured acrylic sheets manufactured through standard processes.
TABLE 2 Change in Haze Change in Gloss Sheet Material (%) (60°) Standard polished acrylic sheet 30.9 89.9 (ACRYLITE ® FF) Standard textured acrylic sheet 27.1 64.1 (ACRYLITE ® FF P-99) Textured cap layer acrylic sheet 8.72 8.0 with 12% bead loading (ACRYLITE ® FF Crystal Ice) Textured cap layer acrylic sheet 0.75 0.7 with 25% bead loading (ACRYLITE ® FF Crystal Ice) - In this experiment abrasion resistance was determined in relation to weight percent of beads in capstock layer. The abrasion resistance properties of an acrylic sheet with a textured capstock layer varies with the weight percent of beads present in the capstock layer. Acrylic sheets with a textured capstock layer having various weight percentages of beads measuring approximately 5 microns in diameter were tested in accordance with DIN 52 348 “Resistance to Falling Sand”. The samples were measured for a change in 60° gloss after being subjected to 3000 kg of sand. Table 3 summarizes the change in gloss with various bead loadings. The results demonstrate that as the weight percentage of beads is increased to 10%, the abrasion resistance of the sheet improves dramatically. However, the results also show that the abrasion resistance properties of the material do not continually improve when the bead loading exceeds 10%.
TABLE 3 Bead Loading Change in 60° Gloss 5% 24.5 10% 6.5 15% 4.8 20% 4.7 - In this experiment, abrasion resistance was determined in relation to capstock layer thickness. The thickness of the capstock layer also affects the abrasion resistant properties of the sheet. Samples with various capstock layer thicknesses of 40 micron diameter beads were measured for abrasion resistance in accordance with CYRO's steel wool rotary test. The test consisted of rotating “0000” fine steel wool on a sample under a weight of 37 lbs for 100 revolutions. Samples were measured for haze before and after steel wool abrasion. The results are reported as a change in haze. A higher change in haze value indicates lower abrasion resistance. Table 4 summarizes the abrasion resistance of the ACRYLITE FF Crystal Ice acrylic sheet. The results show that as the thickness of the cap layer increases, the change in haze decreases. These results indicate that the abrasion resistance of the sheet improves as the thickness of the cap layer increases.
TABLE 4 Cap Layer Thickness (microns) Change in Haze (%) 100 19.96 186 8.22 235 6.72 509 1.41 - In this experiment optical properties were compared. Samples were tested in accordance with the ASTM D 1003 “Test Method for Haze and Luminous Transmittance of Transparent Plastics” using GretagMacBeth Color Eye-7000A spectrophotometer using Illuminant C and a 2° observer. Samples were also measured in accordance with ASTM D 523 “Test Method for Specular Gloss” using BYK-Gardner micro-TRI-gloss (20°, 60° and 85°) with a black felt backing. Table 5 summarizes the optical properties. The results demonstrate that acrylic sheets with a textured capstock layer produce lower gloss values than acrylic sheets, polished and testured, produced by standard manufacturing processes. The results also demonstrate that acrylic sheets with a textured cap layer having 25% weight percent beads produce more consistent gloss readings within a large range of thicknesses than textured acrylic sheet manufactured from standard processes. Capstock layers having approximately 40 micron diameter beads produce lower gloss values than capstock layers having approximately 5 micron diameter beads.
TABLE 5 Thickness Transmission Haze Gloss Sheet Material (mm) (%) (%) 20° 60° 85° Standard polished acrylic sheet 3 92.3 0.18 152 147 117 Standard textured acrylic sheet 3 92.0 1.58 79.1 115 92.2 Standard textured acrylic sheet 6 91.7 2.18 73.8 107 94.9 12% 40 micron beads in cap layer 3 91.7 43.0 6.6 24.0 14.2 25% 40 micron beads in cap layer 3 92.5 86.5 0.7 6.6 1.6 25% 40 micron beads in cap layer 4.5 92.5 90.5 0.6 5.2 2.0 25% 40 micron beads in cap layer 6 92.8 90.6 0.8 5.7 2.7 25% 40 micron beads in cap layer 9 92.3 89.8 0.8 6.3 5.1 5% 5 micron beads in cap layer 6 89.2 90.3 12.6 49.5 76.0 10% 5 micron beads in cap layer 6 87.5 95.5 2.1 16.6 33.5 15% 5 micron beads in cap layer 6 83.8 97.0 2.1 15.3 36.1 20% 5 micron beads in cap layer 6 81.5 97.5 1.6 13.1 32.0 - Haze and Gloss were calculated for various capstock layers made according to Example 2 and described in Table 6. The capstock layers contained 5 micron diameter beads having a refractive index of 1.54. A BYK-Gardner TCS-35 Spectrophotometer was used for light transmission and to measure Haze. A BYK-Gardner Micro-Tri-Gloss Gloss Meter was used for Gloss measurements. The results are set forth in Table 6.
TABLE 6 5 micron, 1.54 rf beads Sample ID Light Light (beads in Transmission Transmission % Y Haze % Y Haze weight %) (texture in) % (texture out) % (texture in) (texture out) 20° Gloss 60° Gloss 85° Gloss Crystal Ice 87.52 88.85 78.02 79.06 1.1 10.9 5.0 20% beads 81.74 81.54 97.35 97.46 3.1 20.1 31.4 15% beads 84.15 83.82 96.88 96.96 3.3 24.7 37.3 10% beads 87.13 87.49 95.31 95.48 2.9 21.8 30.3 5% beads 89.27 89.20 89.93 90.33 9.0 41.6 64.7
These data demonstrate that the weight percent of beads in the capstock layer affects gloss values rather dramatically with relatively less effects on haze. - For lighting fixtures, light diffusers and projection screens, Diffusion Factor and Half Angle measurements are important. In this experiment, Diffusion Factor and Half Angle measurements were calculated for various sheets made according to Example 2 and described in Table 1. The total sheet thickness ranged from about 3 mm to about 6 mm, and the capstock layer thickness ranged from about 102 to about 330 microns as set forth in Table 7. The capstock layers contained either 5 or 40 micron diameter beads having a refractive index of 1.54 or 1.52 respectively. Diffusion Factor and Half angle measurements were performed with a device made at Cyro Industries. Commercial equipment is available, but the Cyro device is a simplified version built in house. The Cyro device consists of a variable power light source (Dolan-Jenner, Fiber-Lite PL900 Illuminator), fiber optic light guide, light meter ( Minolta LS100 Luminance Meter ) and optical element bars, mounting hardware and protractor rotating base to mount the various parts on. The equipment is arranged such that the angle of the light source can easily be adjusted, and the sample with respect to the light meter may be adjusted to measure light intensities at the surface of the sample to be measured at various angles. The results are set forth in Table 7.
- The Half Angle is a measure of the angle at which the light intensity is halved. It therefore provides a measurement of how the light is diffusing in the sheet. The Diffusion Factor is obtained by measuring light intensity at three different angles, namely 5°, 20° and 70°. The values are then related by the following formula:
TABLE 7 Diffusion Factor and Half Angle Measurements for Various Cap Layered Materials All based on acrylic Bead Bead Cap Half Size % Beads Ref Sheet Thickness Angle Diffusion Sample (micron) in Cap Index Thickness (microns) (°) Factor 1 5 5 1.54 6 mm 200 10.0 9.8 2 5 10 1.54 6 mm 330 30.0 42.7 3 5 15 1.54 6 mm 210 24.0 34.3 4 5 20 1.54 6 mm 204 43.0 54.3 5 40 25 1.52 6 mm 174 7.0 3.7 6 40 25 1.52 4.5 mm 195 9.0 6.8 7 40 25 1.52 3 mm 125 8.0 6.1 8 40 12 1.52 3 mm 102 1.8 1.2 - These results demonstrate that the effect of bead size and concentration as well as cap layer thickness on light diffusion for applications such as light diffusing panels and screens.
- This invention may be embodied in other forms or carried out in other ways without departing from the spirit or essential characteristics thereof. The present disclosure is therefore to be considered as in all respects illustrative and not restrictive, the scope of the invention being indicated by the appended Claims, and all changes which come within the meaning and range of equivalency are intended to be embraced therein.
Claims (81)
1. A plastic sheet product having a matte finish comprising a core layer of a first thermoplastic polymer and at least one layer of a capstock composition overlying and bonded to at least one face of the core layer, said capstock composition comprising a second thermoplastic polymer having a refractive index and containing a plurality of discrete particles immiscible with, and dispersed in, the second thermoplastic polymer and having a refractive index, wherein the refractive index of the particles differs from the refractive index of the second thermoplastic polymer.
2. The plastic sheet product of claim 1 wherein the first thermoplastic polymer and the second thermoplastic polymer are independently selected from the group consisting of polyethylenes, polypropylenes, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methylmethacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, polyvinyl chloride, methylmethacrylate-ethylacrylate copolymers acrylonitrile-styrene copolymers, polystyrenes, styrene-methylmethacrylate copolymers, polyethyl acrylates, polymethyl methacrylates, methylmethacrylate-methylacrylate copolymers, polyethylene terephthalates, polyamides, polycarbonates, polyurethanes and silicone resins.
3. The plastic sheet product of claim 1 wherein the first thermoplastic polymer and the second thermoplastic polymer are transparent.
4. The plastic sheet product of claim 1 wherein the second thermoplastic polymer is the same as the first thermoplastic polymer.
5. The plastic product of claim 3 wherein the second and the first thermoplastic polymer comprise a methyl methacrylate-methyl acrylate copolymer.
6. The plastic sheet product of claim 5 , wherein the copolymer comprises about 80 to about 98 wt. % methyl methacrylate and about 2 to about 20 wt. % methyl acrylate.
7. The plastic sheet product of claim 6 , wherein the copolymer comprises 93 to 97 wt. % methyl methacrylate and 3 to 7 wt. % methyl acrylate.
8. The plastic sheet product of claim 1 , wherein the capstock composition is bonded to only one face of the core layer.
9. The plastic sheet product of claim 1 , wherein the capstock composition is bonded to both faces of the core layer.
10. The plastic sheet product of claim 1 , wherein the first and second thermoplastic polymers have weight average molecular weights in the range of about 100,000 to about 175,000.
11. The plastic sheet product of claim 10 , wherein the first and second thermoplastic polymers have weight average molecular weights in the range of 125,000 to 150,000.
12. The plastic sheet product of claim 1 , wherein the core layer has a thickness of about 2 to about 13 mm and said at least one capstock layer has a thickness of about 10 to about 400 microns.
13. The plastic sheet product of claim 12 , wherein the core layer has a thickness of 4 to 10 mm and said at least one capstock layer has a thickness of 150 to 300 microns.
14. The plastic sheet product of claim 1 , wherein the particles have particle size diameters in the range of about 1 micron to about 60 microns.
15. The plastic sheet product of claim 14 , wherein the particles have particle size diameters in the range of 30 to 50 microns.
16. The plastic sheet product of claim 1 , wherein the particles are dispersed in the second thermoplastic polymer in an amount of about 4 to about 30 wt. %.
17. The plastic sheet product of claim 16 , wherein the particles are dispersed in the second thermoplastic polymer in an amount of 22 to 26 wt. %.
18. The plastic sheet product of claim 1 , wherein the refractive indices of the particles and the second thermoplastic polymer are in the range of about 1.40 to about 1.65.
19. The plastic sheet product of claim 18 , wherein the refractive indices of the particles and the second thermoplastic polymer are in the range of 1.49 to 1.55.
20. The plastic sheet product of claim 1 , wherein the refractive index of the particles differs from the refractive index of the second thermoplastic polymer by a value in the range of about 0.001 to about 0.030.
21. The plastic sheet product of claim 20 , wherein the refractive index of the particles differs from the refractive index of the second thermoplastic polymer by a value in the range of 0.005 to 0.020.
22. The plastic sheet product of claim 1 , wherein the particles are comprised of a polymer or a pigment.
23. The plastic sheet product of claim 22 , wherein the particles are comprised of a polymer selected from the group consisting of crosslinked polymethylmethacrylate, crosslinked polymethylmethacrylate modified with an acrylate or methacrylate monomer, crosslinked copolymers of methylmethacrylate and styrene, silicone resins and polyallyl methacrylates.
24. The plastic sheet product of claim 22 , wherein the pigment is selected from the group consisting of barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.
25. The plastic sheet product of claim 1 , wherein plastic sheet is formed by feedblock coextrusion of the core layer and the capstock composition.
26. The plastic sheet product of claim 6 , wherein the copolymer comprises methyl methacrylate in an amount of about 94 to 96 wt. %.
27. The plastic sheet product of claim 1 wherein the core layer has a thickness of about 5 to about 8 mm.
28. The plastic sheet product of claim 13 wherein one capstock layer has a thickness of from about 200 to about 275 microns.
29. The plastic sheet product of claim 16 wherein the particles immiscible in the second thermoplastic polymer are present in the amount of about 10 to 30 wt. %.
30. The plastic sheet product of claim 29 wherein the particles immiscible in the second thermoplastic polymer are present in the amount of about 18 to 28 wt. %.
31. The plastic sheet product of claim 14 wherein the particles have particle size diameters in the range of about 20 to about 80 microns.
32. The plastic sheet product of claim 31 wherein the particles have particle size diameters in the range of about 30 to about 50 microns.
33. The plastic sheet product of claim 1 wherein at least about half the particles have particle size diameters greater than about 30 microns and at least about half of the particles have particle size diameters less than about 50 microns in diameter.
34. The plastic sheet product of claim 21 wherein the difference in the refractive index values of the particles and the second thermoplastic polymer is about 0.015 to about 0.035.
35. The plastic sheet product of claim 1 having a Half Angle of from about 5° to about 10°.
36. The plastic sheet product of claim 1 having a Half Angle of from about 7° to about 9°.
37. The plastic sheet product of claim 1 having a Diffusion Factor may range from about 2 to about 10.
38. The plastic sheet product of claim 1 having a Diffusion Factor may range from about 3 to about 9.
39. The plastic sheet product of claim 1 having a Diffusion Factor may range from about 4 to about 7.
40. The plastic sheet product of claim 1 that when tested in accordance with the ASTM D 1003 “Test Method for Haze and Luminous Transmittance of Transparent Plastics” using a GretagMacBeth Color Eye-7000A spectrophotometer using Illuminant C and a 20° observer demonstrates transmission of light of at least about 92%.
41. The plastic sheet product of claim 1 that when tested in accordance with ASTM D 523 “Test Method for Specular Gloss” using BYK-Gardner micro-TRI-gloss (20°, 60° and 85°) with a black felt backing demonstrates gloss at 20° of about 0.5 to 1.0, demonstrates gloss at 60° of about 5 to about 7, and demonstrate gloss at 85° of about 1 to about 6.
42. A plastic sheet product having a matte finish and improved abrasion resistance and weathering comprising a core layer of a first thermoplastic polymer and at least one layer of a capstock composition overlying and bonded to at least one face of the core layer, said capstock composition comprising a second thermoplastic polymer and containing a plurality of discrete particles immiscible with, and dispersed in, the second thermoplastic polymer, the discrete particles having a diameter between 20 and 80 microns, and being dispersed in the second thermoplastic polymer in an amount of about 1 to about 30% by weight, and said capstock composition having a thickness of from 150 to 400 microns.
43. A plastic sheet product having a matte finish and improved abrasion resistance and weathering comprising a core layer of a first thermoplastic polymer and two layers of a capstock composition overlying and bonded to both top and bottom faces of the core layer, said capstock composition comprising a second thermoplastic polymer and containing a plurality of discrete particles immiscible with, and dispersed in, the second thermoplastic polymer, the discrete particles having a diameter between 20 and 80 microns, and being dispersed in the second thermoplastic polymer in an amount of about 1 to about 30% by weight, and said capstock composition having a thickness of from 150 to 400 microns.
44. The plastic sheet product of claim 42 wherein the first thermoplastic polymer and the second thermoplastic polymer are independently selected from the group consisting of polyethylenes, polypropylenes, ethylene-propylene copolymers, ethylene vinyl acetate copolymers, ethylene methacrylate copolymers, ethylene-ethacrylate copolymers, ethylene-methylmethacrylate copolymers, ethylene vinyl acetate methylmethacrylate copolymers, polyvinyl chloride, acrylonitrile-styrene copolymers, polystyrenes, styrene methylmethacrylate copolymers, polyethylene acrylates, polymethylmethacrylates, methylmethacrylate copolymers, polyethylene terepthalates, polyamides, polycarbonates, polyurethanes, and silicone resins.
45. The plastic sheet product of claim 42 wherein the capstock composition is bonded to only one face of the core.
46. The plastic sheet products of claim 42 wherein the first and second thermoplastic polymers comprise a methylmethacrylate copolymer.
47. The plastic sheet product of claim 42 wherein the core layer has a thickness of 1.5 to 13 mm.
48. The plastic sheet product of claim 42 wherein the particles are dispersed in the second thermoplastic polymer in an amount of 22 to 26% by weight.
49. The plastic sheet product of claim 42 wherein the particles are comprised of spherical, crosslinked, polymeric beads 20-80 microns in diameter.
50. The plastic sheet product of claim 42 wherein the first thermoplastic polymer and the second thermoplastic polymer are transparent.
51. The plastic sheet product of claim 42 wherein the second thermoplastic polymer is the same as the first thermoplastic polymer.
52. The plastic sheet product of claim 43 wherein the first and the second thermoplastic polymer comprise a copolymer of methyl methacrylate and methyl acrylate.
53. The plastic sheet product of claim 42 wherein the copolymer comprises about 80 to about 98 wt. % methyl methacrylate and from about 2 to about 20 wt. % methyl acrylate.
54. The plastic sheet product of claim 53 wherein the copolymer comprises 93% to 97% by weight methyl methacrylate and 3% to 7% by weight methyl acrylate.
55. The plastic sheet product of claim 42 wherein the first and second thermoplastic polymers have weight average molecular weights in the range of 125,000 to 150,000.
56. The plastic sheet product of claim 43 wherein the core layer has a thickness of about 2 to about 13 mm.
57. The plastic sheet product of claim 42 wherein the core layer has a thickness of about 4 to 10 mm.
58. The plastic sheet product of claim 42 wherein the particles have particle size diameters in the range of 30 to 50 microns.
59. The plastic sheet product of claim 43 wherein the particles are dispersed in the second thermoplastic polymer in an amount of about 22 to about 26% by weight.
60. The plastic sheet product of claim 42 wherein the refractive indices of the particles and the second thermoplastic polymer are in the range of about 1:40 to about 1:65.
61. The plastic sheet product of claim 60 wherein the refractive indices of the particles and the second thermoplastic polymer are in the range of about 1.49 to about 1.55.
62. The plastic sheet product of claim 42 wherein the refractive index of the particles differs from the refractive index of the second thermoplastic polymer by a value in the range of about 0.001 to about 0.030.
63. The plastic sheet product of claim 62 wherein the refractive index of the particles differs from the refractive index of the second thermoplastic polymer by a value in the range of 0.005 to 0.020.
64. The plastic sheet product of claim 42 wherein the particles are selected from the group consisting of a polymer, and a pigment.
65. The plastic sheet product of claim 64 wherein the particles are comprised of a polymer selected from the group consisting of crosslinked polymethylmethyacrylate, crosslinked polymethylmethacrylate modified with an acrylate or methacrylate monomer, crosslinked copolymers of methylmethacrylate and styrene, silicone resins, and polyallyl methacrylates.
66. The plastic sheet product of claim 42 wherein the plastic sheet is formed by feedblock coextrusion of the core layer and the capstock composition.
67. The plastic sheet product of claim 64 wherein the pigment is selected from the group consisting of barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.
68. The plastic sheet product of claim 53 , wherein the copolymer comprises methyl methacrylate in an amount of about 94 to 96 wt. %.
69. The plastic sheet product of claim 42 wherein the core layer has a thickness of about 5 to about 8 mm.
70. The plastic sheet product of claim 42 wherein one capstock layer has a thickness of from about 200 to about 275 microns.
71. The plastic sheet product of claim 42 wherein the particles immiscible in the second thermoplastic polymer are present in the amount of about 10 to 30 wt. %.
72. The plastic sheet product of claim 71 wherein the particles immiscible in the second thermoplastic polymer are present in the amount of about 18 to 28 wt. %.
73. The plastic sheet product of claim 42 wherein at least about half the particles have particle size diameters greater than about 30 microns and at least about half of the particles have particle size diameters less than about 50 microns in diameter.
74. The plastic sheet product of claim 62 wherein the difference in the refractive index values of the particles and the second thermoplastic polymer is about 0.015 to about 0.035.
75. The plastic sheet product of claim 42 having a Half Angle of from about 5° to about 10°.
76. The plastic sheet product of claim 42 having a Half Angle of from about 7° to about 9°.
77. The plastic sheet product of claim 42 having a Diffusion Factor ranging from about 2 to about 10.
78. The plastic sheet product of claim 77 having a Diffusion Factor ranging from about 3 to about 9.
79. The plastic sheet product of claim 78 having a Diffusion Factor ranging from about 4 to about 7.
80. The plastic sheet product of claim 42 that when tested in accordance with the ASTM D 1003 “Test Method for Haze and Luminous Transmittance of Transparent Plastics” using a GretagMacBeth Color Eye-7000A spectrophotometer using Illuminant C and a 2° observer demonstrates transmission of light of at least about 92%.
81. The plastic sheet product of claim 42 that when tested in accordance with ASTM D 523 “Test Method for Specular Gloss” using BYK-Gardner micro-TRI-gloss (20°, 60° and 85°) with a black felt backing demonstrates gloss at 20° of about 0.5 to 1.0, demonstrates gloss at 60° of about 5 to about 7, and demonstrate gloss at 85° of about 1 to about 6.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/194,061 US20060019113A1 (en) | 2000-03-24 | 2005-07-29 | Plastic sheet product offering matte appearance and method of preparation |
| DE200660014907 DE602006014907D1 (en) | 2005-07-29 | 2006-02-13 | Plastic film with a matt appearance and method of manufacture |
| PL06250760T PL1747881T3 (en) | 2005-07-29 | 2006-02-13 | Plastic sheet product offering matte appearance and method of preparation |
| AT06250760T ATE471236T1 (en) | 2005-07-29 | 2006-02-13 | PLASTIC FILM HAVING A MATT APPEARANCE AND METHOD FOR PRODUCING IT |
| DK06250760T DK1747881T3 (en) | 2005-07-29 | 2006-02-13 | Matte-looking plastic foil product as well as process for making it |
| ES06250760T ES2347585T3 (en) | 2005-07-29 | 2006-02-13 | PLASTIC SHEET PRODUCT THAT PRESENTS A MATTE ASPECT AND PREPARATION METHOD. |
| EP20060250760 EP1747881B1 (en) | 2005-07-29 | 2006-02-13 | Plastic sheet product offering matte appearance and method of preparation |
| US12/074,718 US7816000B2 (en) | 2000-03-24 | 2008-03-04 | Plastic sheet offering matte appearance and method of preparation |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19205700P | 2000-03-24 | 2000-03-24 | |
| US09/817,788 US20010036543A1 (en) | 2000-03-24 | 2001-03-26 | Plastic sheet product offering matte appearance and method of preparation |
| US11/194,061 US20060019113A1 (en) | 2000-03-24 | 2005-07-29 | Plastic sheet product offering matte appearance and method of preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/817,788 Continuation-In-Part US20010036543A1 (en) | 2000-03-24 | 2001-03-26 | Plastic sheet product offering matte appearance and method of preparation |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/074,718 Continuation US7816000B2 (en) | 2000-03-24 | 2008-03-04 | Plastic sheet offering matte appearance and method of preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20060019113A1 true US20060019113A1 (en) | 2006-01-26 |
Family
ID=36791790
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/194,061 Abandoned US20060019113A1 (en) | 2000-03-24 | 2005-07-29 | Plastic sheet product offering matte appearance and method of preparation |
| US12/074,718 Expired - Fee Related US7816000B2 (en) | 2000-03-24 | 2008-03-04 | Plastic sheet offering matte appearance and method of preparation |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/074,718 Expired - Fee Related US7816000B2 (en) | 2000-03-24 | 2008-03-04 | Plastic sheet offering matte appearance and method of preparation |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20060019113A1 (en) |
| EP (1) | EP1747881B1 (en) |
| AT (1) | ATE471236T1 (en) |
| DE (1) | DE602006014907D1 (en) |
| DK (1) | DK1747881T3 (en) |
| ES (1) | ES2347585T3 (en) |
| PL (1) | PL1747881T3 (en) |
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| US20080113122A1 (en) * | 2006-11-10 | 2008-05-15 | Lg.Philips Lcd Co., Ltd. | Optical film, method of manufacturing optical film and liquid crystal display device having the same |
| US20080242786A1 (en) * | 2005-11-15 | 2008-10-02 | Arkema France | White Light Diffusing Thermoplastic Composition |
| WO2008097733A3 (en) * | 2007-02-02 | 2008-10-23 | Arkema France | Multi-layer screen composites |
| US20130033808A1 (en) * | 2010-03-12 | 2013-02-07 | Wrapsol, Llc | Protective Adhesive Film, Method of Adhering Protective Adhesive Film to a Device, and Device Comprising Protective Adhesive Film |
| US9085681B2 (en) | 2011-02-10 | 2015-07-21 | Polyone Corporation | Low gloss ionomer-based capstock |
| US9615463B2 (en) | 2006-09-22 | 2017-04-04 | Oscar Khaselev | Method for producing a high-aspect ratio conductive pattern on a substrate |
| US10841409B2 (en) | 2018-12-21 | 2020-11-17 | Otter Products, Llc | Tool for installing a screen protector on an electronic device |
| US20200362163A1 (en) * | 2019-05-15 | 2020-11-19 | Ampacet Corporation | Matte finish for plastics |
| US11186031B2 (en) | 2019-08-12 | 2021-11-30 | Otter Products, Llc | Apparatus for installing a screen protector on an electronic device |
| US11665269B2 (en) | 2018-12-21 | 2023-05-30 | Otter Products, Llc | Tool for installing a screen protector on an electronic device |
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| KR20110123240A (en) * | 2008-12-19 | 2011-11-14 | 파이버 콤포지트 엘엘씨. | Wood-Plastic Composites Using Ionomer Capstock and Manufacturing Method Thereof |
| US8480841B2 (en) | 2010-04-13 | 2013-07-09 | Ceralog Innovation Belgium BVBA | Powder overlay |
| US9085680B2 (en) | 2011-01-27 | 2015-07-21 | Polyone Corporation | Low gloss capstock |
| FR2973803B1 (en) * | 2011-04-07 | 2013-04-05 | Arkema France | NEW ACRYLIC MATERIAL REINFORCED WITH SHOCK |
| PT3169532T (en) | 2014-07-16 | 2023-10-27 | Vaelinge Innovation Ab | Method to produce a thermoplastic wear resistant foil |
| MY188739A (en) | 2015-01-14 | 2021-12-27 | Valinge Innovation Ab | A method to produce a wear resistant layer with different gloss levels |
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| US11926089B2 (en) | 2019-08-12 | 2024-03-12 | Otter Products, Llc | Apparatus for installing a screen protector on an electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| US7816000B2 (en) | 2010-10-19 |
| PL1747881T3 (en) | 2011-03-31 |
| ATE471236T1 (en) | 2010-07-15 |
| EP1747881B1 (en) | 2010-06-16 |
| ES2347585T3 (en) | 2010-11-02 |
| US20080226872A1 (en) | 2008-09-18 |
| DK1747881T3 (en) | 2010-08-23 |
| EP1747881A1 (en) | 2007-01-31 |
| DE602006014907D1 (en) | 2010-07-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
| AS | Assignment |
Owner name: EVONIK CYRO LLC, NEW JERSEY Free format text: CHANGE OF NAME;ASSIGNOR:CYRO INDUSTRIES;REEL/FRAME:024744/0381 Effective date: 20080630 |