WO2000024580A1 - Article thermoplastique a metamerisme angulaire - Google Patents

Article thermoplastique a metamerisme angulaire Download PDF

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Publication number
WO2000024580A1
WO2000024580A1 PCT/US1999/020408 US9920408W WO0024580A1 WO 2000024580 A1 WO2000024580 A1 WO 2000024580A1 US 9920408 W US9920408 W US 9920408W WO 0024580 A1 WO0024580 A1 WO 0024580A1
Authority
WO
WIPO (PCT)
Prior art keywords
matrix
article according
article
polycarbonate
opaque
Prior art date
Application number
PCT/US1999/020408
Other languages
English (en)
Inventor
John G. Skabardonis
David Rosendale
Original Assignee
General Electric Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Company filed Critical General Electric Company
Publication of WO2000024580A1 publication Critical patent/WO2000024580A1/fr

Links

Classifications

    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B29C70/585—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres incorporation of light reflecting filler, e.g. lamellae to obtain pearlescent effet
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B44F1/14—Iridescent effects
    • 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
    • B32B2307/409—Iridescent, pearlescent surface

Definitions

  • This application relates generally to an article comprising a pigment which exhibits angular metamerism.
  • the pigment is dispersed in a transparent thermoplastic matrix.
  • This application further relates to a method for producing a thermoplastic article which exhibits angular metamerism.
  • thermoplastic articles have been made more visually exciting to the consumer.
  • various persons have devised ways to color thermoplastics while avoiding unacceptable adverse effects on the physical properties of the thermoplastic.
  • These techniques have improved the commercial acceptance of plastics by allowing plastic parts to be color matched to colored parts made from other materials.
  • the exterior of a car body may have both steel and plastic parts which are painted to have a matching color.
  • thermoplastic parts are increasingly used for various different applications in the marketplace, it has become commercially important for manufacturers to devise new color effects for thermoplastics to make them more visually appealing to the consumer. It is also desirable to create color effects that will not be ruined by minor scratches or chips in the thermoplastic which may be caused by routine wear.
  • thermoplastic that is visually appealing to consumers.
  • an article comprising a transparent thermoplastic matrix having a pigment which exhibits angular metamerism (hereinafter “angular metamerism pigment”) dispersed therein.
  • angular metamerism pigment a pigment which exhibits angular metamerism
  • the viewer looking at the article sees a viewing surface of the thermoplastic matrix.
  • the surface of the thermoplastic matrix opposite the viewing surface is opaque, the color of the viewing surface will shift color depending on the viewing angle with respect to the normal of the viewing surface.
  • the opaque backing may be a coating or a substrate.
  • a part lacking an opaque backing will also give the desired visual effect provided it is sufficiently thick and has a sufficiently high loading of the angular metamerism pigment as to appear opaque.
  • thermoplastic matrix it is also possible to obtain different attractive color effects by further incorporating an optical brightening agent, a light diffuser, additional pigments and /or a fluorescent dye in the thermoplastic matrix.
  • thermoplastic matrix rather than as a coating, to prevent minor chips and scratches from materially changing the appearance of the part.
  • thermoplastic substrate lacking said pigment because the substrate's physical properties will not be adversely affected by the pigment. Therefore, the part, as a whole, will maintain its desirable physical characteristics.
  • the transparent thermoplastic matrix described above may be any transparent thermoplastic material which is compatible with angular metamerism pigments.
  • Preferred transparent thermoplastic materials include polycarbonates, polyetherimides, transparent polyimides, transparent polyamides (nylons), polyesters, transparent polycarbonate-polyester blends, polysulfones, polyether and polyphenyl sulfones, styrene acrylonitrile (SAN), polystyrene, and miscible transparent polystyrene-polyphenylene oxide (PS- PPO) blends, acrylics, polycarbonate-polysiloxanes, polyetherimide- polysiloxanes, polyarylates, and blends and copolymers of all of the above.
  • More preferred transparent thermoplastic matrix materials are polycarbonate homopolymer or copolymers, polyester carbonates and polyethylene terephthalate (PET).
  • the most preferred matrix material is an aromatic polycarbonate homopolymer based primarily on the bisphenol-A monomer. The synthesis of such materials is well known in the art. For example, U.S. Patent No. 5,364,926 describes the melt process for making polycarbonate, and is incorporated by reference herein.
  • Angular metamerism pigments comprise a series of stacked thin film platelets of inorganic materials. Methods of making these pigments are described, for example, in U.S. Patent Nos. 5,059,245; 5,569,535 and 4,434,010, which are all hereby incorporated by reference.
  • Angular metamerism pigments have the unique property that their color changes depending on the angle at which they are viewed. These pigments have been incorporated in security inks used in newer United States $20.00, $50.00 and $100.00 bills, in order to prevent forgery. Many inorganic pigments can not be successfully incorporated into thermoplastics because they cause unacceptable degradation of the plastic. However, the angular metamerism pigments do not degrade polycarbonate to an unacceptable extent.
  • thermoplastic article which exhibits angular metamerism
  • a film of the transparent thermoplastic matrix e.g., polycarbonate
  • an opaque thermoplastic substrate e.g., polycarbonate containing a black pigment, or dyestuff, or a combination of dyestuff s that gives a black color.
  • This film may be coated on the substrate by a casting method or by an extrusion method.
  • the layer of transparent thermoplastic matrix could be coated with an opaque layer, such as paint, on the side opposite the viewer.
  • an opaque layer such as paint
  • a layer of the transparent thermoplastic matrix with dispersed angular metamerism pigment is extruded on a thermoplastic substrate.
  • the thermoplastic matrix may optionally further contain an optical brightening agent, a light diffuser, additional pigments and /or a fluorescent dye. Adding an optical brightening agent helps produce a deeper color and an enhanced metallic appearance for the article.
  • Suitable optical brightening agents include aromatic stilbene derivatives, aromatic benzoxazole derivatives, or aromatic stilbene benzoxazole derivatives. Among these optical brightening agents, Uvitex OB from Ciba Specialty Chemicals [2,5-bis(5'-tert-butyl-2- benzoxazolyl)thiophene] is preferred.
  • Suitable fluorescent dyestuffs include
  • Permanent Pink R (Color Index Pigment Red 181, from Clariant Corporation), Hostasol Red 5B (Color Index #73300, CAS # 522-75-8, from Clariant Corporation) and Macrolex Fluorescent Yellow 10GN (Color Index Solvent Yellow 160:1, from Bayer Corporation). Among these, Permanent Pink R is preferred.
  • Suitable light diffusers included polytetrafluoroethylene, zinc oxide, and polymethylmethacrylate.
  • Techpolymer MBX- series crosslinked polymethylmethacrylate microspheres which are available in various diameters from Nagase America (e.g., 5 -50 micron avg. diameter), are preferred.
  • any type of pigment that is well known for inclusion in thermoplastic materials can also be added to the thermoplastic matrix.
  • Preferred pigments include titanium dioxide, zinc sulfide, carbon black, cobalt chromate, cobalt titanate, cadmium sulfides, iron oxide, sodium aluminum sulfosilicate, sodium sulfosilicate, chrome antimony titanium rutile, nickel antimony titanium rutile, zinc oxide, and polytetrafluoroethylene. It may also be advantageous to include various chemicals to prevent degradation of the thermoplastic matrix due to exposure to UV light (hereinafter "UV stabilizers"). Suitable UV stabilizers include substituted benzotriazoles, or triazines, or tetraalkylpiperidines. The UV stabilizers may be mixed into the thermoplastic matrix, or they can be included only in a
  • resin composition according to the invention may further be added other resins and additives such as reinforcing agents, fillers, impact modifiers, heat resisting agents, antioxidants, anti- weathering agents, lubricants, nucleating agents, plasticizers, flame retardants, flow-improving agents and anti-statics.
  • additives may be introduced in a mixing or molding process, provided the properties of the composition are not damaged.
  • the reinforcing fillers may be metallic fillers such as fine powder aluminum, iron, nickel, or metal oxides.
  • Non-metallic fillers include carbon filaments, silicates such as mica, aluminum silicate or clay, talc and asbestos, titanium oxide, wollastonite, novaculite, potassium titanate, titanate whiskers, glass fillers and polymer fibers or combinations thereof.
  • Glass fillers useful for reinforcement are not particularly limited in their types or shapes and may be, for instance, glass fibers, milled glass, glass flakes and hollow or solid glass beads. Glass fillers may be subjected to surface treatment with coupling agents such as silane or titanate-type agents to enhance adhesion with resin.
  • Reinforcing fillers are preferably used in an amount sufficient to yield the reinforcing effect, usually 1 to 60% by weight, preferably 5 to 50% by weight, based on the total weight of the composition.
  • Glass fibers, or a combination of glass fibers with talc, mica or aluminum silicate are preferred reinforcing agents. These fibers are preferably about 0.00012 to 0.00075 inches long.
  • a polycarbonate derived from brominated bisphenol is added as a flame retardant.
  • inorganic or organic antimony compounds may further be blended in the composition to synergistically enhance flame retardance introduced by such polycarbonate.
  • Suitable inorganic antimony compounds are antimony oxide, antimony phosphate, KSb(OH) 6 , NH 4 SbF 6 and Sb 2 S3.
  • organic antimony compounds may also be used, such as antimonic esters of organic acids, cyclic alkyl antimonite esters and aryl antimonic acid compounds.
  • Examples of typical organic antimony compounds are potassium antimony tarrrate, antimony salt of caproic acid, Sb(OCH2CH3)3, Sb[OCH(CH3)CH2CH3_3, antimony polymethylene glycorate and rriphenyl antimony.
  • a preferred antimony compound is antimony oxide.
  • Phosphites e.g., aromatic phosphite thermal stabilizers
  • metal salts of phosphoric and phosphorous acid may also be added as stabilizers or antioxidants.
  • hindered phenol antioxidants may also be added as stabilizers or antioxidants.
  • aromatic lactone radical scavengers may also be added as stabilizers or antioxidants.
  • Suitable antistatic agents include, but are not limited to, phosphonium salts, polyalkylene glycols, sulfonium salts and alkyl and aryl ammonium salts.
  • Suitable mold release agents include, but are not limited to, pentaerythritol tetracarboxylate, glycerol monocarboxylate, glycerol triscarboxylate, polyolefins, alkyl waxes and amides.
  • the components may be mixed by any known methods. Typically, there are two distinct mixing steps: a premixing step and a melt mixing step.
  • the premixing step the dry ingredients are mixed together. This premixing step is typically performed using a tumbler mixer or a ribbon blender. However, if desired, the premix may be manufactured using a high shear mixer such as a Henschel mixer or similar high intensity device.
  • the premixing step must be followed by a melt mixing step where the premix is melted and mixed again as a melt.
  • melt mixing step it is possible to skip the premixing step, and simply add the raw materials directly into the feed section of a melt mixing device via separate feed systems.
  • the ingredients are typically melt kneaded in a single screw or twin screw extruder, a Banbury mixer, a two roll mill, or similar device.
  • the articles according to present invention may then be manufactured by molding the melt mixed material into various shapes using an injection molding machine.
  • a film can be formed on a substrate for example, by insert molding, in-mold decorating, laminating, co-injection or co- extrusion.
  • a film can be extruded onto sheet or another film, which can then be thermoformed, vacuum-formed, or shaped in some manner. All other known methods for creating multi-layer articles are also suitable.
  • the base formulation comprised the 100 parts LEXAN ® resin mixed with 0.03 parts of Alkanox 240 (phosphite stabilizer) (i.e., 2,4-di-tert- butylphenyl phosphite (3:1), CAS # 31570-04-4) purchased from Great Lakes Chemical, and 0.2 parts of a ChromaFlair angular metamerism effect pigment (Flex Products).
  • Alkanox 240 phosphite stabilizer
  • 2,4-di-tert- butylphenyl phosphite (3:1), CAS # 31570-04-4 purchased from Great Lakes Chemical
  • ChromaFlair angular metamerism effect pigment Fex Products
  • ChromaFlair pigments For each of the four ChromaFlair pigments, four separate compositions were prepared as summarized in Tables I - IV below.
  • the ChromaHair pigments used were silver /green 060, purple/orange 300, green/purple 190 and red /gold 000, for Tables I - IV, respectively.
  • the first composition contained the base formulation together with 0.05 parts of Uvitex OB optical brightener; the second composition contained the base formulation together with 0.03 parts of Permanent Pink R fluorescent dye, which is available from Clariant Corporation; the third composition contained the base formulation together with 0.25 parts Techpolymer MBX-5 (i.e., microspheres of polymethylmethacrylate having an average diameter of 5 microns); and the fourth composition contained the base formulation together with 0.00465 parts carbon black pigment, 0.00460 parts of the Macrolex Blue RR dyestuff (Color
  • a composite part was then prepared by molding the thin (0.010 to 0.075 inches thick) angular metamerism pigment-containing section, inserting the molded angular metamerism part in the cavity of a mold having the same shape, but a larger cross-section, and over-molding with an opaque, black colored PC resin (e.g., Lexan 141-701, which comprises carbon black).
  • an opaque, black colored PC resin e.g., Lexan 141-701, which comprises carbon black.
  • Composition 1 in each of Tables I - IV contains an optical brightener. As noted above, adding an optical brightener helps produce a deeper color and an enhanced metallic appearance for the article.
  • composition 3 in each of Tables I - IV contains a fluorescent dye. As noted above, adding the fluorescent dye modifies the color of the article.
  • Composition 3 in each of Tables I - IV comprises Techpolymer MBX-5, which is polymethylmethacrylate spheres having an average diameter of about 5 microns. Adding such particles makes the article translucent.
  • Composition 4, in each of Tables I - IV comprises carbon black, and a blue and violet dye. This changes the color of the article.
  • this sample When viewed normal to the surface of the plaque (the angle between the surface and the viewing vector is 90 degrees), this sample has an intensely metallic, dark gray appearance. This color was much darker than the light silver color of a control plaque when viewed from the same angle. If this plaque is viewed from an angle 30 degrees from normal (the angle between the surface and the viewing vector is 60 degrees), the color appears dark metallic green.
  • the plaque When viewed normal to the surface, the plaque has a bright metallic green appearance, which appears more metallic than the control plaque. If this is viewed at an angle 30 degrees from normal, the color appears metallic purple.
  • the plaque When viewed normal to the surface the plaque appeared slightly brighter and more red than the control plaque. If this plaque is viewed at an angle 30 degrees from normal, the color is an intense reddish copper, compared to a brown-gold color for the control plaque.
  • the article can be formed by other methods.
  • the thick opaque section can be molded first and then inserted into a thicker mold cavity where the thin angular metamerism section will be over-molded.
  • Other molding methods also exist, whereby the part remains in the variable thickness mold cavity as the first section, and then the second, are injected into the mold from different molding machine barrels which contain the angular metamerism effect resin and the opaque resin.
  • Another method involves partially filling the mold cavity from one molding machine barrel and the mold moving so that the remainder of the cavity can be filled from another molding machine barrel.
  • compositions according to the invention merely show representative compositions according to the invention.
  • the opaque backing is LEXAN polycarbonate comprising different pigments other than carbon black.
  • compositions comprising other Chroma Flair angular metamerism pigments such as: gold/silver 080, cyan/purple 230, blue /red 280 and magenta /gold 330, or any angular metamerism pigments made by others.
  • the compositions described herein may be incorporated in all varieties of articles where thermoplastics are suitable, including, but not limited to business equipment enclosures, enclosures for portable electronic items, parts for automobile bodies and other consumer articles. The article is not limited in any way with respect to shape, size or use.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un nouveau type d'effet de couleur destiné à un article comprenant une matrice thermoplastique attirant l'oeil du consommateur. L'invention concerne, en particulier, un article comprenant une matrice thermoplastique transparente, dans laquelle est dispersé un pigment à métamérisme angulaire. La personne regardant l'article voit une surface de visualisation de la matrice thermoplastique. Lorsque la surface de la matrice thermoplastique à l'opposé de la surface de visualisation est opaque, ou que la matrice elle-même est suffisamment épaisse pour paraître opaque, la surface de visualisation change de couleur selon l'angle de visualisation par rapport à la perpendiculaire à la surface de visualisation.
PCT/US1999/020408 1998-10-23 1999-09-07 Article thermoplastique a metamerisme angulaire WO2000024580A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17820298A 1998-10-23 1998-10-23
US09/178,202 1998-10-23

Publications (1)

Publication Number Publication Date
WO2000024580A1 true WO2000024580A1 (fr) 2000-05-04

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066266A1 (fr) * 2001-02-16 2002-08-29 3M Innovative Properties Company Film à distrosion chromatique marqué avec des colorants fluorescents et non fluorescents
US6506480B2 (en) 2001-02-16 2003-01-14 3M Innovative Properties Company Color shifting film with a plurality of fluorescent colorants
US6712894B2 (en) 2001-05-09 2004-03-30 Cabot Corporation Method of producing secure images using inks comprising modified pigment particles
WO2007040881A2 (fr) * 2005-09-30 2007-04-12 General Electric Company Films plastiques
EP1832415A1 (fr) * 2006-03-07 2007-09-12 Sibylle Wagner-Quinte Matière plastique composite
USD621068S1 (en) 2002-03-01 2010-08-03 3Form, Inc. Architectural panel with thatch reed design
US8047575B2 (en) 2006-05-31 2011-11-01 Cabot Corporation Printable features formed from multiple inks and processes for making them
US8241714B2 (en) 2004-09-01 2012-08-14 3Form, Inc. Architectural panels with objects embedded in resin interlayer
US8318847B2 (en) 2005-09-30 2012-11-27 Sabic Innovative Plastics Ip B.V. Plastic compositions and products produced therefrom
USD691289S1 (en) 2012-09-05 2013-10-08 3Form, Inc. Panel with cut and aligned thatch interlayer
US8790459B2 (en) 2006-05-31 2014-07-29 Cabot Corporation Colored reflective features and inks and processes for making them
US9348065B2 (en) 2007-05-08 2016-05-24 3Form, Llc Multivariate color system with texture application
US9533523B2 (en) 2006-05-31 2017-01-03 Sicpa Holding Sa Reflective features with co-planar elements and processes for making them

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US4199489A (en) * 1977-05-11 1980-04-22 General Motors Corporation Moisture curing polyurethane topcoat paint displaying geometric metamerism
US4900611A (en) * 1988-11-07 1990-02-13 Eastman Kodak Company Paint coated article
US4921755A (en) * 1988-03-23 1990-05-01 Eastman Kodak Company Coating composition and coated article
JPH04214779A (ja) * 1990-12-11 1992-08-05 Ishihara Sangyo Kaisha Ltd 塗料組成物
US5192609A (en) * 1988-11-07 1993-03-09 Eastman Kodak Company Thermoformable sheet material
US5496630A (en) * 1993-09-13 1996-03-05 The Geon Company Thermoplastic multilayer louver with a polished metal look
US5605751A (en) * 1992-01-06 1997-02-25 Shiseido Company, Ltd. Laminates

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US4199489A (en) * 1977-05-11 1980-04-22 General Motors Corporation Moisture curing polyurethane topcoat paint displaying geometric metamerism
US4921755A (en) * 1988-03-23 1990-05-01 Eastman Kodak Company Coating composition and coated article
US4900611A (en) * 1988-11-07 1990-02-13 Eastman Kodak Company Paint coated article
US5192609A (en) * 1988-11-07 1993-03-09 Eastman Kodak Company Thermoformable sheet material
JPH04214779A (ja) * 1990-12-11 1992-08-05 Ishihara Sangyo Kaisha Ltd 塗料組成物
US5605751A (en) * 1992-01-06 1997-02-25 Shiseido Company, Ltd. Laminates
US5496630A (en) * 1993-09-13 1996-03-05 The Geon Company Thermoplastic multilayer louver with a polished metal look

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Title
DATABASE WPI Section Ch Week 199238, Derwent World Patents Index; Class A14, AN 1992-311136, XP002126379 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066266A1 (fr) * 2001-02-16 2002-08-29 3M Innovative Properties Company Film à distrosion chromatique marqué avec des colorants fluorescents et non fluorescents
US6506480B2 (en) 2001-02-16 2003-01-14 3M Innovative Properties Company Color shifting film with a plurality of fluorescent colorants
US6534158B2 (en) 2001-02-16 2003-03-18 3M Innovative Properties Company Color shifting film with patterned fluorescent and non-fluorescent colorants
AU2001280567B2 (en) * 2001-02-16 2007-02-15 3M Innovative Properties Company Color shifting film with a plurality of fluorescent colorants
US6712894B2 (en) 2001-05-09 2004-03-30 Cabot Corporation Method of producing secure images using inks comprising modified pigment particles
USD621068S1 (en) 2002-03-01 2010-08-03 3Form, Inc. Architectural panel with thatch reed design
US8241714B2 (en) 2004-09-01 2012-08-14 3Form, Inc. Architectural panels with objects embedded in resin interlayer
WO2007040881A3 (fr) * 2005-09-30 2008-02-14 Gen Electric Films plastiques
WO2007040881A2 (fr) * 2005-09-30 2007-04-12 General Electric Company Films plastiques
US8318847B2 (en) 2005-09-30 2012-11-27 Sabic Innovative Plastics Ip B.V. Plastic compositions and products produced therefrom
EP1832415A1 (fr) * 2006-03-07 2007-09-12 Sibylle Wagner-Quinte Matière plastique composite
US8047575B2 (en) 2006-05-31 2011-11-01 Cabot Corporation Printable features formed from multiple inks and processes for making them
US8070186B2 (en) 2006-05-31 2011-12-06 Cabot Corporation Printable reflective features formed from multiple inks and processes for making them
US8790459B2 (en) 2006-05-31 2014-07-29 Cabot Corporation Colored reflective features and inks and processes for making them
US9533523B2 (en) 2006-05-31 2017-01-03 Sicpa Holding Sa Reflective features with co-planar elements and processes for making them
US9348065B2 (en) 2007-05-08 2016-05-24 3Form, Llc Multivariate color system with texture application
USD691289S1 (en) 2012-09-05 2013-10-08 3Form, Inc. Panel with cut and aligned thatch interlayer

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