WO2011115992A2 - Panneaux stratifiés produits à partir de biopolymères - Google Patents

Panneaux stratifiés produits à partir de biopolymères Download PDF

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Publication number
WO2011115992A2
WO2011115992A2 PCT/US2011/028524 US2011028524W WO2011115992A2 WO 2011115992 A2 WO2011115992 A2 WO 2011115992A2 US 2011028524 W US2011028524 W US 2011028524W WO 2011115992 A2 WO2011115992 A2 WO 2011115992A2
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WO
WIPO (PCT)
Prior art keywords
biopolymer
panel
temperature
resin
recited
Prior art date
Application number
PCT/US2011/028524
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English (en)
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WO2011115992A3 (fr
Inventor
Charles H. Moore
John E.C. Willham
Original Assignee
Hunter Douglas Industries B.V.
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 Hunter Douglas Industries B.V. filed Critical Hunter Douglas Industries B.V.
Publication of WO2011115992A2 publication Critical patent/WO2011115992A2/fr
Publication of WO2011115992A3 publication Critical patent/WO2011115992A3/fr
Priority to US13/609,073 priority Critical patent/US9186868B2/en

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Classifications

    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • B32B37/085—Quenching
    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/412—Transparent
    • 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
    • B32B2307/414—Translucent
    • 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
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2309/02—Temperature
    • 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
    • B32B2309/04—Time
    • 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
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2451/00—Decorative or ornamental articles
    • 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
    • B32B2607/00—Walls, panels

Definitions

  • the present invention relates to systems, methods, and apparatus for creating laminate structures produced from bio-based polymer materials.
  • Recent architectural designs often include synthetic polymeric resin panels, which may be used as partitions, displays, barriers, lighting diffusers or decorative finishes etc. These polymeric panels are typically constructed using poly vinyl chloride (PVC), polyacrylate materials such as poly methylmethacrylate (PMMA), polyester materials such as polyethylene terephthalate (PET), poly ethylene-co- cyclohexane 1,4-dimethanol terephthalate (PETG) modified with 1,4- cyclohexanedimethanol (CHDM), glycol modified polycyclohexylenedimethylene terephthalate(PCTG), or polycarbonate(PC) materials and the like.
  • PVC poly vinyl chloride
  • PMMA polyacrylate materials
  • PET polyethylene terephthalate
  • PETG poly ethylene-co- cyclohexane 1,4-dimethanol terephthalate
  • CHDM 1,4- cyclohexanedimethanol
  • PCTG glycol modified polycyclohexylenedimethylene terephthalate
  • such petroleum based resin panels have become popular with architects and designers as compared to decorative cast or laminated glass materials, since the polymeric resin materials may be manufactured to be more resilient, but to provide a similar transparent, translucent, and/or colored appearance as cast or laminated glass, at lower cost.
  • Decorative resin panels may also provide greater design flexibility as compared to glass in terms of color, texture, gauge, and impact resistance.
  • decorative resin panels have a fairly wide utility since they may be easily and inexpensively formed and fabricated to include a large variety of artistic colors, images, shapes, structures and assemblies.
  • resin panels can be economically produced in flat or three- dimensional (i.e., curved or other-shaped) forms, such as with compound curvatures.
  • polymer resin panel materials provide relatively wide functional and aesthetic utility, and can be used to easily change the design or function of new or existing structures.
  • Once their useful life is over, such panels are typically disposed of within a landfill, as such large panels are not easily incorporated into existing recycle streams.
  • Such panels are formed of petroleum-derived resins and are typically sent to a landfill when the product or application is no longer of use or needed.
  • polymeric resin materials may be recycled, they are often simply disposed of within a landfill where they do not readily decompose or otherwise degrade and break down.
  • Biopolymers represent a unique and responsible option for use as building materials because they are able to be composted, or are biodegradable upon disposal.
  • Biopolymers derived from natural renewable plant or microorganism materials include polysaccharides (e.g., starch, cellulose), polyesters (e.g., polyhydroxyalconates (PHA), poly-3-hydroxybutyrate (PHB)), as well as polyesters synthesized from bio-derived monomers (e.g., polylactic acid (PLA)). Of these biopolymer materials mentioned, at least PHA, PHB, PLA, and blends thereof are compostable or biodegradable.
  • biopolymer and “bio-based polymer” refer to polymers produced or derived from living organisms or products of living organisms. For example, they may be produced from biomass. Such biopolymers are biodegradable (e.g., degradable to C0 2 and water through the biological processes of microorganisms), and many are compostable (e.g., they may be inserted into an industrial composting process within which they will break down by about 90% in six months).
  • biopolymer resins can be as structurally sound and long-lasting as petroleum- based resin materials, so long as the biopolymer resins are not subjected to degradation triggers.
  • these degradation triggers may include certain combinations of temperature, moisture content, biological activity and pressure over some time interval.
  • Polymeric resin panels are often configured as a plurality of resin sheets that have been thermally fused together. Biopolymer resins are thought to be incompatible with thermal fusion processes (e.g., lamination of panels), since conventional temperatures and pressures employed are likely to initiate or accelerate degradation processes.
  • biopolymer resins are or are more likely to assume a crystalline or semi-crystalline structure, rather than an amorphous structure. Because biopolymer resins are more likely than amorphous petroleum-based resins to assume a crystalline structure, they tend to shift from transparent or semi-transparent to opaque when subjected to conventional temperatures and pressures associated with typical thermal fusion processes. This shift in transparency is believed to be a result of process-induced crystallization. For at least these additional reasons, therefore, biopolymer resins are also thought to be incompatible with the manufacture of high- end decorative and structural laminate panels, where a high degree of optical clarity, aesthetics, long term performance, and functionality are desired.
  • Biopolymers are of particular use as disposable food and other product packaging materials due to their moldability and their biodegradable and/or compostable characteristics.
  • Such packaging applications are primarily directed to single-use or short shelf-life products (e.g., food containers and the like) and the packaging material is typically discarded after a short time. Because of the short shelf- life of such products, the rapid degradability of such biopolymers has not been an issue.
  • Biopolymers are rarely produced in thicknesses greater than about 0.04 inch, as there is little or no demand for thicker materials.
  • Implementations of the present invention provide bio-based polymer panels as well as related methods of manufacture. Such panels provide excellent aesthetics, including optical clarity.
  • the panel comprises a first biopolymer resin sheet, and a second biopolymer resin sheet, wherein the sheets are laminated together to form a single, unitary panel.
  • Each laminated resin sheet is substantially transparent or translucent so as to exhibit substantially no clouding within the resin sheets.
  • the panel may include any number or type of interlayer materials or finishes. Examples of such interlayers or finishes include fabrics, botanical structures (e.g., real or faux plant-like interlayers), metals or films (colored or imaged), each of which contribute positively to one or both of the aesthetic or structural characteristics of the panel.
  • a plurality of biopolymer resin sheets are positioned adjacent to one another to form a pre-laminate assembly, and the assembly is subjected to a laminating temperature between a glass transition temperature and a melting temperature of the biopolymer resin so as to soften the biopolymer resin material of each sheet, allowing chain entanglement between the adjacent sheets resulting in a unitary laminated panel.
  • the unitary laminated panel is then quenched by subjection to a quenching temperature that is well below the glass- transition temperature of the biopolymer resin.
  • the time period between subjection to the laminating temperature and subjection to the quenching temperature is sufficiently short (e.g., preferably less than about 20 minutes) to prevent clouding of the biopolymer such that the resin sheets remain substantially transparent or translucent following processing.
  • the laminate panels are sufficiently rigid, stable, and strong for use as building materials over virtually any desired length of time (e.g., years or decades).
  • the lamination process advantageously does not result in the onset of crystallization of the resin materials, which would reduce optical clarity, as well as strength.
  • the lamination of multiple sheets of biopolymers e.g., achieving a thickness of at least about 0.15 inch results in improved flammability and impact performance, resulting in a panel which meets building code requirements relative to flammability and impact resistance.
  • Such panels are advantageously formed from renewable materials, are biodegradable upon disposal, or may be composted at the end of their useful life.
  • laminate panels in accordance with at least one implementation of the present invention can be processed with appropriate temperatures and pressures, over particularly selected appropriate time intervals, which do not trigger crystallization or degradation mechanisms.
  • appropriate temperatures and pressures for laminating and/or quenching may be by heat and/or pressure rollers, heat and/or pressure flat presses (e.g., batch or semi-batch), or autoclaving (i.e., heat in combination with pressure or vacuum).
  • exposure times to the laminating temperature are sufficiently short (e.g., as a result of quenching) so as to not trigger degradation of the panels and to avoid any substantial crystallization, which would result in clouding and loss of optical clarity.
  • Figures 1A-1B illustrate various exemplary laminate panels that can be made with one or more biopolymer resin sheets and one or more decorative interlayers, such as those that comprise organic, botanical materials;
  • Figure 2A illustrates a prepared layup assembly in a pre-laminated condition including a decorative interlayer to be sandwiched between two biopolymer resin sheets which become thermally fused together upon application of heat and pressure to result in the structure shown in Figure 1 A;
  • Figures 2B illustrates a sequence in which a prepared layup assembly is exposed to a laminating temperature and pressure in order to thermally fuse a decorative interlayer between two biopolymer resin sheets so as to result in the structure shown in Figure IB;
  • Figures 3A-3B illustrate top and side views respectively, of an exemplary laminate panel that can be made from a plurality of biopolymer resin sheets and including a decorative finish;
  • Figure 4 illustrates a prepared layup assembly in a pre-laminated condition which upon subjection to a laminating temperature and pressure followed by subjection to a quenching temperature and pressure forms the unitary laminate panel shown in Figures 3A-3B;
  • Figures 5A-5C show tables including information relative to various examples that were tested for manufacture of biopolymer laminate panels.
  • Figures 6A-6B show tables of including information relative to various examples that were tested for manufacture of biopolymer laminate panels exhibiting particularly good resistance to de lamination of the individual biopolymer resin sheets.
  • a laminate panel includes a first biopolymer resin sheet comprising a biopolymer resin, a second biopolymer sheet comprising a biopolymer resin material, both of which sheets are not derived from petroleum-based products.
  • the sheets are laminated together to form a single unitary panel and each of the laminated sheets of the unitary panel are substantially transparent or translucent so as to exhibit substantially no clouding within the resin sheets.
  • the panel structures provide a high degree of aesthetics, including optical clarity within the biopolymer resin sheets, and can be made with any number or type of interlayer materials or surface finishes.
  • the first and second biopolymer resin sheets are positioned adjacent to one another (optionally with a decorative interlayer between) in a pre-laminate assembly, which is subjected to a laminating temperature that is between the glass-transition temperature and the melting temperature of the biopolymer resin material.
  • a laminating temperature that is between the glass-transition temperature and the melting temperature of the biopolymer resin material.
  • Subjection to heat causes the biopolymer resin material of the sheets to soften, laminating the initially separate sheets together to form a unitary laminated panel.
  • the unitary laminated panel is quenched by subjection to a quenching temperature that is lower than the laminating temperature.
  • the quenching temperature is lower than the glass- transition temperature.
  • the lamination of multiple relatively thin biopolymer sheets (e.g., about 0.03 inch thickness) into a significantly thicker laminate panel (e.g., at least about 0.15 inch thickness) significantly improves the flammability resistance rating and impact resistance (i.e., toughness) of the laminate panel as compared to individual thin biopolymer sheets.
  • the increased strength and flammability resistance allow the laminate panel to meet building code requirements for use of the panel as a replacement for petroleum-based polymeric panels.
  • laminate panels constructed in accordance with implementations of the present invention maintain the desirable characteristics associated with biopolymer materials with respect to their renewable source, as well as ability to biodegrade and/or be composted at the end of their useful life.
  • implementations of the present invention relate to polymeric panel structures (or "biopolymer panels,” or “panels”) that are advantageously manufactured from organic biopolymer resins derived from renewable plant or animal sources, rather than from petroleum based sources.
  • biopolymer-based panels offer "green” building benefits over similar petroleum-based plastic panel constructs due to the fact that the feedstock materials are renewable and the product can be biodegraded and/or composted at the end of the useful life of the product.
  • the panel structures made with biopolymer resins can be manufactured with decorative surface finishes or may include embedded or encased decorative interlayers that provide various performance benefits (e.g., aesthetics, light diffusion, coloring, etc.) as dictated by the particular architectural design or building application.
  • various performance benefits e.g., aesthetics, light diffusion, coloring, etc.
  • Figures 1A and IB illustrate exemplary laminate panels 100 that can be manufactured in accordance with implementations of the present invention.
  • Figure 1A illustrates a biopolymer laminate panel 100 that has been manufactured with a plurality of decorative objects 110a in the form of thatch reed. Thatch reed 110a may comprise an interlayer embedded between layers of biopolymer resin sheets.
  • Figure IB illustrates another biopolymer laminate panel 100 that has been manufactured with a plurality of decorative objects 110b in the form of coffee beans. Coffee beans 110b may similarly be embedded between layers of biopolymer resin sheets.
  • the portion of laminate panels 100 that comprise the biopolymer resin material are substantially translucent or substantially transparent, and portray the aesthetic characteristics of the corresponding interlayer 110a or 110b embedded therein.
  • the biopolymer portions of panels 100 may be manufactured according to the processes of the present invention so as to maintain a relatively high degree of optical clarity (i.e., substantially no added crystallization, clouding, or bubble entrapment) in the final panel 100 while also meeting performance criteria required for building product applications.
  • Figure 2 A illustrates a prepared layup assembly 120 prior to lamination of the biopolymer sheets 130a and 130b with decorative interlayer 110a of thatch reed sandwiched therebetween.
  • a unitary laminate panel 100 e.g., as shown in Figure 1A
  • a decorative surface finish may be applied during or after lamination as will be apparent to one of skill in the art.
  • Figure 2B illustrates a side view a sequential progression during manufacture of panel 100 of Figure IB.
  • the manufacturer may position one or more decorative objects (e.g., coffee beans 110b) an interlayer between the biopolymer resin sheets 130a and 130b to create a pre-laminate laminate assembly 120.
  • one or more decorative objects e.g., coffee beans 110b
  • a manufacturer may include more than just the two biopolymer resin sheets 130a and 130b illustrated, and that as desired, additional or alternative decorative objects may be sandwiched or embedded.
  • the additional biopolymer resin sheets (e.g., see Figure 4) and/or additional or alternative decorative object layers (not shown) can provide additional structural rigidity, thickness, or add different aesthetic characteristics.
  • the manufacturer may include one laminate assembly 120 having thatch reed 110a sandwiched therein, and further include another assembly comprising a textile image layer and an additional biopolymer resin sheet.
  • the resulting laminate panel will include aesthetic characteristics provided by the two or more decorative image layers (i.e., the combined aesthetics provided by a thatch reed interlay er and a textile image interlay er).
  • Figure 2B illustrates the sequential progression as an exemplary pre-laminate assembly 120 is subjected to an appropriate lamination temperature and pressure, e.g., as shown in Figures 5A-6B.
  • the pre-laminate assembly 120 is subjected to a laminating temperature and pressure is simultaneously applied, the biopolymer resin sheets 130a and 130b begin to soften, as shown in Figure 2B.
  • decorative objects 110b become embedded between and within the softened sheets until they may be fully encased as shown in Figure 2B.
  • the unitary laminated panel is then quenched by subjecting the panel to a quenching temperature that is significantly colder than the laminating temperature. Quenching of the panel quickly cools the panel to prevent any significant growth of crystals within the biopolymer material, which reduces strength, toughness, and optical clarity (i.e., it leads to clouding).
  • the final sequence of Figure 2B shows the cross-section of the panel 100 once quenching is complete, and the thermoforming process has resulted in a substantially unitary laminated panel 100.
  • Figures 3A-3B illustrate a biopolymer laminate panel 300 that has been prepared in conjunction with a plurality (e.g., two or more) of similar biopolymer sheet substrates with no interlayer, but where the outermost surfaces 310 and 320 have been enhanced with texturing layers 310, 320 that impart a decorative (e.g., a light diffusing) surface finish.
  • surface finishes 310 and 320 may represent the same finish or may represent two different finishes applied to front and back surfaces of the panel 300.
  • FIG 4 illustrates a pre-laminate assembly 320 for manufacturing the decorative biopolymer laminate structure 300 shown in Figures 3A-3B.
  • biopolymer pre-laminate assembly 320 may include a plurality of biopolymer resin layers or substrates 330a, 330b, and 330c, each of which may comprise a biopolymer resin material.
  • surface finish plates 340a and 340b may be disposed at the top and bottom of the assembly 320.
  • surface finish plates 340a and 340b may include texturing, which imparts a textured or embossed surface finish into the outer surfaces of the finished unitary laminated panel 300 that are a negative of the texturing of finish plates 340a and 340b once biopolymer resin sheets 330a, 330b, and 330c are subjected to appropriate laminating temperatures and pressures.
  • the surface finish plates 340a and 340b may comprise die layers that impart an image or color into the biopolymer resin sheets 330a and 330c upon application of laminating heat and pressure.
  • the surface finish plates 340a and 340b may comprise a colored film which fuses to the biopolymer resin sheets 330a and 330c upon the application of laminating heat and pressure.
  • biopolymer sheets may be included, that combinations of or alternative decorative objects and/or surface finishes may be provided, and that one or more adhesive layers, such as a thermoplastic tie layer, may be provided between one or more of the biopolymer resin sheets 330a, 330b, and 330c depending upon the desired configuration of biopolymer laminate panel 300.
  • adhesive layers such as a thermoplastic tie layer
  • the texture may already be present within a biopolymer sheet (e.g., applied as described above with a texturing plate to a softened biopolymer sheet) when it is positioned within the pre-laminate assembly.
  • a pretextured biopolymer sheet may be positioned at the interior of a pre-laminate assembly, sandwiched between adjacent sheets.
  • the assembly 320 Upon subjecting the pre-lamination assembly 320 to a laminating temperature while simultaneously applying pressure, the assembly 320 will include the aesthetic characteristics of the one or more finish sheets 340a and 340b (as well as any other decorative objects, interlayers, or surface finishes employed) and form a unitary laminate panel 300 with a thickness substantially equal to the combined thickness of the biopolymer resin sheets thermally fused together to form the panel. For example, upon subjection of the pre-laminate assembly 320 to a laminating temperature over an appropriate time period, the biopolymer resin sheets 330a, 330b, and 330c begin to soften and fuse together.
  • the unitary laminated panel is quenched by subjecting the laminated panel to a significantly colder quenching temperature, which prevents any substantial growth of crystals within the biopolymer materials, which otherwise result in clouding and loss of optical clarity within the biopolymer materials.
  • the biopolymer resin sheet substrates may comprise any suitable biopolymer derived from living organisms or products of living organisms.
  • suitable biopolymer derived from living organisms or products of living organisms include, but are not limited to, polyhydroxyalkonates (PHA), polylactic acid (PLA), poly-3-hydroxybutyrate (PHB), poly-trimethylene terephthalate (PTT), cellulose, or starch-derived biopolymeric materials such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, or copolymers thereof.
  • PVA polyvinyl alcohol
  • Information relative to glass-transition temperature, melting points, and crystallization temperatures for selected biopolymers is in Table I, below.
  • all of the biopolymer sheets may be of the same material.
  • one of the biopolymer sheets may comprise a material that is different from another biopolymer sheet. Where different sheet materials are used, preferably the glass- transition temperatures of the different materials are similar to one another. Other suitable biopolymers will be apparent to those of skill in the art.
  • the laminating temperature applied during lamination of the plurality of biopolymer resin sheets to one another is between the glass- transition temperature and the melting temperature of the biopolymer resin material.
  • the laminating temperature is at least about 50°F above the glass -transition temperature, more preferably at least about 75 °F above the glass-transition temperature, and most preferably at least about 110°F above the glass-transition temperature. In one embodiment, the laminating temperature is not more than about 200° above the glass-transition temperature.
  • the laminating temperature may between about 50°F and about 200°F above the glass-transition temperature, more preferably between about 75°F and about 175°F above the glass -transition temperature, and most preferably between about 110°F and about 150°F above the glass-transition temperature.
  • the laminating temperature is selected so as to be below the crystallization temperature of the particular biopolymer being processed. It some embodiments, it may be possible to laminate at temperatures within the crystallization range of the biopolymer so long as the laminating time is sufficiently short and the material is quickly quenched to below the crystallization temperature.
  • the glass-transition temperatures of PLA and cellulose acetate are similar to one another.
  • the glass-transition temperature of PLA specifically a PLLA such as BIOMER PLLA L9000
  • the glass- transition temperature of cellulose acetate is between about 150°F and about 155°F.
  • the inventors have found that a laminating temperature between about 215°F and about 280°F works well.
  • a preferred laminating temperature which works particularly well for such materials is between about 250°F and about 280°F (e.g., about 265 °F), which results in complete or nearly complete thermal fusion of the individual biopolymer sheets so that delamination is not readily possible.
  • Such a laminating temperature is about 110°F to about 125°F above the glass-transition temperature of the biopolymer materials.
  • the quenching temperature applied after lamination in order to quickly cool the laminate panel and prevent hazing or clouding as a result of crystallization is below the glass-transition temperature of the biopolymer material.
  • the quenching temperature may be between about 50°F and about 150°F below the glass-transition temperature. More preferably, the quenching temperature may be between about 60°F and about 140°F below the glass-transition temperature. Most preferably, the quenching temperature may be between about 75 °F and about 100°F below the glass-transition temperature.
  • PLA and cellulose acetate which have similar glass-transition temperatures
  • a preferred quenching temperature for such materials is between about 55°F and about 60°F.
  • the quenching apparatus e.g., a cold press
  • active cooling in order to keep it cooler than the ambient temperature (which is often between about 65 °F and about 75°F).
  • ambient temperature which is often between about 65 °F and about 75°F.
  • the quenching temperature may be somewhat higher.
  • PHB has a glass-transition temperature of about 32°F.
  • a suitable quenching temperature for such biomaterials may be at or near the glass-transition temperature.
  • the laminating sequence and/or the quenching sequence may typically also be accompanied by the application of pressure.
  • Typical pressures applied may range between about 25 psi and about 200 psi, more typically between about 25 psi and about 100 psi, and still more typically between about 40 psi and about 60 psi.
  • the time period associated with the laminating sequence may depend on several factors, including the actual laminating temperature (e.g., with higher temperatures, less time may be required to achieve lamination) and the thickness of the pre-laminate assembly (i.e., longer times may be required for thicker assemblies).
  • the time period spent within the lamination apparatus may be between about 3 minutes and about 25 minutes, more preferably between about 5 minutes and about 20 minutes, and most preferably between about 10 minutes and about 15 minutes. In one implementation, the time period is not more than about 15 minutes.
  • the time period associated with quenching may also depend on several factors, including the laminating temperature employed, the quenching temperature employed, the thickness of the pre-laminate assembly, etc. Typically, the quenching times may be similar to the lamination times. In one embodiment, the lamination time period and quenching time period may be substantially equal to one another.
  • Figures 5 A through 5C show processing information relative to various examples that were tested according to the present invention.
  • sample 1 was prepared with the biopolymer BIOMER PLLA L9000, a polylactic acid biopolymer.
  • Biopolymer sheets having a thickness of about 0.03 inch and a size of about 8 inches by about 10 inches were positioned with a SOLO WHITE interlayer and prepared for lamination.
  • SOLO White is a woven fabric material. Finishing plates with a sandstone surface finish were also positioned to provide the outer faces of the biopolymer sheets with the desired surface finish upon processing.
  • the pre- laminate assembly was placed within the hot press and subjected to a laminating temperature of about 245°F and a pressure of about 54 psi for a period of 11 minutes, which resulted in softening of the biopolymer sheets and thermal fusion of the sheets together, providing a unitary laminated panel.
  • the unitary laminated panel was immediately placed within a cold press and subjected to a quenching temperature of about 56°F and a pressure of about 54 psi, also for a period of 11 minutes. Once removed from the cold press, the biopolymer resin portions of the panel were observed to have approximately equal optical clarity as compared to the biopolymer sheets prior to processing.
  • Figure 5B shows further processing information of the same sample 1 as in Figure 5A, but in which it was attempted to improve thermal fusion and delamination resistance by re-laminating the same sample processed in Figure 5A.
  • the assembly was subjected to a laminating temperature of about 230°F and a pressure of about 54 psi for 11 minutes, followed by quenching in the cold press for 11 minutes at 55°F and 54 psi.
  • lamination of the biopolymer sheets was observed to be better at resisting delamination as compared to sample 1 of Figure 5A, it was still possible to separate the individual laminated biopolymer sheets from one another. As in sample 1, there was no observed crystallization clouding, hazing, or thermally induced degradation.
  • Figure 5C illustrates another implementation including a different biopolymer base resin (i.e., SPARTECH REJUVEN8, a PLA biopolymer material) and with a different interlayer (i.e., NOIR LINEN, a coarse black fabric).
  • sample 2 shown in Figure 5C included a patent polished finish applied to the outer faces of the laminate panel.
  • the pre-laminate assembly was subjected to a laminating temperature within a hot press in which the top platen of the press was at about 225°F and the bottom platen of the press was at about 219°F.
  • the laminating time was 6 minutes.
  • the panel was quenched in a cold press at about 58°F for 6 minutes.
  • Figures 6 A and 6B show processing information relative to samples 3 and 4.
  • sample 3 shown in Figure 6 A used the same SPARTECH REJUVEN8 biopolymer material as sample 2 of Figure 5C, but a different interlayer (DRIFT BLUE, a woven fabric) and a different surface finish (sandstone and supermatte textures).
  • Lamination was for the same 11 minutes as in sample 1 of Figure 5 A, but at a significantly higher temperature, 265°F, which is about 120°F above the glass- transition temperature of PLA. Quenching was achieved at 58°F, also for 11 minutes. In both the laminating and quenching sequences, applied pressure was 54 psi.
  • the biopolymer resin sheets laminated about the decorative interlayer cleanly with no added crystallization, hazing, clouding, or panel degradation.
  • the resulting unitary laminate panel exhibited excellent thermal fusion of the initially separate biopolymer, with no tendency towards delamination. The laminated sheets could not be pried apart without destroying the panel.
  • Sample 4 of Figure 6B included SPARTECH CELLULOSE ACETATE biopolymer sheets and an interlayer of DRIFT BROWN, a woven fabric. Patent and supermatte surface finishes were applied to the outer faces of the laminate panel.
  • the SPARTECH CELLULOSE ACETATE exhibited a translucent bluish hue, rather than being substantially clear or transparent as the biopolymer materials of samples 1-3.
  • lamination was performed at about 265 °F over a time interval of about 11 minutes. After lamination, the unitary panel was quenched at about 58°F for about 1 1 minutes. Applied pressure during both lamination and quenching was about 54 psi. As with sample 3, the resulting panel exhibited substantially complete thermal fusing of the panels, excellent bond strength to resist delamination, no signs of bubbles, clouding, hazing, or thermal degradation of the panel.
  • samples 1-4 were performed within a batch type lamination and quenching process, it will be understood that manufacture of panels according to the present invention may employ any machine capable of providing the necessary conditions (e.g., temperature, pressure, etc.).
  • Exemplary manufacturing structures may include, but are not limited to, continuous rollers, an autoclave, etc.
  • One advantageous characteristic of the biopolymer laminate panels is their ability to be used as building materials for a variety of applications including, glazing, light diffusers, signage, partitioning and the like.
  • building product applications are typically regulated by various building codes, such as the International Building Code (IBC).
  • IBC International Building Code
  • the IBC specifically, establishes criteria for use of plastic or polymeric materials used in various building applications. Further, the IBC identifies a category of plastics as "Light-transmitting Plastics" and considers them "approved plastics” if such materials conform to combustibility classifications as specified for use in a given application. Light transmitting plastics are assessed in accordance with flame spread rates as measured in accordance with ASTM D 635 "Standard Test Method for Rate of Burning and/or Extent and Time of Burning of Plastics in a Horizontal Position".
  • a biopolymer resin panel To be considered as an approved light transmitting plastic per the IBC a biopolymer resin panel must be able to attain a burning extent per the ASTM D 635 method of 63.6 millimeters per minute or less when tested in the thickness intended for use.
  • samples were prepared from clear SPARTECH REJUVEN8 (99% NATUREWORKS PLA) material that were 0.03 inch in thickness and 1 ⁇ 2 inch x 4 inches in size and tested in accordance with ASTM D 635.
  • the burn rate for these specimens was 75.0 mm/min; therefore such materials do not conform to the minimum burn rate criteria for light transmitting plastics as established by the IBC.
  • a second set of samples were prepared from clear SPARTECH REJUVEN8 (99% NATUREWOR S PLA) material, except this particular sample set was comprised of 6 layers of 0.03 inch PLA laminated in a similar manner as described above with respect to samples 1-4 of Figures 5A-6B.
  • Lamination temperature was 245°F
  • quenching temperature was 58°F
  • pressure for both lamination and quenching was 55 psi
  • time periods for both lamination and quenching were 1 1 minutes.
  • the resulting laminated panel was about 0.16 inch in total thickness, did not crystallize and had excellent lamination integrity.
  • the laminated panel was cut to a specimen size of 1 ⁇ 2 inch x 4 inches and then fire tested in accordance with ASTM D 635 and the resulting burn rate was dramatically less, at 24.7 mm/min. Data relative to the testing is recorded in Table II, below.
  • the PETG used in this test was commercial VIVAK 0.03 inch thickness extruded PETG sheet obtained from Sheffield Plastics.
  • the PMMA used in this test was commercial OPTIX 0.06 inch and 0.17 inch thickness extruded PMMA sheet from Plaskolite, Inc. PETG and PMMA are used in comparison as they are known and accepted transparent materials that are often used in plastic glazing and lighting applications.
  • clear extruded SPARTECH REJUVEN8 (99% NATURE WORKS PLA) at 0.03 inch thickness from Spartech Plastics was used.
  • a second set of laminated biopolymer samples were prepared from clear SPARTECH REJUVEN8 (99% NATUREWORKS PLA) material. Again, this particular sample set was comprised of 6 layers of 0.03 inch PLA laminated in the same manner as described above relative to the flammability test. The resulting laminated panel was 0.16 inch in total thickness, did not crystallize and had excellent lamination integrity.
  • the PETG impact resistance was the greatest of all, exceeding the impact limitations of the testing apparatus.
  • the PMMA sheet which is also a commonly used material in such panels, does not demonstrate passing results in a thickness of 0.06 inch, even at impact forces as little as 2 in-lbs.
  • the 0.17 inch PMMA sheet shows better impact resistance, but fails at 5 in-lbs.
  • the 0.03 inch PLA does not provide any significant impact resistance, even at the lowest impact threshold (2 in-lbs) on the testing apparatus.
  • the 0.16 inch PLA sample provides an impact resistance up to 6 in-lbs. This result was 50% more than the 4 in-lbs impact resistance provided by the PMMA specimen that was 0.01 inch (6%) thicker.
  • biopolymer resin panels prepared in accordance with implementations of the present invention can be configured to offer desired properties for virtually any intended application, particularly those related to architectural or building panels.
  • biopolymer panels can be configured to have adequate thickness, impact resistance, good optical characteristics including clarity, and flammability resistance to allow their use as a replacement for petroleum-based polymer panels.
  • the impact resistance and flammability resistance is particularly improved as compared to commercially available thin-gauge biopolymer sheets.
  • biopolymer panels constructed in accordance with implementations of the present invention are no more difficult to fabricate and machine with basic fabrication tools as compared to petroleum-based polymer panels.
  • biopolymer panels can be easily manipulated to control surface and light transmitting and diffusing qualities with textured finishes.
  • such panels may be provided in various shapes, including curved configurations.
  • the temperatures and pressures applied for prescribed durations as described herein advantageously do not trigger natural degradation processes and/or induce crystallization clouding or hazing, which would render the panels aesthetically undesirable.
  • panels made in accordance with implementations of the present invention can be used for both aesthetic and structural purposes in a building and/or architectural design environment while offering the life-cycle benefit of being produced from renewable feedstock materials and being biodegradable and/or compostable at the end of their useful life.

Abstract

La présente invention concerne un procédé de fabrication du panneau à base de biopolymères pouvant comprendre les étapes consistant à positionner une pluralité de feuillets de biopolymères les uns à coté des autres, et à les soumettre à une température de stratification supérieure à la température de transition vitreuse des feuillets pendant un temps suffisant pour réaliser la stratification. Le panneau stratifié est ensuite désactivé en utilisant une température de désactivation qui est inférieure à la température de transition vitreuse. Le temps pendant lequel dure la stratification, ainsi que toute période « restant » entre la stratification et la désactivation, est suffisamment court de sorte à empêcher la formation de tout trouble ou ternissage résultant de la cristallisation des matériaux de résine biopolymère. De plus, le panneau présente une ininflammabilité suffisante pour satisfaire aux codes applicables dans le bâtiment, présente une résistance aux chocs suffisante pour une utilisation comme matériau de construction d'un panneau décoratif ou de structure, et ne présente aucune dégradation thermiquement induite remarquable qui résulterait de l'exposition du panneau à la température de stratification. Les panneaux peuvent être utilisés comme matériaux de construction décoratifs ou de structure.
PCT/US2011/028524 2010-03-16 2011-03-15 Panneaux stratifiés produits à partir de biopolymères WO2011115992A2 (fr)

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CN104845291A (zh) * 2015-05-04 2015-08-19 常州伊柯瑞斯装饰材料有限公司 一种pegt生态树脂板及其制备方法

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WO2014203012A1 (fr) * 2013-06-19 2014-12-24 Rapidsil System Kft. Panneau calorifuge à couches et appareil et son procédé de production
CN104845291A (zh) * 2015-05-04 2015-08-19 常州伊柯瑞斯装饰材料有限公司 一种pegt生态树脂板及其制备方法

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