WO2020210765A1 - Stainable thermoformable sheets, compositions, and methods of manufacture - Google Patents

Stainable thermoformable sheets, compositions, and methods of manufacture Download PDF

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Publication number
WO2020210765A1
WO2020210765A1 PCT/US2020/027853 US2020027853W WO2020210765A1 WO 2020210765 A1 WO2020210765 A1 WO 2020210765A1 US 2020027853 W US2020027853 W US 2020027853W WO 2020210765 A1 WO2020210765 A1 WO 2020210765A1
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WO
WIPO (PCT)
Prior art keywords
stainable
sheet
thermoformable sheet
resin binder
weight percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2020/027853
Other languages
English (en)
French (fr)
Inventor
Adam Curtis FUHR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pressing Developments LLC
Original Assignee
Pressing Developments LLC
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 Pressing Developments LLC filed Critical Pressing Developments LLC
Priority to US17/602,741 priority Critical patent/US12065552B2/en
Priority to CA3132935A priority patent/CA3132935A1/en
Priority to JP2021560693A priority patent/JP7675317B2/ja
Priority to EP20787589.9A priority patent/EP3953171A4/en
Publication of WO2020210765A1 publication Critical patent/WO2020210765A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
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    • B32B21/02—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
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    • 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
    • B32B21/06—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 paper or cardboard
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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    • C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2461/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08J2461/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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    • C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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    • C08J2461/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • thermoformable sheets capable of being stained, including with typical absorbing stains, pigmented sealers or clear sealers.
  • Thermofoil is an inexpensive alternative to wood.
  • Thermofoil is a plastic, vinyl, polyethylene terephthalate (PET), or paper substrate that has been printed with either wood grain or a synthetic wood grain print.
  • PET polyethylene terephthalate
  • Thermofoil is in high production throughout the world because it simulates wood but uses resource alternative to wood.
  • Thermofoil is produced, for example, by extruding a PVC or ABS onto a thin continuous sheet of about 10 mm to 2500 mm wide and then wound onto a roll for secondary processing. Once the PVC or ABS has been successfully extruded and rolled, the roll is loaded onto a machine to unroll to pretreat for adhesion and color uniformity. Ink is applied through, for example, a rotogravure printing using UV-cured, solvent-based, or water-based inks or through a high-speed digital printing using UV-cured inks. After the substrate has been printed with the wood grain or synthetic wood grain print, the product is then coated with one or more UV-cured topcoats for final properties to finalize the product.
  • the product can be embossed for a grain texture or simply re-wound onto a roll and cut to size per customer specifications.
  • the resulting product simulates wood, is water resistant, and has various sheens and ranges in durability.
  • the final products include edge banging, wrapped moldings, furniture components, cabinet components, or completed cabinet doors through various gluing processes.
  • Thermofoil products While the existing process provides some flexibility for the customer, the minimum orders for custom products or colors are very large. Also, the global production quality of Thermofoil products is inconsistent. Accordingly, there is a need for manufacturing Thermofoil products that are capable of being stained any color, for example, with absorbing stains, pigmented sealers or clear sealers as well as finished with a professional, high-quality coating to provide a much better look and increased durability of the overall surface.
  • the products and methods disclosed herein would reduce manufacturing and consumer costs and provide greater flexibility for the consumer.
  • the invention relates to a stainable thermoformable sheet.
  • the stainable thermoformable sheet comprises: a Thermofoil sheet; and a stainable topcoat layer affixed to the Thermofoil sheet.
  • the stainable topcoat layer comprises a resin binder formulation comprising resins, an additive, and a porosity agent, before curing.
  • the stainable topcoat layer preferably has at least 35 weight percent of a porosity agent, before curing.
  • the Thermofoil sheet is a polyvinyl chloride (PVC) sheet, an acrylonitrile butadiene styrene (ABS) sheet, or a polyethylene terephthalate (PET) sheet.
  • the invention is also directed to a method of manufacturing a stainable thermoformable sheet.
  • the method comprises the steps of applying to a Thermofoil sheet a stainable topcoat layer having a resin binder formulation comprising resins, an additive, and a porosity agent, before curing.
  • the stainable topcoat layer has at least 35 weight percent of a porosity agent, before curing.
  • the particle size of the porosity agent in one particular non-limiting embodiment is 0.4-70 pm.
  • FIGs. 1-2 depict non-limiting exemplary perspective views of stainable Thermofoil products having one stainable topcoat layer.
  • FIGs. 3-4 depict non-limiting exemplary perspective views of stainable Thermofoil products having two stainable topcoat layers.
  • FIGs. 5-6 depict non-limiting exemplary cross-sectional views of stainable
  • Thermofoil products having one stainable topcoat layer.
  • FIGs. 7-8 depict non-limiting exemplary cross-sectional views of stainable
  • Thermofoil products having two stainable topcoat layers.
  • FIGs. 9-10 depict example processes of manufacturing a stainable Thermofoil product. Optional steps of the process are indicated.
  • references to an element by the indefinite article“a” or“an” does not exclude the possibility that more than one of the elements are present unless the context clearly requires that there is one and only one of the elements.
  • the indefinite article“a” or“an” thus usually means“at least one.”
  • “a” or“the” porosity agent refers to one porosity agent or a combination of porosity agents.
  • the term“about” refers to plus or minus a tolerance that is 20% (e.g, “about 1” refers to 0.8-1.2, and“about 5” refers 4-6).
  • thermoformable sheet or“Thermofoil” refers to a plastic or paper material which is capable of being thermoformed or affixed to the profile of an underlying substrate (e.g., an engineered wood core such as medium-density fiberboard) to produce a surface finish.
  • an underlying substrate e.g., an engineered wood core such as medium-density fiberboard
  • the term“stainable” refers to an ability of the surface of a material to have absorption characteristics that allow a pigment or dye to penetrate which creates a“stain” effect.
  • the term“absorbing stains” refers to a colorant, e.g., one or more dyes and/or pigments, suspended or dissolved in an agent or solvent.
  • a colorant e.g., one or more dyes and/or pigments, suspended or dissolved in an agent or solvent.
  • Non-limiting examples include an oil stain, varnish stain, water-based stain, solvent-based stain, gel stain, lacquer stain, water-soluble dye stain, ultra-violet (UV) light cured colorant, and metal or complex (metalized) dye stain, etc.
  • UV-cured colorant include sealants (e.g, pigmented sealers), stains, etc. Similar stains or colorants now existing or yet to be discovered may also be used.
  • the term“resin” refers to a solid or highly viscous substance of plant or synthetic origin that is typically convertible into polymers.
  • topcoat or“topcoat layer” refers to a layer of resins and compositions overlaying an interior layer of a Thermofoil material.
  • the topcoat is used to give a uniform, smooth or textured, durable, aesthetically appealing, and stainable finish.
  • the term“pigment volume concentration” or“PVC” refers to the volume percentage of solid particles in the system after film formation. The calculation is as follows: the volume of the porosity agent divided by the volume of the porosity agent plus the resin volume solids.“Pigment volume concentration” determines if there is enough mineral in the resin system to actually realize the absorbency of the minerals in the final surface.
  • additive refers to compounds that make the product flow, level, dilute, reduce, react, and/or defoam, e.g., a deaerator, a dispersant, a catalyst, a photoinitiator, a wetting agent, and, etc. Accordingly, additives include surface modifiers, curing agents, and the like.
  • photoinitiator refers to a compound that can transform the physical energy of light into suitable chemical energy in the form of reactive intermediates. On absorption of light, a photoinitiator undergoes a photoreaction and produces reactive species which initiate or catalyze chemical reactions that result in significant changes in the solubility and physical properties of suitable formulations.
  • the present disclosure relates to the discovery that certain porosity-promoting surface agents included in a formulation of a resin binder (e.g., epoxy acrylates or acrylics) applied to a thermoformable sheet result in the resin binder treated thermoformable sheet having a porous surface that is capable of absorbing stains, pigmented sealers or clear sealers after being manufactured.
  • the absorption of the stainable topcoat layer can be controlled by the process of adding finely ground minerals in high concentrations into the stainable (e.g., UV- cured or air-cured) coating.
  • the present disclosure creates even more flexibility and end product control by the customer. Additional benefits include reduced cost and greatly increased water resistance compared to the wood counterpart.
  • a stainable thermoformable sheet comprising a Thermofoil sheet and a stainable topcoat layer affixed to the Thermofoil sheet, wherein the stainable topcoat layer comprises a resin binder formulation comprising resins, an additive, and at least 35 weight percent of a porosity agent, before curing.
  • a method of manufacturing a stainable thermoformable sheet comprising applying to the Thermofoil sheet a stainable topcoat layer comprising a resin binder formulation comprising resins, an additive, and at least 35 weight percent of a porosity agent, before curing.
  • the stainable topcoat layer is pliable and wrappable and allows varying surface effects for staining.
  • a stainable thermoformable sheet is formed by adding at least one porosity agent 150 and at least one additive to a resin binder layer 120 before curing the resin binder layer 120.
  • Existing formulations of energy-curable resins may be used in the present disclosure to create stainable resin binder layers 120 by adding porosity agents 150 as disclosed herein.
  • the stainable thermoformable sheet 130 is a polyvinyl chloride (PVC) sheet, an acrylonitrile butadiene styrene (ABS) sheet, a polyethylene terephthalate (PET) sheet, or a cellulose paper.
  • the stainable thermoformable sheet 130 (FIG. 1) is a polyvinyl chloride (PVC) sheet, an acrylonitrile butadiene styrene (ABS) sheet, or a polyethylene terephthalate (PET) sheet.
  • the stainable thermoformable sheet 130 (FIG. 1) is not a cellulose paper.
  • the stainable thermoformable sheet 130 is a polyvinyl chloride (PVC) sheet. In another aspect, the stainable thermoformable sheet 130 (FIG. 1) is an acrylonitrile butadiene styrene (ABS) sheet. In another aspect, the stainable thermoformable sheet 130 (FIG. 1) is a polyethylene terephthalate (PET) sheet.
  • PVC polyvinyl chloride
  • ABS acrylonitrile butadiene styrene
  • PET polyethylene terephthalate
  • Thermoformable sheets made of PVC, ABS or PET are not capable of being saturated with a resin system (e.g., urea-formaldehyde resins or melamine formaldehyde resins) due to several factors: 1) Chemical compatibility is not present; 2) The PVC, ABS and PET sheets are not capable of withstanding the amount of heat and pressure used to create a laminate surface; and 3)
  • the melamine resin systems can be adapted to have short term adhesion to the surface of PVC, ABS or PET sheets, but the resin system will lose adhesion over time due to the large differences in their modulus of elongation (i.e., the amount the substrate (PVC, ABS or PET) moves versus the amount the coating (melamine resin system) moves over time and tension).
  • the last factor is of particular interest because the process of creating a Thermofoil sheet must allow the sheet to wrap around moulding, door center panels, and the like.
  • the Thermofoil sheet must be pliable and wrappable.
  • the coating system to apply must also have these characteristics.
  • the present invention provides just such a coating system (i.e., a pliable, wrappable, and stainable topcoat layer) that is applied over the thermoformable sheet in contrast to other systems and methods that provide a stainable sheet that is saturated with or embedded in the resin system.
  • Impregnating a thermoformable sheet with the resin system functions differently than coating the thermoformable sheet with a resin system.
  • a resin system saturates a paper sheet, excellent bonding to the substrate as well as uniform stainability result.
  • Having the resin system on the surface as provided by the present invention allows varying surface effects for staining. In other words, applying the resin system topically allows for more creative patterns for staining that cannot be achieved through the impregnated process.
  • the stainable thermoformable sheet 130 is thermoformed or affixed onto an underlying substrate 110 (FIG. 2).
  • substrates 110 include edge banging, wrapped moldings, furniture components, cabinet components, or completed cabinet doors, etc.
  • no additional sealers or topcoats are applied to the thermoformed sheet 130 before the application of the stainable topcoat layer 120.
  • the stainable thermoformable sheet comprises a wood grain design 132 (FIG. 5).
  • the method further comprises producing a wood grain print onto the Thermofoil sheet using an ink selected from the group consisting of: a solvent reduced ink, water reduced ink, and UV curable ink before applying the stainable topcoat layer.
  • the method further comprising applying a seal coating between producing the wood grain print and applying the stainable topcoat layer.
  • the resin binder layer (total applied weight) is in an amount of between 5 and 190 grams per square meter (gsm) of the Thermofoil sheet per layer, or any number range in between, e.g., 5-175 gsm, 5-160 gsm, 5-145 gsm, 5-130 gsm, 5-115 gsm, 5-100 gsm, 5-85 gsm, 5-70 gsm, 10-190 gsm, 10-175 gsm, 10-160 gsm, 10-145 gsm, 10-130 gsm, 10-115 gsm, 10-100 gsm, 10-85 gsm, 10-70 gsm, 15-190 gsm, 15-175 gsm, 15-160 gsm, 15-145 gsm, 15-130 gsm, 15-115 gsm, 15-100 gsm, 15-85 gsm, 15-70 gsm, 15-190 g
  • the resins are energy-curable resins.
  • energy-curable resins include ultraviolet (UV)-curable resins, electron beam (EB)-curable resins, or conventional heat source-curable (non-UV/EB) resins, etc.
  • the resin binder formulation comprises a photoinitiator.
  • the resins require a catalyst to form a film (catalyzed system).
  • the resins form a film without the requirement of additional catalyzation (non-catalyzed system).
  • the resin binder formulation does not require a catalyst.
  • the non- catalyzed system forms a film through air drying due to a relatively low (e.g., lower than room temperature) glass transition temperature (Tg).
  • Tg glass transition temperature
  • the non-catalyzed system uses solvents to decrease the Tg to allow the resin to form a film through evaporation.
  • the energy-curable resins are selected from the group consisting of: urethane acrylates, polyester acrylates, epoxy acrylates, acrylics, and combinations thereof. In other non-limiting implementations, the energy-curable resins are selected from the group consisting of: epoxy acrylates, acrylics, and a combination thereof.
  • Epoxy acrylates are commercially available from manufacturers such as: Sartomer, BASF, or Miller-Stephenson, etc. Non-limiting examples of epoxy acrylates are described in greater detail, and hereby incorporated by reference in their entirety, in the following patents and references: U.S. Patent No. 3,989,610; U.S. Patent No. 4,472,019; U.S. Patent No. 4,789,620; U.S. Patent No. 5,086,088; U.S. Patent No. 5,356,949; US Patent No. 6,844,034; EP Patent No.
  • Acrylics are commercially available from manufacturers such as: Advanced Plastiform, Inc., etc. Non-limiting examples of acrylics are described in greater detail, and hereby incorporated by reference in their entirety, in the following patents: U.S. Patent No. 5,242,968; U.S. Patent No. 5,686,186; U.S. Patent No. 7,252,786; China Patent No. 101044023; and Germany Patent No. DE 69725,422.
  • the resin binder formulation before curing, comprises between 15 and 45 weight percent of the resins (e.g., epoxy acrylates or acrylics), or any percent range in between, e.g., 15-43%, 15-40%, 15-38%, 15-35%, 16-45%, 16-43%, 16-40%, 16-38%, 16-35%, 17-45%, 17-43%, 17-40%, 17-38%, 17-35%, 18-45%, 18-43%, 18-40%, 18-38%, 18-35%, 19-45%, 19-43%, 19-40%, 19-38%, 19-35%, 20-45%, 20-43%, 20-40%, 20-38%, or 20-35% of the resins, etc.
  • the resins e.g., epoxy acrylates or acrylics
  • the resin binder formulation comprises between 5 and 45 weight percent of the resins (e.g., epoxy acrylates or acrylics), or any percent range in between, e.g., 5-40%, 5-35%, 5-30%, 5-25%, 6-45%, 6-40%, 6-35%, 6- 30%, 6-25%, 7-45%, 7-40%, 7-35%, 7-30%, 7-25%, 8-45%, 8-40%, 8-35%, 8-30%, 8-25%, 9-45%, 9-40%, 9-35%, 9-30%, 9-25%, 10-45%, 10-40%, 10-35%, 10-30%, or 10-25% of the resins, etc.
  • the resins e.g., epoxy acrylates or acrylics
  • the resin binder portion of the applied weight is between 2 and 100 gsm per resin binder layer of the Thermofoil sheet, or any number range in between, e.g., 2-95 gsm, 2-90 gsm, 2-85 gsm, 2-80 gsm, 2-75 gsm, 2-70 gsm, 2-65 gsm, 2-60 gsm 2-55 gsm, and 2-50 gsm, etc.
  • the resin binder formulation further comprises urea-formaldehyde resins, melamine formaldehyde resins, or both.
  • the porosity agent comprises one or more mineral (e.g., two, three, four, etc.) to enable the thermoformable sheet to be stained.
  • the particle size of the porosity agent 150 typically ranges from 0.4 pm to 80 pm, or any other number range in between, e.g., 0.4-70 pm, 0.5-70 pm, 0.5-60 pm, 0.6-60 pm, 0.6-50 pm, 0.7-50 pm, 0.7-40 pm, 0.8-40 pm, 0.8-30 pm, 0.9-30 pm, 0.9-20 pm, 0.9-15 pm, 0.4-60 pm, 0.4-45 pm, 0.4-30 pm, or 0.4-15 pm.
  • the density of the porosity agents 150 typically ranges from 0.5 g/cm 3 to 4.5 g/cm 3 , or any other number range in between, e.g., 0.5- 4.2 g/cm 3 , 0.6-4.2 g/cm 3 , 0.6-4.0 g/cm 3 , 0.7-4.0 g/cm 3 , 0.7-3.8 g/cm 3 , 0.8-3.8 g/cm 3 , 0.8-3.6 g/cm 3 , 0.9-3.6 g/cm 3 , 0.9-3.5 g/cm 3 , 1-3.5 g/cm 3 , 1-3.4 g/cm 3 , 1.1-3.4 g/cm 3 , 1.1-3.3 g/cm 3 , 1.1-3.2 g/cm 3 , 1.2-3.2 g/cm 3 , 1.4-3.2 g/cm 3 , 1.4-3.1 g
  • Non-limiting examples of the porosity agents 150 include: calcium carbonate (e.g., precipitated calcium carbonate), crystalline silica (e.g., microcrystalline silica, silica, and silicate minerals), kaolin clay, talc; another mineral commonly used in the production of paint and coatings; another agent that result in a cured resin binder surface having porous characteristics that enable a stain to penetrate into the resin binder layer 120, or combinations thereof, etc.
  • Silica includes untreated silica, treated silica, or both.
  • At least one of the porosity agents 150 is selected from the group consisting of: calcium carbonate, kaolin clay, silica, and talc. In other embodiments, at least one of the porosity agents 150 is selected from the group consisting of: kaolin clay, silica, and talc. In yet other embodiments, the porosity agent 150 is selected from the group consisting of: kaolin clay and talc.
  • the porosity agent 150 is calcium carbonate.
  • the calcium carbonate is ground (natural) calcium carbonate (GCC).
  • the particle size of the calcium carbonate is between about 0.5 pm and about 500 pm, between about 0.5 pm and about 400 pm, between about 0.5 pm and about 300 pm, between about 0.5 pm and about 200 pm, between about 0.5 pm and about 100 pm, between about 0.5 pm and about 90 pm, between about 0.5 pm and about 80 pm, between about 0.5 pm and about 70 pm, between about 0.5 pm and about 60 pm, between about 0.5 pm and about 50 pm, between about 0.5 pm and about 40 pm, between about 0.5 pm and about 30 pm, between about 0.5 pm and about 20 pm, or between about 0.5 pm and about 10 pm.
  • the particle size of the calcium carbonate is between about 0.5 pm and about 100 pm.
  • the particle size of the calcium carbonate is between about 0.5 pm and about 50 pm.
  • the porosity agent 150 is not silica.
  • silica may have an adverse effect on the ability of the final surface to absorb stains.
  • the porosity agent 150 comprises kaolin clay, silica, and talc in the ratio of about 3 to 2 to 1 by weight (i.e., a formulation comprising 600 grams of mineral would comprise about 300 grams of kaolin clay, about 200 grams of silica, and about 100 grams of talc).
  • the porosity agent 150 comprises kaolin clay, silica, and talc in the ratio of about 2.5-3.5 to 1.5-2.5 to 1 by weight, or any ratio range in between, e.g., 2.6-3.4 to 1.6-2.4 to 1, 2.7-3.3 to 1.7-2.3 to 1, 2.8-3.2 to 1.8-2.2 to 1, 2.9-3.1 to 1.9-2.1 to 1, etc.
  • the typical amount of the one or more porosity agents 150 per resin binder layer is at least 2 gsm of the Thermofoil sheet, e.g., at least 2.5 gsm, at least 3 gsm, at least 3.5 gsm, or at least 4 gsm of the Thermofoil sheet.
  • the typical amount of the one or more porosity agents 150 per resin binder layer is between 2-100 grams per square meter (gsm) of the Thermofoil sheet, or any number range in between, for example, 3-70 gsm, 3-65 gsm, 3-60 gsm, 3-55 gsm, 3-50 gsm, 3-45 gsm, 3-40 gsm, 3-35 gsm, 3-30 gsm, 3-25 gsm, 3-20 gsm, 3.5-70 gsm, 3.5-65 gsm, 3.5-60 gsm, 3.5-55 gsm, 3.5-50 gsm, 3.5-45 gsm, 3.5-40 gsm, 3.5-35 gsm, 3.5-30 gsm, 3.5-25 gsm, 3.5-20 gsm, 4-70 gsm, 4-65 gsm, 4-60 gsm, 4-55 gsm, 3-35 g
  • the resin binder formulation 124 comprises at least 35 weight percent of the porosity agent, before curing, e.g., at least 40 weight percent, at least 45 weight percent, at least 50 weight percent, at least 55 weight percent, or at least 60 weight percent of the porosity agent, before curing.
  • the resin binder formulation 124 comprises between 30% and 70% of the porosity agent, before curing, or any percent range in between, e.g., 30% and 68%, 35-68%, 35-65%, 36-65%, 36-63%, 37-63%, 37-60%, 38-60%, or 40- 60%, etc., before curing.
  • the pigment volume concentration (PVC) is very important in the overall functionality of the system to become absorbent.
  • the pigment volume concentration (PVC) is between 25%-80%, or any percent range in between, for example, 25%-70%, 25%-65%, 25%-60%, 25%-55%, 30%-80%, 30%-75%, 30%-70%, 30%- 65%, 30%-60%, 30%-55%, 35%-80%, 35%-75%, 35%-70%, 35%-65%, 35%-60%, 35%- 55%, 40%-80%, 40%-75%, 40%-70%, 40%-65%, 40%-60%, 45%-80%, 45%-75%, 45%- 70%, 48%-80%, 48%-75%, or 48%-70%, etc.
  • the resin binder further comprises an additive, wherein at least one additive is selected from the group consisting of: a deaerator, a dispersant, a wetting agent, a photoinitiator, a catalyst, and combinations thereof.
  • the resin binder formulation before curing, comprises between 0.01 and 1 weight percent of the deaerator, or any percent range in between, for example, 0.01 and 0.9 weight percent, 0.01-0.8 weight percent, 0.01-0.7 weight percent, 0.01- 0.6 weight percent, 0.01-0.5 weight percent, 0.015 and 1 weight percent, 0.015 and 0.9 weight percent, 0.015-0.8 weight percent, 0.015-0.7 weight percent, 0.015-0.6 weight percent, 0.015-0.5 weight percent, 0.02-1 weight percent, 0.02 and 0.9 weight percent, 0.02-0.8 weight percent, 0.02-0.7 weight percent, 0.02-0.6 weight percent, or 0.02-0.5 weight percent of the deaerator, etc.
  • the resin binder formulation comprises between 0.01 and 1 weight percent of the dispersant, or any percent range in between, for example, 0.01 and 0.9 weight percent, 0.01-0.8 weight percent, 0.01-0.7 weight percent, 0.01- 0.6 weight percent, 0.01-0.5 weight percent, 0.015 and 1 weight percent, 0.015 and 0.9 weight percent, 0.015-0.8 weight percent, 0.015-0.7 weight percent, 0.015-0.6 weight percent, 0.015-0.5 weight percent, 0.02-1 weight percent, 0.02 and 0.9 weight percent, 0.02-0.8 weight percent, 0.02-0.7 weight percent, 0.02-0.6 weight percent, or 0.02-0.5 weight percent of the dispersant, etc.
  • the resins are ultraviolet (UV)-curable, electron beam (EB)- curable, or both
  • the resin binder formulation comprises, before curing, between 0.4 and 5 weight percent of the photoinitiator, or any percent range in between, for example, 0.4-4.5 weight percent, 0.4-4 weight percent, 0.5-5 weight percent, 0.5-4.5 weight percent, 0.5-4 weight percent, 0.8-5 weight percent, 0.8-4.5 weight percent, 0.8-4 weight percent, 1-5 weight percent, 1-4.5 weight percent, 1-4 weight percent, 1.5-5 weight percent, 1.5-4.5 weight percent, 1.5-4 weight percent, 2-5 weight percent, 2-4.5 weight percent, or 2-4 weight percent of the photoinitiator, etc.
  • the resin binder formulation comprises, before curing, between 0.4 and 5 weight percent of the catalyst, or any percent range in between, for example, 0.4-4.5 weight percent, 0.4-4 weight percent, 0.5-5 weight percent, 0.5 -4.5 weight percent, 0.5-4 weight percent, 0.8-5 weight percent, 0.8-4.5 weight percent, 0.8-4 weight percent, 1-5 weight percent, 1-4.5 weight percent, 1-4 weight percent, 1.5-5 weight percent, 1.5-4.5 weight percent, 1.5-4 weight percent, 2-5 weight percent, 2-4.5 weight percent, or 2-4 weight percent of the catalyst, etc.
  • the resin binder layer is between 90-100% cured, or any percent range in between, e.g., 90-99%, 90-98%, 90-97%, 90-96%, 92-100%, 92-99%, 92-98%, 92-97%, 92-96%, 94-100%, 94-99%, 94-98%, 94-97%, 94-96%, 95-100%, 95-99%, 95-98%, 95-97%, 95-96%, 100% cured, etc.
  • more than one stainable topcoat layers are affixed to the Thermofoil sheet.
  • the first stainable topcoat layer is the top most layer, and the amount of the porosity agents is higher in the first stainable topcoat layer than the second stainable topcoat layer.
  • a pattern is applied to the first stainable topcoat layer using a printing cylinder, thus creating the pattern on the final surface, and no pattern is applied to the second stainable topcoat layer.
  • the resin binder formulation of the first stainable topcoat layer comprises about 50 weight percent of a porosity agent, before curing. In other non-limiting implementations, the resin binder formulation of the first stainable topcoat layer comprises 40-60 weight percent of a first porosity agent, before curing, or any percentage number in between, e.g., 41-59%, 42-58%, 43-57%, 44-56%, or 45-55%, etc.
  • the resin binder formulation of the second stainable topcoat layer comprises 15-40 weight percent of a second porosity agent, before curing, or any percentage number in between, e.g., 15-35%, 15-30%, 15-25%, 20-40%, 20- 35%, 20-30%, 25-40%, 25-35%, 25-30%, or 30-40%, etc.
  • Non-limiting examples of the first and/or the second porosity agents 150 include: calcium carbonate (e.g., precipitated calcium carbonate), crystalline silica (e.g., microcrystalline silica, silica, and silicate minerals), kaolin clay, talc; another mineral commonly used in the production of paint and coatings; another agent that result in a cured resin binder surface having porous characteristics that enable a stain to penetrate into the resin binder layer 120, or combinations thereof, etc.
  • Silica includes untreated silica, treated silica, or both.
  • At least one of the first and/or the second porosity agent 150 is selected from the group consisting of: calcium carbonate, kaolin clay, silica, and talc. In other embodiments, at least one of the first and/or the second porosity agent 150 is selected from the group consisting of: kaolin clay, silica, and talc. In yet other embodiments, the first and/or the second porosity agent 150 is selected from the group consisting of: kaolin clay and talc.
  • a stain is applied to the stainable thermoformable sheet.
  • one or more additional coatings are applied after the stain.
  • the additional coatings applied after the stain include resins, and clear sealers, etc. (When a sealer is applied over the stainable topcoat layer, the thermoformable sheet is no longer stainable.)
  • FIGs. 1-4 depict non-limiting examples of the stainable Thermofoil product 100.
  • the exemplary stainable Thermofoil product 100 comprises a Thermofoil sheet 130 and one or more stainable resin binder layer 120 applied to the surface of the Thermofoil sheet 130.
  • there is one stainable resin binder layer 120 (FIGs. 1 and 2).
  • there are two stainable resin binder layers FIGs. 3 and 4
  • there are more than two stainable resin binder layers (not shown).
  • the stainable Thermofoil product 100 further comprises a substrate 110 (FIGs. 2 and 4).
  • the Thermofoil sheet 130 is thermoformed or affixed onto the substrate 110 via, for example, heat melting glue.
  • the Thermofoil sheet 130 is a polyvinyl chloride (PVC) sheet, an acrylonitrile butadiene styrene (ABS) sheet, a polyethylene terephthalate (PET) sheet, or a cellulose paper.
  • the“complete” Thermofoil products available on the market are intended to be finished products not designed to retain staining and/or clear finish.
  • Stainable Thermofoil products however, have open and porous surfaces capable of retain staining and/or clear finish.
  • applying a resin binder layer 120 comprising minerals and additives to the Thermofoil during the production process creates the open and porous surfaces. Additionally, the porous surfaces physically harden, allowing the final layer to be sanded without impacting the underlying print.
  • the adhesion of the Thermofoil sheet 130 to the substrate 110 is based on heat melting glue that is applied to the back of the foil or by actually applying glue to the back of the foil and part to affix the foil to the substrate.
  • the foil can be formed around contoured surfaces and wrapped around surfaces that have been previously formed through molding and cutting.
  • the stainable Thermofoil can be applied to the substrate in both heated and cold press processes.
  • FIGs. 5-8 depict non-limiting examples of the stainable resin binder layer 120.
  • the stainable resin binder layer 120 includes only one porosity agent 150 (150, 151 in FIGs. 5 and 7).
  • the stainable resin binder layer 120 includes two porosity agents 150 (150, 151 and 150, 152 in FIG. 6 and the first stainable topcoat layer of FIG. 8).
  • the stainable resin binder layer 120 includes more than two porosity agents 150 (not shown).
  • the resin binder layer 120 is the final, topmost layer. In other non-limiting embodiments, the resin binder layer 120 includes more than one layer.
  • the stainable Thermofoil product 100 includes a stainable resin binder layer 120, and the stainable resin binder layer 120 is formed by applying to the surface of the Thermofoil sheet with an energy curable resin 124 that contains at least one porosity agent 150.
  • the stainable topcoat layer 120 comprises sufficient porosity agent 150 to allow for the absorption of both the energy curable resin 124 and the subsequent stain applied after curing.
  • the thermoformable sheet 130 is a polyvinyl chloride (PVC) sheet, an acrylonitrile butadiene styrene (ABS) sheet, a polyethylene terephthalate (PET) sheet, or a cellulose paper.
  • a stainable topcoat layer 120 comprising high-volume porosity agents 150 e.g., based on printing one of the stainable topcoats
  • highly repeatable, yet realistic substrate can be created for the industry to use in mass production.
  • a sealer that does not contain a porosity agent is applied below the stainable topcoat layer.
  • the substrate would be sealed, and a stain would not be able to reach past the sealer to the Thermofoil sheet 130.
  • the stainable topcoat layer 120 is printed as a pattern onto the Thermofoil sheet 130.
  • the porosity agents 150 can contribute to creating a stainable Thermofoil product 100 in a number of different ways.
  • the porosity agents 150 distributed throughout the resin binder layer 120 provide a path for a stain to seep into and ultimately reach the sheet 130, where the sheet 130 then soaks in, distributes, and holds the stain. Additionally, the porosity agents 150 themselves can soak in stain and help add more of the stain color throughout the resin binder layer 120. Experiments have shown that deep and even stain penetration often occurs when the pigment volume concentration of the porosity agent(s) 150 to the energy curable resin 124 reaches or exceeds the critical pigment volume concentration of the energy curable resin 124.
  • the critical pigment volume concentration of the thermosetting polymer resin 124 often depends on the physical and chemical characteristics of the porosity agents 150 and how these characteristics interact with the energy curable resin 124. Thus, it is understood that the critical pigment volume concentration of the energy curable resin 124 will vary across different porosity agents 150.
  • FIG. 9-10 depict non-limiting examples of manufacturing the stainable Thermofoil product.
  • the methods comprise applying to the surface of the Thermofoil sheet with a stainable topcoat layer comprising porosity agent 150 (960) followed by curing the Thermofoil sheet (970).
  • the process started with an extruding process, for example, extruding the PVC or ABS onto a thin continuous sheet (910).
  • the sheet is between 10mm - 2500mm wide.
  • the sheet is then wound onto a roll for secondary processing (920).
  • the roll is then loaded onto a machine to unroll (930) and pretreated for adhesion and color uniformity (940).
  • ink is applied to the sheet (950).
  • the ink is applied through either a rotogravure printing using UV- cured, solvent-based, or water-based inks.
  • the ink is applied with high-speed digital printing using UV cured inks.
  • the product is then coated with one or more topcoats (960).
  • a UV-cured topcoat or an air-cured topcoat is used.
  • the sheet is then cured (970). Once the foil has all of the layers completed, the product can be embossed for a grain texture or simply re-wound onto a roll and cut to size per customer specifications.
  • the transformable sheet is transformed onto a substrate before the application of the stainable topcoat layer. See, e.g.. FIG. 10.

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PCT/US2020/027853 2019-04-11 2020-04-11 Stainable thermoformable sheets, compositions, and methods of manufacture Ceased WO2020210765A1 (en)

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US17/602,741 US12065552B2 (en) 2019-04-11 2020-04-11 Stainable thermoformable sheets, compositions, and methods of manufacture
CA3132935A CA3132935A1 (en) 2019-04-11 2020-04-11 Stainable thermoformable sheets, compositions, and methods of manufacture
JP2021560693A JP7675317B2 (ja) 2019-04-11 2020-04-11 染色可能な熱成形シート、組成物、及び製造方法
EP20787589.9A EP3953171A4 (en) 2019-04-11 2020-04-11 COLORABLE THERMOFORMABLE FILMS, COMPOSITIONS AND MANUFACTURING PROCESSES

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US20220195135A1 (en) 2022-06-23
CA3132935A1 (en) 2020-10-15

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