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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
  • B29C64/255—Enclosures for the building material, e.g. powder containers
• • 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
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • 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
  • B32B27/285—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 comprising polyethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
• • 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
  • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
  • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
• • 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
  • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
• • 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
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
  • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal 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
  • 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
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
• • 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
  • B32B2457/00—Electrical equipment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing

Definitions

• This invention relates to 3D printers and to polymeric laminates for use in 3D printers.
• 3D printers make use of a film or sheet having desired permeability characteristics.
• Some types of 3D printer e.g. CLIP printers (CLIP being an abbreviation for Continuous Liquid Interface Production or Continuous Liquid Interface Printing), DLP printers (3D printers which are based on a digital light projector or digital light processor), DLV printers (3D printers which are based on a digital light valve) and some SLA 3D printers require the use of a film or sheet which is permeable to oxygen.
• Some other types of 3D printer can benefit from, or require the use of, a film or sheet which can be, but is not necessarily, permeable to oxygen.
• this invention provides apparatus for preparing an article having a desired configuration, the configuration comprising different parts which are on top of or otherwise adjacent to each other, the apparatus comprising
• a photo-polymerizable polymeric composition (2) a window, preferably a planar window, having an upper surface and an opposite lower surface,
• the window is an oxygen-permeable laminate comprising a first layer and a second layer, the first layer being composed of a first polymeric composition comprising a PMP polymer as hereinbefore defined, and/or a PPO polymer as hereinafter defined, and/or a carbon molecular sieve membrane as hereinafter defined, and/or a polyacetylene, and/or a para-substituted polystyrene, and/or a polynorbomene, and the second layer being composed of an amorphous fluoropolymer as hereinafter defined.
• this invention provides apparatus for preparing an article having a desired configuration, the configuration comprising different parts which are on top of or otherwise adjacent to each other, the apparatus comprising
• a window preferably a planar window, having an upper surface and an opposite lower surface
• the window is an oxygen-permeable laminate comprising a first layer and a second layer, the first layer being composed of a first polymeric composition, the first polymeric composition being a single polymer or a mixture of polymers, the polymer or at least one of the polymers being a non-elastomeric polymer and having a glass transition temperature of at least 0°C.
• this invention provides a laminate which is useful in the apparatus described above and which comprises a first layer and a second layer, the first layer being composed of a first polymeric composition comprising a PMP polymer as hereinafter defined and/or a PPO polymer as hereinafter defined, and/or a carbon molecular sieve membrane as hereinafter defined, and/or a polyacetylene, and/or a para-substituted polystyrene, and/or a polynorbornene.
• a laminate which is useful in the apparatus described above and which comprises a first layer and a second layer, the first layer being composed of a first polymeric composition comprising a PMP polymer as hereinafter defined and/or a PPO polymer as hereinafter defined, and/or a carbon molecular sieve membrane as hereinafter defined, and/or a polyacetylene, and/or a para-substituted polystyrene, and/or a polynorbornene.
• the laminate of the invention preferably comprises
• a first layer which transmits light and is composed of a first polymeric composition the first polymeric composition being a single polymer or a mixture of polymers, the polymer or at least one of the polymers preferably being a non- elastomeric polymer and preferably having a glass transition temperature of at least 0°C., for example a PMP polymer as hereinafter defined, and
• the first layer (which comprises the first polymeric composition) preferably has an oxygen permeability of at least 10 Barrer.
• the second layer (which comprises the fluoropolymer) preferably has an oxygen permeability of at least 100 Barrer.
• a thin layer of a primer which is between the first and second layers and which promotes adhesion of the two layers to each other.
• the layer of primer when it is present, is so thin (for example less than 80 nm) that its oxygen permeability is not significant
• this invention provides methods of making a laminate according to the third aspect of the invention.
• the method comprises the steps of
• first film which is a preformed film of the first polymeric composition (which may for example be a PMP polymer as hereinafter defined),
• the activation step comprising, for example, subjecting a surface of the preformed film to a corona discharge and/or plasma etching treatment, and/or applying a primer to a surface of the preformed film,
• Figure 1 is an exemplary schematic diagram of a DLP 3D printer.
• Figure 2 is a diagrammatic cross-sectional view of an exemplary laminate of the invention.
• Figure 3 is a diagrammatic enlarged cross-sectional view of a portion of Figure 2.
• Figure 4 diagrammatically illustrates the steps in one method of preparing the laminate of the invention.
• compositions or devices comprising or “which comprises”) components A, B and C can contain only components A, B and C, or can contain not only components A, B and C but also one or more other components.
• At least followed by a number is used herein to denote the start of a range beginning with that number (which may be a range having an upper limit or no upper limit, depending on the variable being defined). For example, “at least 1” means 1 or more than 1 , and “at least 80%” means 80% or more than 80%.
• At most followed by a number is used herein to denote the end of a range ending with that number (which may be a range having 1 or 0 as its lower limit, or a range having no lower limit, depending upon the variable being defined). For example, “at most 4" means 4 or less than 4, and “at most 40%” means 40% or less than 40 %.
• a range is given as " (a first number) to (a second number)" or "(a first number) - (a second number)"
• “from 8 to 20 carbon atoms” or “8-20 carbon atoms” means a range whose lower limit is 8 carbon atoms, and whose upper limit is 20 carbon atoms.
• the terms “plural”, “multiple”, “plurality” and “multiplicity” are used herein to denote two or more than two features.
• first and second features this is generally done for identification purposes; unless the context requires otherwise, the first and second features can be the same or different, and reference to a first feature does not mean that a second feature is necessarily present (though it may be present).
• reference is made herein to "a" or “an” feature this includes the possibility that there are two or more such features (except where the context excludes that possibility).
• item A and/or item B and/or item C discloses seven possibilities, namely (1) only item A is present, (2) only item B is present, (3) only item C is present, (4) both item A and item B are present, but item C is not present, (5) both item A and item C are present, but item B is not present, (6) both item B and item C are present, but item A is not present, and (7) all of item A, item B and item C are present.
• the selected component can be a single one of the specified sub-components or a mixture of two or more of the specified sub-components.
• fluoropolymer is used herein to denote an amorphous polymer comprising units derived from a monomer containing at least one fluorinated carbon atom, preferably at least one perfluorinated carbon atom, for example one or more of (i) a monomer which is a perfluorinated ethylenically unsaturated hydrocarbon, for example tetrafluoroethylene, and/or (ii) perfluoro methyl vinyl ether, and/or (iii) perfluoro propyl vinyl ether, and/or (iv) perfluoropropylene, and/or (v) a monomer containing a perfluoro-1,3-dioxole moiety.
• the fluoropolymer can be a homopolymer, or a copolymer (including a terpolymer). Examples of the monomers that can be used are (i) perfluoro-
• the fluoropolymer preferably contains at least 80 mol percent, for example about 100 mol percent, of units derived from one or more monomers each of which contains at least one fluorinated, preferably perfluorinated, carbon atom.
• Examples of commercially available perfluoropolymers include the products sold under the tradenames Teflon AF 1100, Teflon AF 1300, Teflon AF 2400, Teflon AF 1600, Teflon AF 1601 and Hyflon AD.
• the term “PMP polymer” is used herein to denote a polymer containing units derived from 4-methyl-1-pentene.
• the PMP polymer preferably comprises at least 80 mol percent, for example about 100 mol percent, of repeating units derived from 4-methyl- 1-pentene.
• the PMP polymer can be a copolymer of 4-methyl-1-pentene and a monomer containing functional units, for example functional units which improve the adhesion between the first and second layers of the laminate or, when the laminate includes a primer, to the primer.
• Such copolymers are, for example, disclosed in US 7,524,913 (publication No. 2008 0021172), the entire disclosure of which is incorporated herein by reference for all purposes.
• PMP polymers examples include those sold under the tradenames MX 004, MX 0020, MX 002, R-18 and DX 485.
• PPO polymer is used herein to denote a polymer derived from one or more substituted phenylene oxides (including mixtures thereof), in which the phenyl group is substituted by 1 , 2 or 3 alkyl, substituted alkyl, phenyl, substituted phenyl, halogen, alkoxy, alkenyl, alkynyl or amino groups, for example poly (2,6-dimethyl-p- phenylene oxide) and related polymers in which one or both of the methyl groups is replaced by a different group, for example the polymer in which each of the methyl groups is replaced by a phenyl group.
• carbon molecular sieve membrane is used herein to denote the CMSM materials described by Xiao-Hau, Gas Separation Membranes, Adv Poly. Materials, 2018),
• the first layer of the laminate is composed of a first polymeric composition, the first polymeric composition being a single polymer or a mixture of polymers, the polymer or at least one of the polymers preferably being a non-elastomeric polymer and preferably having a glass transition temperature of at least 0°C.
• the first polymeric composition comprises a PMP polymer as hereinbefore defined.
• the first composition can consist essentially of a homopolymer or copolymer of 4-methyl-1-pentene.
• the first layer is composed of a different polymeric composition, for example a polyester such as Mylar, poly (2.6- diphenyl-p-phenylene oxide), CMSMs as described by Xiao-Hau, Gas Separation Membranes, Adv Poly. Materials, 2018, a polyacetylene, a para-substituted polystyrene, or a polynorbornene, for example poly (trimethylsilylnorbornene).
• a polyester such as Mylar
• CMSMs as described by Xiao-Hau, Gas Separation Membranes, Adv Poly. Materials, 2018, a polyacetylene, a para-substituted polystyrene, or a polynorbornene, for example poly (trimethylsilylnorbornene).
• the thickness of the first layer can for example be 0.25-15 mil, e.g. 0.25-10 mil, or 0.25-5 mil, or 0.75-2 mil.
• the oxygen permeability of the first layer is preferably at least 10 Barrer.
• the second layer of the laminate is composed of a second polymeric composition, the second polymeric composition being a single polymer or a mixture of polymers, the polymer or at least one of the polymers being a fluoropolymer as hereinbefore defined.
• the thickness of the second layer is preferably 0.5 -500 pm, for example 1-100 pm, e.g. 5-25 pm.
• the Layer of Primer is preferably 0.5 -500 pm, for example 1-100 pm, e.g. 5-25 pm.
• the laminate optionally comprises a layer of a primer between the first and second layers.
• a preferred process for preparing the laminate includes the creation of a layer of primer on the surface of the preformed film of the first polymeric composition.
• the layer of the primer need not be continuous, but can for example be a series of lines, a pattern of rectangles or a series of drops in a regular or irregular pattern.
• the primer is preferably a compound comprising functional groups which can interact with one or both of the first and second layers.
• the primer can include a fluorinated portion which promotes adhesion to the layer containing a fluoropolymer and/or another portion which adheres to the other layer of the laminate.
• the primer compound can for example be a fluoropolymer as defined which contains one or more functional groups, for example a carboxylic group.
• the presence in the primer of one or more perfluorinated carbon atoms assists adhesion to the second (fluoropolymer) layer, and the presence of suitable functional groups, for example terminal and/or pendant carboxyl groups or phosphate groups, assists adhesion to the first layer, which may for example comprise a PMP polymer.
• Suitable primers include dicarboxy-(polyperfluoro- 2,3-dimethylene-1-oxolane), a copolymer of perfluoroethylene and perfluoro-2,2-bis- methyl-1 ,3-dioxole with terminal and/or pendent carboxylic acid groups or phosphate groups, Fluorolink AD 1700, Fluorolink phosphate, Fluorolink MD 700 and amide- terminated Fluorolink.
• Other solvents can be used include the Fluorinert solvents the Galden fluids from Solvay (e.g. Galden HT135) and Flutec from Rhone-Poulenc (e.g. Flutec PP6.)
• the primer can be applied to the preformed film of the first polymeric composition (which is for example a PMP polymer) as a solution in a solvent which is later wholly or almost completely removed, thus creating a thin layer of the primer compound on the surface of the first film.
• the amount of the solvent remaining in the layer of primer is preferably less than 5%, particularly less than 2%, by weight of the layer of primer.
• the primer can be applied as a solution in a fluorinated solvent, e.g. Fluorinert or Novack, the solution containing for example 0.5-5 % by weight of the primer.
• the solution of the primer can be applied in any way, for example by means of an ultrasonic spray nozzle, or manual wiping.
• the thickness of the dried layer can for example be from about 10 nm to about 5 pm
• That method preferably employs both activation of the preformed film composed of the first polymeric composition (for example containing the PMP polymer) and application of the primer solution to the activated surface of the preformed film.
• the activation can for example comprise exposing the surface of the film to corona etching and/or plasma etching.
• the application of the primer solution should be carried out while the effect of the activation is still present.
• a solution of the second polymeric composition (comprising the fiuoropolymer) is then coated on the surface of the preformed film, and heated to remove most of the solvent and produce a hard layer of the second composition comprising the fiuoropolymer.
• the laminate according to the first aspect of the invention is prepared by the steps of (A) providing a preformed film comprising the first or the second polymeric composition; (B) activating a surface of the preformed film and/or applying a primer composition to a surface of the preformed film; and (C) providing a film comprising the first or the second polymeric composition, the composition being different from the polymeric composition in the preformed film in step (A), on the surface of the preformed film.
• step (C) includes two possibilities, namely (i)) applying a preformed film of a polymeric composition, the composition being different from the polymeric composition in the preformed film in step (A) to the surface of the preformed film used in step (B), or (ii) applying a liquid comprising the polymeric composition to the film resulting from step (A), and (iii) solidifying the liquid composition resulting from step (C iii).
• the laminate is prepared by a process which comprises the steps of
• step (C) applying to the surface of the preformed film from step (B) a solution comprising either the first or second polymeric composition, the composition being different from the polymeric composition in the preformed film, for example the second polymeric composition comprising a fluoropolymer, and drying the solution
• step(D) repeating step(C) at successive coating stations until the desired thickness of the dried polymeric composition has been achieved.
• the laminate is prepared using an extrusion line capable of co-extruding two or more polymeric compositions.
• Each of the first and second polymeric compositions is loaded into its hopper and the laminate is extruded with one layer consisting of the first polymeric composition and a second layer consisting of the second polymeric composition.
• EXAMPLE 1 A 1 mil film of poly (4-methyl-1pentene) [available from Air-Tech, Huntington California] was given a corona etch treatment [using a Model BD-20 available from Electro-Tech, Chicago, Illinois] and then spray coated, using an ultrasonic sprayer [available from Sono-Tech, , Milton, New York] with a thin layer of a primer in the form of a 1 % solution of dicarboxy-(polyperfluoro-2,3-dimethylene-1 -oxolane) in Fluorinert FC-40. The oxolane solution was evenly spread over the entire surface of the PMP film and allowed to dry, initially at room temperature and then at 150°C for 15 minutes.
• the primed surface of the PMP film was coated with a solution of Teflon AF 2400 in Fluorinert FC-40.
• the resulting product was initially cured at 80°C with a final cure in vacuo at an elevated temperature. The layers in the resulting film could not be separated by hand.
• the oxygen permeability of the dried layer of oxolane primer was less than or equal to 10 Barrer.
• the primed PMP film was coated with a 4.41 % solution of Teflon AF2400 and dried initially at 80 and then occurred at 180° C under a vacuum of 0.060 mm Hg.
• the layers in the resulting film could not be separated by hand.
• a non-contact thin film measurement device [Filmetrics, Sunnyvale, California] the thickness of the laminate was measured and showed that the Teflon AF2400 layer had a thickness of 25 pm and the PMP layer had a thickness 50 pm.
• a 2 mil film of PMP [MX 002, Honeywell] is corona etched and then spray coated with a thin layer of a primer which is a copolymer of perfluoroethylene and perfluoro-2,2- bis-methyl-1,3-dioxole with terminal carboxylic acid groups [Chemours, Wilmington, Delaware].
• This primer has an oxygen permeability greater than 10 Barrer and is typically greater than 50 Barrer.
• the spray-coated layer is dried and the film is then coated with a 6% solution of Teflon AF 1600 in FC-40.
• the product is cured, initially at 80°C and then in vacuo at the glass transition temperature of the Teflon AF 1600. This is an example of using a primer with oxygen permeability greater than or equal to 10 Barrer.
• a 2.5 mil film of DX 485 PMP [Specialty Extruders, Royersford, Pennsylvania] is corona etched and then spray coated with a thin layer of 1% solution of a copolymer of perfluoroethylene and perfluoro-2,2-bis-methyl-1 ,3-dioxole with terminal phosphate groups.
• the spray-coated layer is dried and the spray-coated film is coated with a 4.4 % solution of Teflon AF 2400 in FC-43.
• the product is cured, initially at 80°C and then in vacuo at an elevated temperature.
• a 5 mil film of DX 485 PMP [Westlake Plastics, Lenni, Pennsylvania] is corona etched and then spray coated with a thin layer of 1% solution of SF60 [Chemours, Wilmington, Delaware].
• the spray-coated layer is dried and the spray-coated film is coated with a 4.4 % solution of Teflon AF 2400 in FC-40.
• the product is cured, initially at 80°C and then in vacuo at 100°C.
• EXAMPLE 6 A 2 mil film of DX 485 PMP [Specialty Extruders, Royersford, Pennsylvania] is plasma etched and then spray coated with a 1% solution EVE-P [Chemours,
• a B9 Core 550 3D printer [B9 Creations, Rapid City South Dakota] is used to produce 3D print of the standard B9 Creations test piece.
• the conventional Teflon AF 2400 window is removed and replaced by a window prepared as in Example 2.
• the vat is filled with resin and a sample of the standard test piece is run at the same speed.
• a laminate prepared as described in Example 2 was mounted in the tray of a different 3D printer. A number of 3D prints were made and it was observed that there was no apparent difference in the 3D prints made with a monolithic Teflon AF 2400 film and those made with the laminate prepared according to Example 2. The printer speed, resolution, and pull forces were the same when a monolithic Teflon AF 2400 film was used and when the laminate prepared according to Example 2 was used. Additional information about the invention follows.
• the preferred laminate of this invention comprises at least two layers in which one layer consists of an amorphous fluoropolymer and the second layer consists of a material which is a non-elastomeric material having a glass transition temperature equal to or higher than 0°C.
• Examples of the types of 3D printers that can have their performance increased by the use of these materials include, but are not limited to, DLP (3D printers based on a digital light projector or digital light processor), DLV (3D printers based on a digital light valve), CLIP 3D printers, SLA 3D printers and other 3D printers.
• Some 3D printers operate on the basis of a light source that launches light through a transparent build area (also known as the build plate or build assembly), usually a transparent area of the tray that holds the resin that will form the part, and said light triggers a chemical polymerization in the resin according to the pattern of the light that is launched.
• a transparent build area also known as the build plate or build assembly
• the transparent build area typically has a non-stick surface such as a perfluoropolymer, the part will have greatly reduced adhesion to the build area.
• the transparent build area is oxygen permeable then, with some resins, the polymerization will be quenched in a narrow region between the part that is being built and the build area.
• a method of forming a three-dimensional object is carried out by (a) providing a carrier and a build plate, the build plate comprising a semipermeable member, the semipermeable member comprising a build surface with the build surface and the carrier defining a build region there between, and with the build surface in fluid communication by way of the semipermeable member with a source of polymerization inhibitor; (b) filling the build region with a polymerizable liquid, the polymerizable liquid contacting the build surface, ( c) irradiating the build region through the build plate to produce a solid polymerized region in the build region, while forming or maintaining a liquid film release layer comprised of the polymerizable liquid formed between the solid polymerized region and the build surface, wherein the polymerization of which liquid film is inhibited by the polymerization inhibitor; and ( d) advancing the carrier with the polymerized region adhered thereto away from the build surface on the build plate to create a subsequent build region between the polymerized region and the build
• Statement 1A Apparatus for preparing an article having a desired configuration, the configuration comprising different parts which are on top of or otherwise adjacent to each other, the apparatus comprising
• a window preferably a planar window, having an upper surface and an opposite lower surface
• the window is an oxygen-permeable laminate comprising a first layer and a second layer, the first layer being composed of a first polymeric composition comprising a PMP polymer as hereinbefore defined, and/or a PPO polymer as hereinbefore defined, and/or a carbon molecular sieve membrane as hereinbefore defined, and/or a polyacetylene, and/or a para-substituted polystyrene, and/or a polynorbornene, and the second layer being composed of an amorphous fluoropolymer as hereinbefore defined.
• Statement 1 B Apparatus according to Statement 1 A wherein at least 80% by weight, preferably substantially 100% by weight, of the first layer is composed of a first polymer which comprises at least 80 mol % of repeating units derived from 4-methyl-1- pentene.
• Statement 1 C Apparatus according to Statement 1 B wherein the first polymer contains substantially 100 mol % of units derived from 4-methyl-1-pentene.
• Statement 1 D Apparatus according to any one of Statements 1 A-1 C wherein the second layer of the laminate is composed of a second polymeric composition which comprises an amorphous fluoropolymer comprising units derived from a monomer containing at least one perfluorinated carbon atom.
• Statement 1 E Apparatus according to Statement 1 D wherein the monomer comprises a perfluorinated ethylenically unsaturated hydrocarbon.
• Statement 1 F Apparatus according to Statement 1 E wherein the monomer is (i) tetrafluoroethylene, and/or (ii) perfluoro methyl vinyl ether, and/or (iii) a monomer containing a perfluoro-1,3-dioxole moiety.
• Statement 1 G Apparatus according to Statement 1 E wherein the monomer is (i) tetrafluoroethylene, and/or (ii) perfluoro methyl vinyl ether, and/or (iii) a monomer containing a perfluoro-1,3-dioxole moiety.
• the monomer comprises (i) perfluoro-2,2-dimethyl-1,3-dioxole, and/or (ii) perfluoro-1 ,3-dioxole, and/or (iii) perfluoro-1 ,3-dioxolane, and/or (iv) perfluoro-2,2-bis-methyl-1 ,3-dioxole, and/or (v) 2,2,4-trifluoromethyl-5- trifluoromethoxy-1.3-dioxole, and/or (vi) perfluoro-2-methylene-
• the fluoropolymer preferably contains at least 80 mol percent, for example about 100 mol percent, of units derived from one or more monomers each of which contains at least one fluorinated, preferably perfluorinated carbon atom.
• Statement 1 H Apparatus according to any of Statements 1 A-1 G which comprises a primer between the first and second layers.
• Statement 11 Apparatus according to any of Statements 1 A-1 H wherein the dimensions of the laminate remain unchanged and the layers of the laminate remain secured to each other throughout the operation of the apparatus.
• Statement 1 J Apparatus according to any of Statements1A-1H wherein the layers of the laminate cannot be separated manually.
• Statement 1 K Apparatus according to any of Statements 1 A-1 J wherein the thickness of the first layer is 0.25-15 mil, e.g. 0.75-10 mil.
• Statement 1 L Apparatus according to any of Statements 1 A-1 K wherein the thickness of the second layer is 0.5-500 pm, for example 1-100 pm, e.g. 5-25 pm.
• Statement 1 M Apparatus according to any of the preceding Statements wherein the oxygen permeability of the first layer is at least 10 Barren
• a window preferably a planar window, having an upper surface and an opposite lower surface
• the window is an oxygen-permeable laminate comprising a first layer and a second layer, the first layer being composed of a first polymeric composition, the first polymeric composition being a single polymer or a mixture of polymers, the polymer or at least one of the polymers being a non-elastomeric polymer and having a glass transition temperature of at least 0°C.
• Statement 2B Apparatus according to Statement 2A wherein the laminate is as defined in any of Statements 1A-1N.
• a laminate comprising a first layer and a second layer, the first layer being composed of a first polymeric composition comprising a PMP polymer as hereinbefore defined and/or a PPO polymer as hereinbefore defined, and/or a carbon molecular sieve membrane as hereinbefore defined, and/or a polyacetylene, and/or a para-substituted polystyrene, and/or a polynorbornene.
• Statement 3B A laminate according to Statement 3A wherein the laminate is as defined in any of Statements 1 A-1 N.

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• 2020
  • 2020-12-18 EP EP20902104.7A patent/EP4076905A4/en not_active Withdrawn
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