WO2013154695A2 - Film et/ou stratifié traité en surface - Google Patents

Film et/ou stratifié traité en surface Download PDF

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Publication number
WO2013154695A2
WO2013154695A2 PCT/US2013/029016 US2013029016W WO2013154695A2 WO 2013154695 A2 WO2013154695 A2 WO 2013154695A2 US 2013029016 W US2013029016 W US 2013029016W WO 2013154695 A2 WO2013154695 A2 WO 2013154695A2
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WO
WIPO (PCT)
Prior art keywords
substrate
polymeric substrate
film
treatment composition
layer
Prior art date
Application number
PCT/US2013/029016
Other languages
English (en)
Other versions
WO2013154695A3 (fr
Inventor
Ming Kun Shi
Daniel L. Holguin
Larry CO
Original Assignee
Avery Dennison Corporation
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
Priority claimed from PCT/US2012/032746 external-priority patent/WO2012141994A2/fr
Priority claimed from PCT/US2012/048124 external-priority patent/WO2013133862A1/fr
Application filed by Avery Dennison Corporation filed Critical Avery Dennison Corporation
Publication of WO2013154695A2 publication Critical patent/WO2013154695A2/fr
Publication of WO2013154695A3 publication Critical patent/WO2013154695A3/fr

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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
    • 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
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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

Definitions

  • the present su bject matter relates generally to the art of protective films and/or laminates. Particu lar relevance is found in connection with adhesive sheets useful for protecting various surfaces to which the adhesive sheets are applied, e.g., such as the surfaces of automotive bodies, consumer electronics, wind mill blades, home appliances, and accordingly the present specification makes specific reference thereto. However, it is to be appreciated that aspects of the present su bject matter are also equally amena ble to other like applications.
  • Patent No. 6,383,644 to Fuchs discloses one such multilayer sheet. Additionally, the pu blished U.S. Patent Application of McGuire (Pu b No.: US 2008/0286576 Al) also discloses a multilayer protective sheet. Both of the foregoing references are incorporated by reference herein in their entirety.
  • a protective film and/or laminate which performs suita bly in accordance with one or more evaluation criteria, e.g., such as good chemical resistance, good scratch and impact resistance, non-stick and non-wetting properties, good stain resistance, anti-graffiti and anti-fou ling properties, good weather resistance, a low degree of yellowing over time, good optical clarity for see-through applications, a high degree of flexibility for conforming to non-planar surfaces, etc.
  • the polyurethane film largely retains its flexibility/stretchability, an effect associated with the diffusion of ingredients from the treatment composition into the PU film.
  • PU polyurethane
  • as much as 90% of the non-volatile ingredients from the treatment composition diffuse into the PU film, with a diffusion depth of as much as 25 ⁇ into the PU film.
  • Diffusion of a liquid or coating ingredients into a macroscopically porous substrate such as paper, foams, or other porous media, is known and can be promoted by capillary effect.
  • the present subject matter provides a method of forming a layered substrate.
  • the method comprises providing a first layered assembly that includes a first carrier layer defining a first face and an oppositely directed second face.
  • the first layered assembly also includes a pressure sensitive adhesive layer disposed on the first face of the first carrier.
  • the method also comprises providing a second layered assembly that includes a second carrier layer defining a first face and an oppositely directed second face.
  • the second layered assembly also includes a polymeric substrate disposed on the first face of the second carrier.
  • the method also comprises contacting a face of the pressure sensitive adhesive layer of the first layered assembly with a face of the polymeric substrate of the second layered assembly to thereby adhere the first layered assembly to the second layered assembly and form an adhered layered assembly.
  • the method also comprises removing the second carrier from the polymeric substrate to thereby expose a face of the polymeric substrate of the adhered layered assembly.
  • the method also comprises applying a liquid treatment composition to the exposed face of the polymeric substrate of the adhered layered assembly.
  • the treatment composition includes at least one non-volatile agent which diffuses at least partially into the polymeric su bstrate.
  • the method further comprises drying and curing the liquid treatment composition located both above and/or within the layered assembly to thereby form a surface treated layered substrate.
  • the liquid treatment composition includes an agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups, and combinations thereof.
  • the treatment composition also comprises at least one carrier fluid also diffusible in the polymeric substrate.
  • a layer is formed on the polymeric substrate with a decreasing concentration of the low surface energy component(s) from the layer outer surface to the interface, and (ii) at least a portion of the carrier fluid(s) diffuses into the polymeric substrate and away from the layer of low surface energy component(s) formed on the polymeric substrate. Drying and curing are performed to eliminate the carrier fluids(s) and to cure the diffused agents and the treatment materials remaining above the polymeric substrate.
  • the present subject matter provides a method for forming a substrate having a protective layer including low surface energy components.
  • the method comprises providing a polymeric substrate.
  • the method also comprises providing a liquid treatment composition which is diffusible into the polymeric substrate.
  • the treatment composition includes (i) at least one agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups, and combinations thereof, and (ii) at least one carrier fluid.
  • the method also comprises applying the formulation on the polymeric substrate to form a layer on the polymeric substrate.
  • the method also comprises drying and curing the treatment materials that are disposed on the polymeric substrate and diffused into the substrate to thereby form a su bstrate having a protective layer thereon and therein.
  • the present subject matter provides a protective film comprising a polymeric substrate defining at least one face.
  • the film also comprises a layer disposed on the face of the polymeric substrate.
  • the layer includes at least one agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups and combinations thereof.
  • the coated film also comprises a region of diffused components within the polymeric substrate. The components are spaced from the coating layer after diffusion through at least a portion of the polymeric substrate.
  • the present subject matter provides a method for selecting a photoinitiator used in a polymerizable composition that is applied to a polymeric substrate and curable by photo-polymerization.
  • the method comprises identifying one or more spectral regions within which the polymeric substrate exhibits maximum transmission of light.
  • the method also comprises selecting a photoinitiator that exhibits a maximum absorbance within one or more spectral regions where the polymeric substrate exhibits maximum transmission. Particular interest is given to curing by UV and LED methods.
  • a typical LED light emits a much narrower spectral distribution of +/- lOnm, with central wavelengths at 365nm, 385nm, 405nm, or 410nm that can be pre-determined by the LED light manufacturer.
  • Many plastic substrates including polyurethane are highly transparent in the wavelength range from 365nm to 410nm. Therefore a LED light can penetrate much deeper, e.g. much farther, into the polymeric film than the traditional UV light to effectively cure the treatment materials diffused inside the polymeric film.
  • a LED light also eliminates infrared heating and potential damages from the shorter wavelength UV emissions, particularly the UV-C components, from the traditional broadband UV lamp. As a result, the polymeric su bstrate remains cold and there are no harmful UV-C emissions and generation of ozone. It will also be appreciated that a combination of LED lights of different central wavelengths and intensity could be employed depending on the curing needs.
  • the present subject matter also provides a method for selectively varying optical gloss of a layered substrate resulting from a treatment material applied on a polymeric substrate.
  • the method comprises selecting a polymeric substrate defining at least one face.
  • the method also comprises providing a liquid treatment composition including one or more liquid component(s) and particulates dispersed in the liquid component(s) and having a size such that the particulates do not diffuse or substantially diffuse into the polymeric substrate.
  • the method also comprises applying the treatment composition to the at least one face of the polymeric substrate.
  • the method also comprises drying and curing the treated polymeric substrate the applied treatment materials (both above and within the polymeric substrate) to thereby form the layered substrate.
  • the optical gloss of the layered substrate is reduced (i) significantly by selecting the polymeric substrate and/or processing conditions such that at least a majority proportion of the liquid component(s) diffuse into the polymeric substrate, and (ii) to a lesser extent by selecting the polymeric substrate and/or processing conditions such that at least a majority proportion of the liquid component(s) do not diffuse into the polymeric substrate.
  • the present subject matter provides a method for reducing surface defects in a layered substrate resulting from a liquid treatment composition applied to a substrate.
  • the method comprises incorporating at least one surfactant in the treatment composition prior to application to the substrate.
  • the surfactant is selected from the group consisting of fluorinated surfactants, silicone surfactants, and combinations thereof.
  • the present subject matter provides a method for forming a layered substrate.
  • the method comprises providing a polymeric substrate.
  • the method also comprises providing a liquid treatment composition comprising liquid component(s), nano-sized particles dispersed in the liquid component(s), and at least one surfactant in the material.
  • the surfactant is selected from the group consisting of fluorinated surfactants, silicone surfactants, and combinations thereof.
  • the method additionally comprises forming a layer of the treatment composition on the substrate.
  • the method also comprises drying and curing the treated polymeric substrate to cure the treatment materials that are disposed on the polymeric substrate and diffused into the substrate to thereby form a substrate having a protective layer thereon and therein.
  • the present subject matter provides a method of forming a layered polymeric substrate exhibiting a relatively high gloss.
  • the method comprises providing a thermally curable composition comprising at least one high optical index component in the vehicle having an optical index of greater than 1.50.
  • the method also comprises providing a polymeric substrate defining at least one face.
  • the method also comprises applying the composition on the face of the polymeric substrate to form a layer of the composition.
  • the method comprises heating the layer of the coating composition to thereby dry and cure the composition to form the layered polymeric substrate.
  • the treated polymeric substrate exhibits a 60 degree gloss of at least 95.
  • the present subject matter provides a method of forming a layered polymeric substrate comprising at least one diffusion-enabled treatment layer within the substrate, in which the treatment layer is an intermediate layer.
  • the intermediate layer can serve as a primer layer, a bonding layer, etc.
  • the treatment liquid serves as a primer layer.
  • the method in this particular embodiment provides a polymeric su bstrate defining at least one face.
  • the method also provides a first liquid treatment composition applied to the face of the polymeric substrate to form the primer layer. The agents in the treatment composition diffuse at least partially into the polymeric substrate.
  • the method further comprises drying and curing the treated polymeric substrate to cure the treatment materials that are disposed on the polymeric substrate and diffused into the substrate to thereby form a primed polymeric substrate.
  • Additional treatment compositions can be applied over the primer layer.
  • the additional liquid treatment composition includes at least one agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups and combinations thereof.
  • the treatment agents from the additional treatment composition may or may not partially diffuse into the first treatment layer and if diffused, are cured therein with the layer disposed above the primer layer. Drying may be performed prior to the curing step to eliminate the carrier fluid and/or promote diffusion of other non-volatile ingredients from the additional treatment composition into the primer layer.
  • the primer layer ensures good adhesion between the additional treatment composition and the polymeric substrate.
  • a layered polymeric substrate comprising at least one diffusion-enabled treatment layer within the substrate and a liquid treatment layer or an intermediate layer that serves as a bonding layer.
  • the layered substrate is formed by a method as follows. The method provides a polymeric substrate defining at least one face. The method also provides a liquid treatment composition applied to at least one face of the polymeric substrate to form the intermediate bonding layer. The agents in the treatment composition diffuse at least partially into the polymeric substrate. Drying and curing are performed to cure the diffused agents along with the treatment materials disposed above the polymeric substrate. The treated polymeric substrate is subsequently attached to another polymeric or multilayered substrate via the treatment layer by, for example, adhesive lamination and/or thermal lamination, to form a multilayered substrate comprising the intermediate bonding layer within the multilayered substrate.
  • the present subject matter provides a method of forming a layered polymeric substrate to produce a styling film comprising multiple regions exhibiting different visual appearances including but not limited to, a glossy finish, a matte finish, color, text, graphics, etc. At least one of these regions is formed by surface treatment from a liquid composition wherein at least one agent from the treatment composition diffuses at least partially into the polymeric substrate and cured therein along with the treatment materials disposed above the polymeric substrate.
  • the present subject matter provides a method of forming a layered polymeric substrate comprising a diffusion-enabled treatment layer on a top or outer surface.
  • the method provides a polymeric substrate defining a first surface and a second surface.
  • the method also provides a liquid treatment composition applied to at least a portion of the first surface of the polymeric substrate to form an intermediate layer.
  • the treatment composition includes at least one agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups and combinations thereof.
  • the agents in the treatment composition diffuse at least partially into the polymeric substrate and are cured therein along with treatment materials disposed above the polymeric substrate.
  • the treated polymeric substrate is subsequently attached to another polymeric or multilayered polymeric substrate via the second surface by, for example, adhesive lamination, thermal lamination, etc. to form a multilayered substrate with the treatment materials on an exterior surface.
  • the present subject matter provides a method of forming a layered polymeric substrate wherein the polymeric substrate is pre-treated prior to a treatment with a liquid treatment composition.
  • the method comprises providing a polymeric substrate defining a first and a second surface.
  • the polymeric substrate and specifically at least the first surface is pre-treated by, for example, stretching, embossing, exposing to UV light, laser, etc. Additional pre-treatment operations are described herein.
  • the method also comprises providing a liquid treatment composition applied to at least a portion of the first surface of the polymeric substrate.
  • the treatment composition includes at least one agent having a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups and combinations thereof.
  • the agents in the treatment composition diffuse at least partially into the polymeric substrate and are cured therein along with treatment materials disposed above the polymeric substrate.
  • su bject matter disclosed herein may take form in various components and arrangements of components, and in various steps and arrangements of steps.
  • the drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting. Further, it is to be appreciated that the drawings may not be to scale.
  • Figure 1 is diagrammatic illustration showing an exemplary construction of a surface treated film and/or laminate in accordance with aspects of the present subject matter.
  • Figure 2 is diagrammatic illustration showing another exemplary construction of a surface treated film and/or laminate in accordance with aspects of the present subject matter.
  • Figure 3 is graph showing measured 60 degree gloss values for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples.
  • Figure 4 is graph showing measured b values for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples after exposure to a used motor oil test.
  • Figure 5 is graph showing measured b values for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples after exposure to a used motor oil test.
  • Figure 6 is graph showing measured tensile stress at 100% elongation for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples.
  • Figure 7 is graph showing measured delta b and delta E values for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples after exposure to weathering testing.
  • Figure 8 is graph showing the pencil hardness and hand stretcha bility of different plastic films with and without a hard coat.
  • Figure 9 is photomicrograph showing a comparative sample film treated with an exemplary treatment composition prepared in accordance with the present subject matter.
  • Figure 10 is photomicrograph showing an exemplary sample film treated with an exemplary treatment composition prepared in accordance with the present subject matter.
  • Figure 11 is graph showing the relative intensity of an I spectral analysis peak associated with an exemplary radiation curable treatment composition prepared in accordance with the present subject matter as a function of depth into an exemplary film receiving the treatment.
  • Figure 12 is photomicrograph showing an exemplary sample film treated with an exemplary treatment composition with a continuous transition from and a treatment layer above the film
  • Figure 13 is photomicrograph showing an exemplary sample film treated with an exemplary treatment composition wherein all the treatment materials have diffused into the film.
  • Figure 14 is graph showing measured b values for each of several tested sample films treated with another exemplary treatment composition prepared in accordance with the present subject matter and comparative examples after exposure to a used motor oil test.
  • Figure 15 is graph showing measured tensile stress at 100% elongation for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the present subject matter and comparative examples.
  • Figure 16 includes graphs showing the variation of elongation% as a function of polyacrylate [wt %] in a treatment composition ( Figure 16a) and of polyisocyanate/polyacrylate weight ratio ( Figure 16b).
  • Figure 17 is graph showing the variation of IR spectra as a function of depth into the film treated with an exemplary treatment composition.
  • Figure 18 is graph showing the variation of elongation% upon exposure to high temperature for the film treated with an exemplary treatment composition.
  • Figure 19 is graph showing the variation of elongation% upon exposure to high humidity for the film treated with an exemplary treatment composition.
  • Figure 20 is graph showing the changes in the b values and in the total color for sample films treated with an exemplary treatment composition after exposure to an accelerated UV weathering test.
  • Figure 21 is graph showing the changes in the elongation% for sample films treated with an exemplary treatment composition after exposure to an accelerated UV weathering test.
  • Figure 22 is a graph showing elongation% and Young's modulus values for various treated films using various exemplary treatment compositions.
  • Figure 23 is a graph showing changes in elongation% after aging for sample films treated with exemplary treatment compositions.
  • Figure 24 is a graph showing changes in Young's modulus after aging for sample films treated with exemplary treatment compositions.
  • Figure 25 is a graph showing changes in elongation% for sample films treated with exemplary treatment compositions after humidity aging.
  • Figure 26 is a graph showing changes in Young's modulus for sample films treated with exemplary treatment compositions after humidity aging.
  • Figure 27 is a graph of release and adhesion values for sample films treated with various treatment compositions.
  • Figure 28 is a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition in which a distinct interface is formed.
  • Figure 29 is a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition in which a distinct interface is not formed.
  • Figure 30 is a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition in which a distinct interface is formed.
  • Figure 31 is a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition in which a distinct interface is formed.
  • Figure 32 is a graph illustrating transmission and absorption properties of a commercially available polyurethane film.
  • Figure 33 is a graph illustrating absorbance spectra of two photoinitiators.
  • Figures 34A-34F schematically illustrate a one pass technique for forming a protective coated layered assembly in accordance with the present subject matter.
  • Figure 35 is a flow chart illustrating a one pass method in accordance with the present subject matter.
  • Figure 36 is a flow chart illustrating a method of forming a coated substrate having a protective layer including low surface energy components, in accordance with the present subject matter.
  • Figure 37 is a flow chart illustrating a method of varying optical gloss of a coated substrate in accordance with the present subject matter.
  • Figure 38 is a flow chart illustrating a method of forming a coated substrate having a reduced potential for surface defects in accordance with the present subject matter.
  • Figure 39 is a flow chart illustrating a method of forming coated polymeric substrate exhibiting a high gloss in accordance with the present subject matter.
  • Figure 40 illustrates a multilayered plastic film comprising a diffusion-enabled liquid treatment layer as a primer layer (Figure 40A), a bonding layer (Figure 40B), or a top layer (Figure 40C).
  • Figure 41 illustrates a plastic film comprising multiple regions of different visual appearance with at least one of the regions comprising a diffusion-enabled liquid treatment layer.
  • Figure 42 illustrates a surface treated plastic film in which the plastic film is pre-treated prior to the application of a diffusion-enabled liquid treatment composition.
  • Figure 43 illustrates a surface treated plastic film in which textures are introduced into the surface of a treated plastic film by printing ( Figure 43A), embossing ( Figure 43B) or by curing through a mask ( Figure 43C).
  • the term "surface treatment region” as used herein refers to a region of material having no clear boundary.
  • the surface treatment region typically includes a coating and extends into a region of an adjacent su bstrate containing both coating material and substrate material, into which the coating permeates, diffuses, or at least partially migrates into.
  • surface treatment refers to treatment of a surface such as a substrate surface by application of a coating which results in no clear boundary between the coating and the substrate.
  • elongation% at deformation refers to the elongation % at which a plastic film begins to change appearance such as hazy, cracking, etc. Unless otherwise stated, the term “elongation %” used herein refers to "elongation% at deformation”.
  • modulus represents the Young's modulus.
  • pot life refers to the time period during which the liquid treatment composition can be used. Typically the end of the pot life is reached when the viscosity of the liquid treatment composition has been doubled.
  • nano-materials refers to materials having particle size ranging from a few nanometers up to ⁇ . ⁇ .
  • particles refers to materials having particle size ranging from 1.0 ⁇ up to 20 ⁇ .
  • used motor oil refers to automotive engine oil after about 5000 mile usage under normal driving conditions.
  • carrier fluid refers to a low molecular weight compound such as an organic solvent or water that is used to dissolve or carry a compound with higher molecular weight. Unless otherwise stated, the term “carrier fluid” in the present subject matter refers to an organic solvent.
  • the term "residence time” refers to the time period that a film sample is exposed to a treatment agent such as a solvent, temperature, etc.
  • hydrophobically modified compound refers to a compound bearing hydrophobic functional groups such as hydrocarbon, silicone, fluorinated groups, etc.
  • hydrophobically modified silica refers to a silica particle comprising hydrophobic groups on the surface.
  • solid film refers to a film that does not contain interconnected or enclosed voids that are present in a porous or foamy medium. Unless otherwise stated, the film used in the various preferred embodiments refers to a solid film.
  • coating when used as a noun refer to a layer, film, or covering of a liquid composition described herein on, either partially or entirely, an underlying surface or region. These terms when used as a verb refer to applying the liquid compositions described herein in any manner and as described herein in greater detail, can include spraying, dipping, wiping, liquid printing, applying by immersion, and other techniques.
  • substrate typically refers to a polymeric or plastic film having one or more faces or surface regions which are to receive coatings, layers, or other applications of the compositions described herein. However, the term “substrate” also includes other components and/or shapes such as polymeric resin pellets, finished or semi-finished articles such as tubes, conduits, piping, buckets, containers, shelves, counters, . . . etc.
  • the term "graded interpenetrating network” refers to a composite and/or an interpenetrating network formed by the curing of one or more agents or components that diffused into a polymeric substrate and whose concentration varies with distance from a region or face of the substrate.
  • Interpenetrating networks are known in the literature and are generally defined as networks formed by intermixing of two different polymeric networks at a molecular level.
  • the agents or components are initially contained in a liquid treatment composition as described herein. Upon application to a region or face of the substrate, the agents or components diffuse to varying extents and/or distances into the substrate to form a concentration gradient within the substrate. Thus, the distribution of the agents or components is referred to as a "graded".
  • the diffused ingredients and/or other agents are then at least partially cured by thermal curing techniques, irradiation curing techniques, or by a combination of these techniques with or without other curing means to form an "interpenetration network".
  • the non-volatile ingredient or agent in the liquid treatment composition refers to those ingredients that remain on or beneath the treated plastic film after the treatment.
  • non-volatile diffusible ingredients include but are not limited to, coloring agents, photoinitiators, thermal initiators, light absorbers, light stabilizers, anti-oxidants, polymeric binders, conductive pigments, particles, monomers, oligomers, diluents, etc.
  • the non-volatile ingredient(s) diffusible in the polymeric substrate excludes carrier fluid(s) that may be used in the treatment liquid and can diffuse into the plastic substrate.
  • the carrier fluid(s) is considered as volatile and is typically eliminated by drying prior to curing.
  • drying also promotes diffusion of the non-volatile ingredients from the liquid treatment composition into the plastic substrate. Heating the liquid treatment composition and/or the polymeric substrate is considered particularly important for promoting diffusion of liquid treatment compositions which do not contain a carrier fluid.
  • non-volatile diffusible agents that are reactive upon activation by a curing source such as monomers, oligomers, reactive diluents, etc.. Once diffused into the polymeric substrate, these agents are dispersed within the matrix of the polymeric substrate.
  • the concentration of these agents decreases gradually from the top surface to the bulk of the polymeric substrate.
  • a composite or a graded interpenetrating network is formed within the polymeric substrate.
  • GIPN graded interpenetrating network
  • the diffusion of colorants and light absorbers/stabilizers into a polymeric substrate has been described in U.S. 6,221,112, U.S. 6,316,531, and U.S. 2007/0231502 for making colored polymeric film or to improve the film's UV stability.
  • the process described in these documents does not include a post-curing step to cure the diffused agents as well as the treatment composition disposed above the polymeric su bstrate, which is an aspect of the present subject matter.
  • the diffusion of non-volatile ingredients from the treatment composition into the plastic film effectively eliminates the sharp boundary typically present in a conventional coating process and forms instead, an interfacial transition layer beneath the plastic film along with an ultra thin coating layer disposed above the plastic film.
  • the transition layer With a composition and physical properties lying between the treatment materials and the plastic film, the transition layer leads to a gradual transition in properties from the plastic film to the treatment layer disposed above the plastic film which produces several benefits. First, it leads to excellent adhesion between the treatment layer and the plastic film via physical interlocking. It also significantly retains the intrinsic properties of the plastic film, such as the stretchability/flexibility of the PU film.
  • a protection film/laminate made from such treatment process effectively combines the outstanding surface properties provided by the top coating layer, such as stain resistance, anti-graffiti characteristics, chemical/scratch resistance, and the unique bulk properties of the plastic film such as the flexibility, stretchability, etc.
  • the release liner 12 is first removed from the construction and the PSA layer 14 is then used to adhere the treated film 10 to the surface of a desired object with the surface 16 facing outward therefrom.
  • the film is optionally applied in this manner to an auto body surface or other like surface that one wishes to protect.
  • the treatment materials For protective film applications in which the surface properties of the treated film are important, typically it is desirable that the treatment materials only partially diffuse into the polymeric substrate and a layer of the treatment materials is formed above the polymeric substrate. This strategy leverages the surface properties resulting from the treatment materials. For applications in which the bulk properties of the resulting film are more important, however, it is advantageous to allow all (or a significant proportion) of the treatment materials to diffuse into the polymeric substrate to maximize the improvements in the bulk properties of the resulting system. As demonstrated herein, the present subject matter provides selectively adjusting the amount or degree of diffusion of the treatment materials by varying certain process conditions, without changing the composition of the surface treatment liquid. Thus, by tuning the amount or degree of diffusion of treatment materials, films can be produced which exhibit desired properties and characteristics that are tailored to specific applications.
  • the film 10 shown in Figure 1 can be readily and smoothly applied to complex geometries and/or otherwise curved surfaces.
  • alternate means can be used to adhere or otherwise stick the film 10 to a desired surface.
  • the present specification discloses a new protective film or laminate that has at least one major surface of a plastic substrate treated with a suitable material to enhance the properties of the protective film or laminate while retaining a sufficient portion of the pristine plastic substrate property, such as flexibility and/or extensibility.
  • the surface treatment proposed herein is distinguished from a top coating in that a substantial portion of the material applied during the surface treatment does not ultimately remain extending above or disposed on top or proud of the upper surface of the underlying film or laminate so treated.
  • the coating material used in the surface treatment generally includes a liquid coating solution or dispersion.
  • a coating solution is typically a clear liquid in which the coating ingredients are either totally soluble in an organic solvent or water, or their size is smaller than the visible wavelength of light and so the coating ingredients do not scatter light. Nano-sized particles generally fall into this latter category.
  • a coating dispersion refers to a coating liquid that appears cloudy either because the coating ingredients are not totally soluble in or miscible with an organic solvent or water, or their size is larger than the visible wavelength of light and scatter light.
  • FIG. 1 illustrates a suitable construction in accordance with aspects of the present subject matter.
  • a plastic film 10 is laminated to a release liner 12 coated with a pressure sensitive adhesive (PSA) 14.
  • PSA pressure sensitive adhesive
  • reference numeral 16 identifies a surface created via surface treatment of the plastic film 10 with the coating material as disclosed herein.
  • the film 10 is optionally a polyurethane (PU) film.
  • PU polyurethane
  • the surface treatment of the film 10 creates a surface 16 which is not a distinct layer with respect to the film 10. That is to say, there is no strictly defined border between the surface 16 and the film 10 which separates the two into otherwise distinct layers. Rather, the surface 16 is formed by a chemical treatment of the film 10 such that the material composition gradually transitions from one material to the next.
  • the diffusion and formation of a gradual transitioning layer of the treatment materials into the plastic film substrate contributes largely to the retention of the film flexibility/extensibility. This is particularly the case when the treatment material is from a protective hardcoat composition as illustrated in one of the embodiments herein.
  • Several mechanisms or factors can contribute to the diffusion and formation of a gradual transition such as the physical size of the coating ingredients, the compatibility with the plastic film, the type and amount of carrier fluid or solvent, the temperature of the plastic film substrate, the temperature of the coating ingredients, the residence time, . . . etc.
  • the carrier fluid or the solvent is selected to have good compatibility with the PU film.
  • the solvent swells the PU film and carries the solid coating materials from the surface treatment inside the matrix of the PU film.
  • the inclusion of the coating solids from the treatment in the PU film matrix increases the density of the sub-surface.
  • the diffusion is generally more pronounced for a lower viscosity composition, at higher drying temperatures, and/or with longer residence time.
  • the viscosity of the coating ingredients decreases and the free volume of the plastic film increases at high temperatures during the solvent drying process, both favoring penetration of coating ingredients.
  • the outermost surface of the PU film like all plastic materials, is generally rough on a nano-meter scale. Upon treatment with the coating material, the valley areas are filled with the coating materials, which also beneficially lead to a smoother surface.
  • the thickness and/or amount of the coating material from the treatment which remains above or proud of the top surface of the underlying substrate material is relatively small in view of the coating weight used to apply the treatment material. In fact, in some embodiments it may even be unperceivable.
  • the carrier fluid or solvent in the liquid treatment composition which is small in size operates to expand the matrix of the underlying film or substrate material to facilitate penetration of one or more coating ingredient(s) into the film or substrate.
  • the solvent is selected to be compatible with the chosen film or substrate material in this fashion, and the coating materials are likewise chosen, e.g., based on physical size and/or other appropriate properties, to achieve the desired penetration in view of the film material and selected solvent.
  • the amount or degree of diffusion can also be tuned by adjusting the process conditions such as the substrate temperature, the residence time, etc..
  • the coating materials used in the surface treatment include one or more of the following curable ingredients: monomer and oligomer, such as radiation curable (electron beam, gamma irradiation, UV, and LED including both free radical and cationic) or thermally curable (peroxide, azo compound, ect.) monomer and oligomer, additives such as surfactant and defoamer, and small particles of organic compounds, inorganic compounds or hybrid organic-inorganic compound. These materials are small in size and easily penetrate into the matrix of the plastic film or laminate.
  • the size of the monomer or oligomer or particle is less than ⁇ , more preferably less than 5 ⁇ , and even more preferably less than ⁇ .
  • the temperature during the treatment process has significant effects on the diffusion of treatment ingredients into the plastic film.
  • the viscosity of the coating ingredients such as monomers or oligomers, decreases with increasing the temperature.
  • the free volume of the plastic film substrate increases with the temperature. Therefore, the diffusion of coating ingredients can be significantly enhanced simply by increasing the processing temperatures and in some cases the presence of organic solvent may not be necessary, i.e., diffusion can also occur from a solvent- free or 100% solid treatment composition.
  • a PU film of about 150 to 200 ⁇ in thickness is particularly suitable for such applications.
  • polyurethane films made by Deerfield Urethane, Inc. (Whately, Massachusetts) and sold under the trade name Dureflex * (periodically referred to herein as a first sample or exemplary film material) and polyurethane films made by Argotec, Inc. (Greenfield, Massachusetts) and sold under the trade name ARGOTHANE * (periodically referred to herein as a second sample or exemplary film material) have been found acceptable.
  • the elastic property of the PU film also provides additional cushion that benefits the impact resistance of the final film or laminate.
  • These PU films are extruded onto a PET carrier (PU/PET).
  • the ARGOTHANE * film Compared to the Dureflex' film, the ARGOTHANE * film exhibits higher optical clarity and is more attractive for applications which require see-through properties.
  • the ARGOTHANE * film has a melting temperature of 60 to 80°C as measured by DSC and a softening temperature of 80 to 110°C as measured by DMA, both at a ramping rate of 5°C/min.
  • the film has an elongation of 450 to 588% and Young's modulus of about 22 to 29 MPa.
  • the treatment composition may be cured at temperatures substantially higher than the melting or softening temperatures, which is beneficial for diffusion of treatment ingredients into the plastic film.
  • the coating material used in the surface treatment comprises POSS * (Polyhedral Oligomeric Silsesquioxanes) or other like nano-structured organic-inorganic hybrid material.
  • POSS * Polyhedral Oligomeric Silsesquioxanes
  • suitable silsesquioxane derivatives are disclosed in U.S. Patent No. 7,235,619 issued June 26, 2007 to Morimoto, et al. and U.S. Patent No. 7,053,167 issued May 30, 2006 to Ito, et al., both of which are incorporated herein by reference in their entirety.
  • POSS * materials with various functionalities are available from Hybrid Plastics Inc. (Hattiesburg, MS).
  • the surface treatment liquid is a solvent based, UV (ultraviolet) curable solution comprising a POSS * material applied to the underlying substrate or film.
  • the treatment solution contains a silsesquioxane compound dissolved in an organic solvent.
  • a silsesquioxane compound dissolved in an organic solvent.
  • One such suitable solution is available from Chisso Corporation (Osaka, Japan) and is sold under the trade name Sila-MaxTM U1006-40.
  • the Sila-MaxTM U1006-40 contains about 40% solid dissolved in an organic solvent.
  • other ingredients in the Sila-MaxTM U1006-40 treatment solution include UV curable acrylate monomer/oligomer and a photoinitiator mixed in an organic solvent.
  • a film surface treated with the Sila-MaxTM U1006-40 treatment solution exhibits a low surface energy (e.g., approximately 21.8 mN/m) which leads to good chemical resistance while providing added properties such as non-stick and non-wetting properties, anti-graffiti characteristics, anti-fouling, easy-clean properties, water and oil resistance, and anti-smudge properties and a low coefficient of friction which also contributes to good scratch and impact resistance.
  • the preferred treatment material also possesses excellent optical clarity, e.g., with less than approximately 1% haze, which is advantageous for applications that call for see-through properties.
  • the preferred embodiment treatment material when coated to a film with low porosity such as polyester or polycarbonate, the preferred embodiment treatment material also possesses a high surface hardness (e.g., around 3H pencil hardness: 750 g weight, 45 deg angle), which makes it highly impact resistant and well suited for surface protection, e.g., of automotive bodies, consumer electronics, and other products.
  • a high surface hardness e.g., around 3H pencil hardness: 750 g weight, 45 deg angle
  • a suitable, extensible polymeric film is surface treated as described herein (e.g., using the noted preferred embodiment treatment material), such as by gravure coating, spray, flexography, slot die coating, roll coating or other suitable methods, the surface, physical, and chemical properties of the film or the laminate are substantially altered.
  • the modulus of the film is substantially increased.
  • the elongation of the film is largely retained, an effect associated with the diffusion of the treatment ingredients into solid film substrate.
  • the optical clarity is largely improved due to smoothing of the film surface by the treatment materials.
  • the changes in the mechanical properties of the treated plastic film are caused mainly by the materials diffused into the plastic film and to a much lesser extent, by the presence of an ultra thin treatment layer disposed above the plastic film.
  • the modulus of a 150 ⁇ thick Argotec PU film treated with the first treatment solution was increased from about 29M Pa to above 50MPa and the elongation at deformation was maintained at above 150% while no treatment layer could even be detected by optical microscopy, i.e. all the treatment materials diffused into the PU film.
  • the surface energy of the thus treated PU film was reduced from about 40.1mN/m to about 24.9mN/m, and the color changes after exposure to used motor oil were reduced from 16.5 to 1.71.
  • the Sila-MaxTM treatment solution can be further modified to tailor special properties or to reduce the cost.
  • the Sila-MaxTM coating solution is diluted using common organic solvents such as alcohol, ketones, acetates, ethers, etc. Dilution is particularly beneficial for treatment with low coat weight because it allows for more accurate control of the wet coating thickness. Dilution is also beneficial for promoting diffusion of the coating materials into the substrate.
  • the Sila-MaxTM solution was diluted to 35% solids by adding ethyl acetate, methyl ethyl ketone (MEK), or isopropanol solvent into the initial solution.
  • MEK methyl ethyl ketone
  • the Sila-MaxTM solution was diluted to about 30% solids using ethyl acetate solvent.
  • UV curable monomer(s) or oligomer(s) are added into the Sila- MaxTM coating solution.
  • an acrylate oligomer is added to the Sila-MaxTM coating solution to increase the solids content, i.e. solid %, and/or reduce the cost. Higher solid % is advantageous for achieving a thick coating. While any known monomers and oligomers that are compatible with the Sila-MaxTM treatment solution can be used, certain acrylate(s) are particularly attractive for their high flexibility and long term environmental stability.
  • One exemplary acrylate oligomer is available from Sartomer Company, Inc. (Exton, PA) and sold under the product designation CN2285. With an elongation at break of 120%, the CN2285 was especially developed for UV/EB-cure thermoforming applications where high elongation is desired. Without adding a new or additional photoinitiator, the mixture of the Sila-MaxTM treatment solution and the foregoing acrylate can be UV cured at the same rate (i.e., at 100 feet/min. using a mercury lamp with 206mJ/cm 2 irradiation energy) with up to about 75% wt of the acrylate in the formulation.
  • the photo curing agent contained in the Sila-MaxTM treatment solution is sufficient to cure the composite. Additional photoinitiator may be added upon further increase in the acrylate content in order to maintain a suitable curing rate.
  • the wt % of acrylate relative to the Sila-MaxTM treatment solution is less than 75 wt %, and more preferably less than 40 wt %.
  • the diffusion inside the plastic film and smoothing of the plastic film surface described above lead at least in part to the relatively thin thickness of the surface treatment material which remains above the top surface of the underlying substrate. Accordingly, this relatively thin thickness along with the gradually transitioning nature contribute to the fact that the flexibility and/or extensibility of the treated film or laminate is largely retained even though the treatment materials (e.g., such as the Sila-MaxTM) are only more generally known for rigid surface applications due to their relatively high surface hardness.
  • the treated film or laminate disclosed herein withstands at least 20% elongation without failing (i.e., cracking, breaking, clouding, etc.).
  • the treated film or laminate disclosed herein withstands at least 50% elongation without failing. And in still another embodiment, the treated film or laminate disclosed herein withstands at least 80% elongation without failing.
  • elongations of up to about 150% or even 300% may be achieved without failure of the treated laminate/film. In general, lower coat weight and/or higher penetration into the plastic film leads to higher extensibility.
  • failing refers to the start of loss of clarity and/or increase in haze, e.g., as exhibited by cracking, hazing or whitening.
  • a low-gloss, matte finish stretchable protective film/laminate is made by treatment with a solvent based composition comprising a matting agent.
  • the matting agent comprises an ultra-fine polyamide powder having an average particle size of 5 ⁇ (available under the designation Orgasol 2001 UD Nat 2 from Arkema Inc.). This polyamide particle is widely used as a matting agent for providing low gloss and smooth surfaces.
  • the treatment composition was made comprising the polyamide particle, a UV curable acrylate oligomer (i.e., CN2285 available from Sartomer Inc.); a UV curable POSS * material (i.e., Acrylo POSS * Cage Mixture (MA0736) obtained from Hybrid Plastics Inc.); and benzophenone (available from Sigma-Aldrich) as photoinitiator.
  • a UV curable acrylate oligomer i.e., CN2285 available from Sartomer Inc.
  • a UV curable POSS * material i.e., Acrylo POSS * Cage Mixture (MA0736) obtained from Hybrid Plastics Inc.
  • benzophenone available from Sigma-Aldrich
  • the loading of the polyamide particle in the coating composition is less than 20 wt %, more preferably less than 15 wt %.
  • a matte coating surface with 60° gloss of less than 10 can be achieved at a wet coating thickness of about ⁇ .
  • the coating ingredients diffuse into the PU film, more so for other coating ingredients than for the polyamide particle. This non-uniform diffusion leads to a higher concentration of the polyamide particle in the coating layer a bove the PU surface. Because of such "filtering" effect, a much more efficient anti-glare or low gloss can be achieved at lower particle loading in the starting composition. Reduced particle loading is very advantageous because it reduces the dispersion effort and the viscosity of the starting composition.
  • plastic film be at least partially transparent to the curing radiation for treatment with radiation curable composition so that the material diffused into the film receives and/or is otherwise exposed to the curing radiation.
  • the PU film surface was treated with treatment compositions that are thermally curable.
  • treatment compositions that are thermally curable.
  • two treatment compositions were made, each containing two parts, namely, a resin solution part and a curing agent part.
  • the thermally curable treatment compositions were prepared by mixing 0.5wt parts of the curing agent in lOOwt parts of the resin solution.
  • the dry thickness of the coating be less than ⁇ , as thicker coatings lead to a higher haze %.
  • the PU films treated with such thermally curable treatment compositions exhibit excellent optical clarity, more than 100% elongation at deformation, excellent stain resistance to used motor oil, and a surface energy of about 21.8mN/m.
  • the thermally curable treatment composition comprises at least one compound bearing hydroxyl functional groups and at least one crosslinker capable of reacting with the hydroxyl groups.
  • exemplary hydroxyl-bearing compounds include various polyols such as polyether polyol, polyester polyol, polycaprolactone polyols, caster oil based polyol, acrylic polyol, polyurethane polyol, and their mixtures or copolymers.
  • the hydroxyl-bearing compounds may further contain add itional functionalities, such as silicone, fluorine, amine, carboxylic acid, urethane, urea, etc., and either with or without unsaturated dou ble bonds.
  • a hydrophobically modified compound such as silicone modified or fluorinated compound
  • silicone modified compounds bearing hydroxyl functionalities include hydroxy-fu nctional silicone modified polyacrylates availa ble from BYK Chemie (Wallingford, CT) under the trade name BYK® SIL-CLEAN® 3700, 3710, and 3720.
  • fluorinated compounds bearing hydroxyl functionalities include Lumiflon® compounds availa ble from Asahi Glass Co. Ltd. (Exton, PA) and PolyfoxTM compounds availa ble from Omnova Solutions Inc. (Mogadore, OH).
  • BYK® SIL-CLEAN® 3700 is a pale yellow solution comprising 25% of hydroxy-functional silicone modified polyacrylate in Metroxypropyl acetate (M PA) solvent.
  • M PA Metroxypropyl acetate
  • polyacrylate refers to the hydroxy-functional silicone modified polyacrylate in the BYK® SIL-CLEAN® 3700 solution.
  • the crosslinker reacts with the hydroxyl functional groups in the hyd roxy-bearing compound, leading to a crosslinked structure.
  • silicone or fluorine groups are present in the hydroxyl-bearing compound, the treated film exhibits low surface energy which imparts hydrophobic and oleophobic properties.
  • Any crossslinkers that are capa ble of reacting with the hydroxyl groups can be used, including but not limited to, aminoplastic resins, diacetal crosslinkers such as 2, 2'-diacetyl- bisacetoacetates and bis (beta-ketoesters) as described in U.S. 5,453,464, aluminum containing crossslinkers having hydroxyl fu nctionalities such as disclosed in U.S.
  • an aliphatic or a cyclo-aliphatic isocyanate based crosslinker consisting of an average of 2 to 5 isocyanate groups per compound and their mixtures.
  • Such compound is typically used as a crosslinker for hydroxyl bearing compounds, especially polyesters and polyacrylic polyols, to prepare two-component polyurethane coatings and varnishes.
  • Such coating and vanishes possess excellent outdoor dura bility and mechanical properties in conjunction with outstanding resistance to solvents, a brasion, chemicals, and UV weathering.
  • a hydrophobically modified crosslinker, such as that containing silicone or fluorinated groups, is particularly attractive for imparting low surface energy to the treated film.
  • the aliphatic or cyclo-aliphatic isocyanate-functional crosslinker is a polyisocyanate or modified polyisocyanate such as aliphatic, cyclo-aliphatic or their mixtures with low amount of monomeric isocyanates.
  • aliphatic polyisocyanates are availa ble from Bayer Materials under the trademark of Desmodur ® N such as N-3300A, N-3600, and N-3900.
  • the modified aliphatic polyisocyanates are available from Nippon Polyurethane Industry Co. (Tokyo, Japan) under the trademark of Coronate HXLV and HX .
  • NCO % content ranges from 21.5 to 23.9 and the residual HDI monomer is typically ⁇ 0.2% (wt).
  • Additional functionalities can be introduced into the isocyanate crosslinkers.
  • the at least one hydroxy-bearing compound and the at least one crosslinker can be mixed and used as is. This is for example the case when one or more of these components possess low viscosities, such as with low molecular weight or is supplied as a solution in one or more carrier fluid(s).
  • at least one (additional) carrier fluid may be added to the composition to obtain appropriate viscosities and/or to promote diffusion of the ingredients into the plastic substrate which has been found essential to maintain the high flexibility/stretcha bility of the treated plastic film.
  • the use of an additional fluidic carrier with higher vapor pressure may also facilitate evaporation of carrying fluid(s) during the drying process.
  • the carrier fluid should act as a solvent with respect to both the hydroxy-bearing compound and the crosslinker, and in case these components already contain a carrier fluid, the additional carrier fluid should also be compatible with the existing carrier fluid.
  • the additional carrier fluid is a polar organic solvent. More preferably, the additional carrier fluid is a polar aliphatic solvent or polar aromatic solvent. Still more preferably, the additional carrier fluid is a ketone, ester, acetate, aprotic amide, or their mixtures.
  • carrier fluids examples include water, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), amyl acetate, ethylene glycol butyl ether-acetate, ethyl acetate, propylene glycol monomethyl ether acetate, etc.
  • the thermally curable treatment composition comprises (a) a solution of silicone modified hydroxy-functional silicone modified polyacrylate available from BYK Chemie under the treated name of BYK ® SIL-CLEAN ® 3700; (b) a modified aliphatic polyisocyanate available from Nippon Polyurethane Industries (Tokyo, Japan) under the trade name of Coronate HXLV; and (c) a MEK solvent.
  • the BYK ® SIL-CLEAN ® 3700 has a hydroxyl (-OH) number of about 30 mg KOH/g in the supplied liquid form and about 124 mg KOH/g on solids. This leads to an equivalent weight of 1870 g/eq.
  • the BYK ® SIL-CLEAN ® 3700 is designed to be used as an additive in paint or coating formulations which contain, among other ingredients, a polymeric binder to provide mechanical strength to the paint or coating so that it does not crack upon drying or handling.
  • the BYK ® SIL-CLEAN ® 3700 additive is recommended to be included in the following binder systems: two-pack (2K) polyurethanes, alkyd- melamine, polyester-melamine, acrylate-melamine, and epoxy phenolic resins.
  • the BYK® SIL- CLEAN® 3700 is added to such paint or coating formulation at 3-6 wt % based on the total formulation.
  • the polyacrylate migrates to the top surface wherein the silicone groups provide low surface energy to impart anti-graffiti characteristics or ease of surface cleaning for the paint or coating and the polyacrylate is crosslinked into the paint or coating system via the hydroxyl groups to provide long term dura bility.
  • WO 2003/05776A1 describes the use of a hydroxy- functionalized silicone modified polyacrylate additive in a coating composition comprising an UV a bsorber, a polyacrylate binder, and a methoxy propanol solvent.
  • the coating is aimed to reduce the adhesion of contaminants to a polymeric su bstrate.
  • a polymeric binder was not necessary because the coating ingredients diffuse into the plastic film su bstrate and the coating layer and the PU su bstrate behave like a single entity. That is, the diffusion of coating ingredients creates a smooth and gradual transition layer beneath and adjacent to the PU film surface, leaving a very thin coating layer a bove the PU film.
  • the coating layer and the PU su bstrate are effectively linked together and behave like a single entity.
  • the polyisocyanate Coronate HXLV is known for producing non-yellowing polyurethane paints with su perior performance to biuret or adduct types of hardeners.
  • the Coronate HXLV is resistant to high heat, has high solu bility in solvents, and has good compatibility with polyol materials.
  • the Coronate HXLV has a NCO content of 22.5 to 23.9%. At NCO content of 23.5%, the Coronate HXLV has an equivalent weight of 182 g/eq.
  • the weight ratio of Coronate HXLV to the polyacrylate needs to be 0.40.
  • M EK solvent reduces the viscosity of the treatment composition, which in turn promotes diffusion of the ingredients into the plastic film su bstrate.
  • the diffusion into the plastic film was found essential to achieve an accepta ble flexibility/stretcha bility of the treated plastic film.
  • the polyacrylate or component (a) ranges from a bout 10 wt% to a bout 85 wt% based on the total solids in the treatment composition, and the polyisocyanate or component (b) ranges from a bout 90 wt% to a bout 15 wt% in the composition. This corresponds to a weight ratio of polyisocyanate to polyacrylate of a bout 0.2 to 10.
  • the surface of the coated PU film exhibits no a nti-graffiti property as illustrated by the capa bility of being writa ble using a permanent marker or a king size Sharpie and the ink cannot be wiped off using a KLEEN EX® paper, tissue or cloth. This is due, most proba bly, to the presence of the hydroxyl functionalities which have high surface energy and compromise the effect of low surface energy from the silicone grou ps. In addition, the coated PL) film cracks easily u pon hand stretching.
  • the Coronoate HXLV crosslinker when coated alone onto the PL) film, or the ratio of polyacrylate/polyisocyanate equals zero, the surface of the coated PL) film remains tacky after drying.
  • the amount of polyacrylate in the treatment composition is greater than 85 wt% or the ratio of polyisocyanate to polyacrylate is smaller than 0.2, the anti-graffiti property or Sharpie performance is very poor meaning that the writing inks contract slowly and cannot be wiped off cleanly.
  • the coating could be tacky, exhibit very poor chemical/scratch resistance, and/or has very poor anti- graffiti or Sha rpie performance.
  • the M EK solvent (c) is preferably present in the coating composition in an amount of 0 wt% to 80 wt%, more prefera bly, in an amount of 4 wt% to 70 wt%.
  • a non-tacky coating can be obtained on a PL) su bstrate from treatment compositions with 10 to 85 wt% of polyacrylate based on the total solids.
  • a tacky coating could be obtained on aluminum (Al) or PET su bstrates when the wt% of polyacrylate in the total solids is less than a bout 40%, or a weight ratio of polyisocyanate/polyacrylate is greater than 1.2 (i.e. 3 times the stoichiometric ratio of 0.4 based on the equivalent weight).
  • H PLC measurements indicate that the Coronate HXLV has a major component with a molecular weight of a bout 631. This compares to the molecular weight of a bout 17000 for the polyacrylate. Therefore, the higher diffusion of the Coronate HXLV relative to the polyacrylate can be attributed to its smaller size.
  • the thermally curable treatment composition comprises (a) BYK® SI L-CLEAN® 3700; (b) Coronate HXLV crosslinker; (c) M EK solvent, and (d) at least one additional aliphatic or cyclo-aliphatic hydroxyl-bearing compound.
  • additional hydroxy- bearing compounds include ethylene glycol, propylene glycol, glycerol, BYK® SIL-CLEAN® 3720, etc.
  • the use of additional hydroxy-bearing compounds may speed u p the reaction rate and/or provide more flexibility/stretcha bility to the treated plastic film.
  • the amount of the additional hydroxyl- bearing compound is from 10 to 85 wt% based on total solids in the compositions, or from 0 to 100% based on the hydroxy-bearing materials.
  • An optional reaction catalyst can be included into the a bove thermally curable treatment compositions to enhance the curing reactions.
  • Suita ble reaction catalysts include known polyurethane catalysts and/or their mixtures, e.g., organic compounds such as tertiary amine including triethyl amine, pyridine, methyl pyridine, ⁇ , ⁇ -dimethylamino cyclohexane, N-methylpiperidine, pentamethyl diethylene amine, and ⁇ , ⁇ '-dimethyl piperzine; metal salts such as iron chloride, zinc chloride, and metal-organic compounds such as zinc-2-ethyl caproate, tin-ethyl caproate, dibutyltin-dilaurate, and mobybdenum glycolate.
  • Such catalysts can be used alone or in combinations. Examples of tin-organic compound catalysts are availa ble from Arkema Inc. under the trade name of FASCAT®.
  • the reaction catalyst consists of FASCAT® 2003 which consists of stannous octoate or tin 2-ethylhexanoate (referred to herein as component (e)).
  • the FASCAT® 2003 is a solvent-free liquid that can be easily incorporated into a coating solution and has been extensively used in polyisocyanate and hydroxy-bearing compound reactions.
  • the FASCAT® 2003 catalyst does not require extensive or rigorous handling conditions and can be charged at any point during the reaction.
  • the catalyst is used from 0 to 0.3 wt% in the composition, more preferably from 0 to 0.2 wt% in the coating composition. Under such conditions, the coating formulation shows a pot life of several hou rs.
  • the a bove thermally cura ble treatment compositions may further contain inorganic particles, inorganic-organic hybrid particles/materials, polymeric particles, and/or their mixture. These particles may be surface treated and/or contain various functionalities. They may be attached to a monomeric or polymeric backbone or incorporated as segments in a copolymer.
  • Suita ble inorganic particles include, for example, calcium carbonate, titaniu m dioxide, silica, alumina, zinc sulfide, zinc oxide, antimony oxide, barium sulfate, etc.
  • Suita ble organic-inorganic particles include materials derived from silsesquinoxane compounds.
  • ble organic particles include, for example, polyolefin, polyamide, polyester, and polyurethane particles. These particles can be used alone or in com binations. Of particular interest are nano-size particles or compounds that can provide special properties without adversely affecting the optical clarity of the treated plastic film.
  • alu minum oxide and silicon dioxide particles provide surface hardness and scratch-resistance; zinc oxide and titanium dioxide particles provide UV/light-sta bility and anti-microbial properties; indium/antimony tin oxide particles provide antistatic and Infrared a bsorption properties; photocatalytic titanium dioxide nanoparticles provide self-cleaning, anti-microbial, super-hydrophilicity, and UV/light-sta bility; copper oxide and silver nanoparticles offer anti-microbial property; iron oxide offer UV/light-stability and magnetism; cerium oxide particles provides UV/light-sta bility and mecha nical properties; bismuth oxide particles for X-ray attenuation, etc.
  • fu nctionalities can be introduced to the surface of these particles to render these particles hydrophilic or hydrophobic, and reactive or non-reactive towards other components in the treatment compositions.
  • the thermally cura ble surface treatment composition described a bove further includes at least one silicon-containing nano-particle or compound (referred to herein as component (f)) e.g., such as an organic-inorganic hybrid material or the like that are derived from silsesquinoxane compounds (POSS®).
  • component (f) silicon-containing nano-particle or compound
  • component (f) such as an organic-inorganic hybrid material or the like that are derived from silsesquinoxane compounds (POSS®).
  • POSS® silsesquinoxane compounds
  • the POSS® material may contain hydrogen or various carbon moieties such as hydrocarbon, hydroxyl, acid, amine, and epoxy groups, of which some may be capable of reacting with the crossslinker.
  • the POSS® material may be attached to a monomer or oligomer as side groups or as a segment in the backbone of a copolymer.
  • the component (f) consists of a triphenyl silanol POSS® availa ble from Hybrid Plastics (Hattiesburg, MS) under the trade name of POSS® S01458.
  • the amount of POSS® S01458 in the dry coating ranges from 0 to 40 wt%, more prefera bly from 5 to 30 wt%, based on the total solids in the treatment composition.
  • the thermally cura ble treatment solution optionally comprises (a), (b), and at least one inorganic nano-particle that contain reactive groups (g).
  • One such inorganic nano-particle consists of a colloidal silica availa ble from Nissan America (Houston, TX) under the trade name M I BK-ST.
  • the amount of silica based on the total solids in the treatment solution ranges from 0 to 30 wt%, more prefera bly from 0 to 20 wt%, and even more preferably from 0 to 10 wt%.
  • the use of nano-pa rticles can enhance the hardness of the coating which is beneficial to scratch resistance.
  • the elongation decreases with increasing the silica wt%.
  • the thus treated plastic film/laminate from the a bove thermally cura ble treatment compositions exhibits a hydrophobic surface (e.g., with a surface energy of around 21.8 m N/m) which is resistant to writing by permanent/Sharpie markers, has excellent optical clarity, excellent stain and scratch resistance, and can be stretched to more than 100% elongation without failure.
  • a hydrophobic surface e.g., with a surface energy of around 21.8 m N/m
  • the word “failure” refers to any noticea ble changes in the appearance of the treated film/laminate.
  • Typical failure mechanisms include hazy appearance and cracking which are associated with peeling off or cracking of the coating.
  • the surface treated plastic film is laminated to a release liner coated with a pressure sensitive adhesive (PSA) to form the aforementioned la minate ( Figure 1).
  • PSA pressure sensitive adhesive
  • the Sharpie performance of the surface treated PU film tends to improve fu rther during storage due to post-curing reactions with moisture.
  • thermally curable treatment compositions achieve the desired results without the addition of halogen or fluorine containing materia ls, and the aforementioned surface energy remains lower than most conventional silicone release coatings.
  • the formulation does not contain additional binder and as such it behaves as a "surface treatment" as opposed to a conventional paint or coating.
  • the d iffusion of coating ingredients may cause further reactions with the functional groups or residual reactive moieties present in the plastic film.
  • the isocyanate crosslinker is known to react with urethane functionalities in a PU film to form allophanate functionalities.
  • the isocyanate crosslinker also reacts with residual hydroxyl or carboxylic functionalities possibly present in a polyurethane film.
  • the crosslinker not only reacts with the reactive component in the coating composition but also possibly reacts with the plastic su bstrate, both on the surface and inside the plastic film due to the aforementioned diffusion - thereby providing three dimensional (3 D) curing reactions.
  • the viscosity of the a bove treatment compositions is less than 1000 cps, more prefera bly, less than 100 cps, and even more prefera bly less than 50 cps, as measured using a Brookfield Viscometer or a rotational rheometer.
  • the dry coating thickness as measured by coating on a PET su bstrate, ranges from ⁇ . ⁇ to 25 ⁇ , more prefera bly from 0.5 ⁇ to 15 ⁇ , and even more prefera bly from 0.5 ⁇ to ⁇ .
  • the elongation% at deformation decreases with increasing the coating thickness.
  • the ink from a permanent marker or Sharpie pen or other chemicals may leak through the coating and stain the PU su bstrate beneath, both causing cha nges in the optical properties of the protective film or laminate.
  • Additional agents such as surfactants, wetting agents, dispersing agents, defoamers, thermal sta bilizers, UV absorbers, hindered amine sta bilizers, thickeners, etc. may be incorporated into the a bove rad iation and thermally cura ble treatment compositions.
  • the treatment may include both thermal and radiation curing by including curing agents in the coating composition.
  • curing agents for example, radiation cura ble acrylate monomers or oligomers with or without hydroxyl groups and a radiation cu ring initiator can be added into the a bove mentioned thermally cura ble formulations for curing by an irradiation source.
  • the thermally cura ble components in the a bove thermal cura ble compositions can be added into a UV curable composition and cured thermally. In both cases, curing ca n be started either in sequence or simultaneously.
  • the coating can be applied to the plastic film by any means including but not limited to, slot die, flexo-graphy, wire-bar coating, blade coating, gravure coating, spray coating, dip coating, curtain coating, flexography, roll coating or other suita ble methods.
  • the coating solution can also be applied by digital printing, such as by UV or solvent Inkjet printing.
  • the diffusion of ingredients from the treatment compositions into the plastic film leads to a su bstantial reduction in the layer thickness that is disposed a bove the plastic film.
  • the layer formed on and/or over the surface of the PU film is less than ⁇ , more preferably less than 5 ⁇ .
  • excellent Sharpie performance and up to 100% elongation can be obtained with less than 5 ⁇ thickness a bove the PU film surface.
  • the su rface treatment penetrates, d iffuses or migrates as much as 5 ⁇ into the film.
  • the surface treatment penetrates, diffuses or migrates as much as ⁇ into the film.
  • the surface treatment penetrates, diffuses or migrates as much as 20 ⁇ into the film.
  • the su rface treatment penetrates, diffuses or migrates as much as 50 ⁇ into the film.
  • the treatment solution migrates into or penetrates the film such that it has a concentration gradient that gradually decreases with the depth of penetration into the film.
  • the diffusion of ingredients from the treatment compositions results in significant changes in the mechanical properties of the plastic film.
  • the modulus of a 150 ⁇ thick Argotec PU film was increased from 29.0M Pa to 51.5M Pa and the elongation % decreased from over 300% to 175% after treatment with a preferred em bodiment treatment solution wherein all the treatment materials diffused into the PU film.
  • the modulus was further increased to 121.2M Pa and elongation % decreased to 47.1% when more treatment material was applied and a thin layer of treatment materials formed a bove the PU film.
  • the low surface energy component present in the noted treatment compositions also diffuses to the top surface simultaneously and leads to low surface energy to the treated plastic film. This two-way simultaneous diffusion leads to highly stretchable protection film/laminate with desired low surface energy properties.
  • the surface treatment described above can be applied to any suitable substrates, e.g., including both rigid and flexible or extensible substrates.
  • suitable substrates include but are not limited to plastics, glass, metal, ceramics, woods, composites, etc.
  • a flexible plastic film substrate is advantageous.
  • plastic films include but are not limited to, e.g., polyurethanes, polyvinyl chloride, polyolefins, polyesters, polyamides, polyacrylates, polysilicones, etc.
  • the surface treatment described above is beneficial for achieving strong adhesion between the treatment layer and the substrate. It reduces the stress at the treatment layer and the su bstrate, and minimizes the mismatch in physical properties between the treatment layer and the substrate which often lead to delamination, cracking, or other defects, particularly under severe environmental conditions. For example, a mismatch in thermal expansion has been a major cause for deformation, delamination, or cracking of plastic or metal substrates with a protective hardcoat.
  • the above treatment compositions can be applied to the plastic substrate discontinuously, e.g. in discrete areas which may be either random or regular patterns.
  • discrete areas which may be either random or regular patterns.
  • the pattern of the discrete areas and/or the amount of coating ingredients diffused into the polymeric substrate many interesting properties can be achieved. For examples, a "soft-feel" hand-touch property of the pristine polymeric film can be preserved, a matte finish polymer surface can be obtained having excellent chemical/stain resistance, and/or a stretchable plastic film having optical properties that change upon stretching can be obtained, etc.
  • the treatments in discrete areas can be made by conventional coating methods including but not limited to, pattern printing using flexo-graphy, gravure printing, or by digital printing such as inkjet printing.
  • localized heating can be applied to a plastic web to tune the amount of diffusion such as by I , lasers, or through a mask to create coatings with variable properties at different local areas. In the heated areas, more coating ingredients will penetrate into the plastic substrate and the treated plastic film/laminate will have higher elongation % at deformation. For areas that are not heated or exposed to low temperatures, less coating materials will penetrate into the plastic substrate and better mechanical or chemical resistance can be achieved.
  • a plastic substrate with discrete treatment areas can also be achieved by first treating the plastic substrate in the entire surface area followed by embossing using either thermal or I heating sources.
  • plastic substrates with discrete treatment areas can be achieved by first embossing the plastic substrate followed by surface treatment wherein the treatment materials partially fill in the valleys of the embossed plastic film/laminate.
  • the plastic film can be pre-treated prior to treatment with a liquid composition by, for example, corona, plasma or flame surface treatment, heat treatment, mechanical stretching, embossing, exposure to irradiations, laser etching, etc.
  • Pre-treatment of the plastic film by corona, plasma or flame can introduce new functionalities to the polymeric surface which may chemically react with agents in the liquid treatment composition to form strong chemical linkages.
  • Heat treatment or mechanical stretching can help eliminate stress and other variations in the plastic film.
  • UV light treatment and laser etching may fragment the polymeric chains to facilitate the diffusion of the treatment liquid.
  • the method comprises applying the treatment liquid to a pre-treated polymeric substrate.
  • the liquid treatment composition diffuses at least partially into the plastic film. Drying is applied to eliminate the carrier fluid. Curing is performed to cure the materials both above and within the plastic film.
  • sequential treatments can be conducted upon the plastic substrate.
  • a first liquid treatment composition can be applied onto the polymeric su bstrate and the coated substrate can be processed at high temperatures to enhance diffusion, and cured.
  • a second liquid treatment composition which may be same or different than the first treatment composition, is pattern coated over the first treatment layer. The coating ingredients from the second treatment will reside above the surface of the first treatment layer and provide better chemical and mechanical properties.
  • textures can be created on the plastic film either before or after surface treatment by for example, printing or embossing techniques. Textures produced by printing methods are formed above the horizontal surface or face of the plastic film whereas those formed by embossing are located below the horizontal surface or face of the plastic film.
  • a textured surface particularly those mimicking natural species, may provide special properties to the treated films. Examples of such textured surfaces include an anti-reflection surface from a moth eye; a reduced friction surface from a shark skin; an ultra-hydrophobic surface from lotus leaves; etc.
  • a textured surface is also useful for providing a retro-reflective surface for road signs, graphics, and for anti-fingerprint properties.
  • the textures created on treated film surfaces can be random or regular patterns, with variable depth, and above or beneath the surface of the plastic film. Embossing after surface treatment is advantageous because the treated plastic surface has low surface energy which is beneficial for separation from the embossing tool. On the other hand, embossing can be conducted first, followed by printing of the treatment composition wherein the treatment materials partially fill the valley areas to preserve the embossing features.
  • textures can also be created on the plastic film surface by applying the liquid treatment materials and curing through a mask.
  • the method comprises applying the liquid treatment materials on the surface of the plastic film.
  • the method also comprises drying the treated plastic film to eliminate the carrier fluid.
  • the method further comprises curing through a mask to cure the areas exposed to the curing source.
  • the method also comprises heating the plastic su bstrate to a temperature higher than a temperature employed in the drying step, applying hot air to the treatment materials, using vacuum beneath the plastic film, and/or their combinations to allow the unexposed, uncured materials to diffuse into the plastic substrate, either partially or totally, randomly or uniformly, and cure therein.
  • the plastic film may be a multilayered film of which at least one of the layers is surface treated with a diffusion-enabled liquid treatment composition. If the layer to be treated by a liquid treatment composition is located inside or within an interior of a multilayered film, the surface treatment may be used as a primer layer to enhance adhesion with an additional treatment layer, or as a bonding layer for attaching to another polymeric su bstrate. In such applications, it is advantageous to use a liquid treatment composition that does not contain low surface energy agents. On the other hand, if the layer to be treated by a liquid treatment composition is located on the outside of a multilayered film, the surface treatment may be used as a dirt-repellent and/or anti-graffiti layer. It may be beneficial to use a liquid treatment composition comprising low surface energy agents.
  • a multilayered film can be made by many means including but not limited to, coating, co- extrusion, bonding via an adhesive, etc.
  • the use of a multilayer film is advantageous for several reasons.
  • the capability of coating ingredients diffusing into a plastic substrate depends on many factors and no or minimum diffusion may occur for many substrates.
  • a suitable organic solvent may not be readily available for promoting the diffusion process.
  • a PVC film becomes brittle when exposed to a ketone type solvent.
  • a thin layer of PU or other materials can be first attached onto such a plastic substrate by one of the means discussed above prior to application of the treatment. The coating ingredients will diffuse into the PU layer.
  • the treated plastic film/laminate can be thermoformed into three dimensional shapes and used as a protective film/laminate.
  • the treated plastic film can also be attached to a support, such as an ABS backing sheet, prior to em bossing to make a three dimensional part or component that can be handled easily without breaking.
  • Colors can be introduced by adding a colorant such as dyes or pigments into the treatment compositions to achieve an aesthetic effect or for self-protection.
  • a colorant such as dyes or pigments
  • the colorant diffuses into the plastic film su bstrate.
  • the depth of diffusion can be tu ned or adjusted by varying the process conditions which lead to various optical effects or an aesthetic appearance. Because of diffusion into the plastic film, the colorant is also protected by the plastic film against environmental degradations.
  • the plastic film ca n be treated in discrete areas using different liquid treatment compositions to produce different visual appearances such as a combination of high gloss, low gloss, color, text, or graphics. At least one of the appearances is made using a diffusion-enabled treatment liquid.
  • the release liner 12 is removed from the construction and the PSA layer 14 is used to ad here the treated film 10 to the surface of a desired object with the treated su rface 16 of the film 10 facing outward therefrom.
  • the film is optionally applied in this manner to an auto body surface or other like surface one wishing to protect.
  • stretcha bility, flexibility and/or extensibility is maintained, the film 10 can be readily and smoothly applied to complex geometries and/or otherwise curved surface.
  • alternate means can be used to adhere or otherwise stick the film 10 to a desired surface.
  • an optionally adhesive free functional layer may be employed.
  • a layer of silicone material with weak cohesion and/or low surface tension i.e., excellent weta bility
  • the functional layer easily spreads and/or conforms onto the surface of the object to which it is applied, and as air is squeezed out from between the functional layer and the object surface, a vacuum is created therebetween. This vacuum and/or the external air pressu re act to hold the film 10 to the surface of the object.
  • other adhesive free options known in the art may also be employed, e.g., such a gecko-mimetic functional material.
  • the laminate shown in Figure 1 can be manufactured in different ways.
  • a 150 ⁇ thick PU film extruded onto a 2mil thick polyester carrier is obtained from Argotec Inc.
  • the PU film has the first and second major surfaces. The first major surface is exposed and the second major surface is attached to the polyester carrier.
  • a pressure sensitive layer (PSA) was first coated onto the first major surface of the PU film and the PSA coated PU film was su bsequently laminated to a polyester release liner 12 as shown in Figure 1, the polyester carrier being peeled off.
  • the second major surface of the PU film is now exposed.
  • the treatment composition described a bove is applied to the second major surface, dried at high temperatures to eliminate the solvent and to initiate curing reactions for thermally curable composition, and subsequently cured using a mercury UV lamp when radiation curable composition is used.
  • the laminate shown in Figure 1 may further comprise a protective layer on the top surface of the treated film/laminate to protect the laminate from contamination or physical damages prior to application (Figure 2).
  • the new laminate comprises a protective layer 28, a PU film 20, a PSA layer 24, and a PET release layer 22.
  • the new laminate can be manufactured in different ways.
  • a 150 ⁇ thick PU film 20 extruded onto a 2mil thick polyester carrier is obtained from Argotec Inc.
  • the PU film has the first and second major surfaces. The first major surface is exposed and the second major surface is attached to the polyester carrier.
  • a pressure sensitive layer (PSA) 24 was first coated onto the first major surface of the PU film and the PSA coated PU film was subsequently laminated to a polyester release liner 22 as shown in Figure 2, the polyester carrier being peeled off.
  • the second major surface of the PU film is now exposed.
  • the treatment composition described above is applied to the second major surface, dried at high temperatures to eliminate the solvent and to initiate curing reactions for thermally curable compositions, and subsequently cured using a mercury UV lamp when a radiation curable composition is used.
  • the protective layer 28 is applied to the treated top surface via thermal lamination or adhesive.
  • the PSA layer 24 was first applied to a polyester release liner 22, and subsequently laminated to a first major surface of the PU film 20.
  • the polyester carrier on a second surface of the PU film is peeled off, thus exposing the second major surface to receive the treatment by the thermal or irradiation curable treatment compositions.
  • the treated PU surface is laminated to the protective layer 28 by lamination or via an adhesive.
  • the treatment composition described above is first applied to the first major surface of the PU film, dried at high temperatures to eliminate the solvent and to initiate curing reactions for thermally curable compositions, and subsequently cured using a mercury UV lamp when a radiation curable composition is used.
  • the protective layer 28 is then applied to the treated surface 26 by lamination or via an adhesive.
  • a pressure sensitive layer (PSA) 24 is coated onto a polyester release liner 22 as shown in Figure 2 and subsequently laminated to the second PU surface after peeling off the polyester carrier.
  • a region of diffusion exists typically extending from a top or upper surface of a film into at least an interior location in the film.
  • This region includes one or more coating ingredients of a coating composition at least initially disposed along the upper surface of the film.
  • the concentration of the coating ingredients within the film typically varies within the region of diffusion, and usually decreases with increasing distance from the upper surface of the film.
  • this region of diffusion is referred to herein as a surface treatment region.
  • This surface treatment region in which diffusion of coating ingredients within the film material occurs provides a wide array of benefits such as changes in one or more physical properties of the surface treated film.
  • films and/or laminates which are free of regions of diffusion can be prepared which exhibit many if not all of the changes in properties previously described herein with regard to films having regions of diffusion.
  • a mechanical property of a film may be significantly changed by applying a treatment composition on the film such that one or more components of the treatment composition diffuse into the film.
  • a film property e.g., any of the film properties described herein
  • a treatment composition can also be significantly changed by applying a treatment composition on the film such that diffusion does not occur and instead a distinct interface forms.
  • a particular coating composition applied to a film produces (i) a treated film with a surface treatment region, i.e., a region of diffusion; or (ii) a treated film free or substantially free of a surface treatment region.
  • a surface treatment region i.e., a region of diffusion
  • a treated film free or substantially free of a surface treatment region i.e., a region of diffusion
  • the treatment composition is free of a diffusion promoting solvent.
  • the diffusion promoting solvent is a ketone or acetate type solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, etc.
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • the treatment composition is typically free of MEK, MIBK, ethyl acetate or similar solvent(s).
  • the protective sheets exhibit particular and unique combinations of properties. Many of these combinations relate to elongation characteristics and surface energies. For example, in one aspect a protective sheet is provided which can withstand elongation of at least 40% without failing and which exhibits a surface energy of less than 35mN/m. In another aspect, a protective sheet is provided which can withstand elongation of at least 70% without failing and which exhibits a surface energy of less than 35mN/m. In yet another aspect, a protective sheet is provided which can withstand elongation of at least 40% without failing and which exhibits a surface energy of less than 25mN/m.
  • a protective sheet that can withstand elongation of at least 70% without failing and which exhibits a surface energy of less than 25mN/m.
  • the subject matter includes protective sheets exhibiting these particular combinations of properties which are formed using thermally curable compositions and those which are formed using irradiation curable, e.g., UV curable, compositions.
  • the subject matter includes protective sheets exhibiting these particular combinations of properties which include an interface between a coating composition and a film.
  • the subject matter includes protective sheets exhibiting these particular combinations of properties which are free of a region of diffusion of the coating composition on the film.
  • the su bject matter includes protective sheets exhibiting these particular combinations of properties and which include a region of a gradual transition between the coating composition and the film.
  • the present subject matter also provides methods of forming coated substrates in a single or one pass method.
  • the coating formulation includes one or more co-solvent(s) having a boiling temperature less than and/or a vapor pressure higher than, those properties associated with the primary solvent(s) in the formulation.
  • a paper or film carrier is first coated with a pressure sensitive adhesive.
  • the assembly is then laminated to a polymeric film and carrier assembly such as a polyurethane/PET carrier assembly via the PSA surface.
  • the PET carrier is peeled off from the polyurethane film, and a Sila-MaxTM coating as described herein is applied to the exposed polyurethane surface and subsequently processed and/or cured.
  • This one pass process enables production of the protective film much more efficiently than a two pass process described in the prior art.
  • Figures 34A-34F schematically depict a one pass technique for forming a coated layered su bstrate in accordance with the present su bject matter.
  • a first layered assembly 100 that includes a carrier layer 110 and a layer of an adhesive such as a pressure sensitive ad hesive layer 120.
  • the PSA layer 120 is disposed along a face of the first carrier 110.
  • a second layered assembly 130 is also provided that includes a polymeric su bstrate 140 on a second carrier layer 150.
  • One or more other layers can be interposed between the polymeric su bstrate 140 and the second carrier layer 150.
  • Representative examples for the polymeric su bstrate 140 include polyurethane.
  • the second carrier 150 include polyethylene terephthalate (PET) carrier films.
  • the one pass technique also comprises an operation of contacting a face 122 of the adhesive layer 120 of the first layered assem bly 100 with a face 142 of the polymeric su bstrate 140 of the second layered assembly 130 and adhering the two assem blies 100 and 130 together to thereby form an adhered layered assem bly 160 as shown in Figure 34B.
  • the one pass technique also comprises an operation of removing or otherwise separating the second carrier layer 150 from the polymeric su bstrate 140 to thereby expose another face 144 of the polymeric su bstrate 140. This is shown in Figure 34C.
  • a coating material or treatment composition as described herein which is typically in a liquid form, is applied to the face 144 of the polymeric su bstrate 140 to thereby form a coating layer 170.
  • a nonlimiting example of a suita ble coating layer is the previously described Sila-MaxTM treatment solution.
  • the intermediate product is depicted in Figure 34D.
  • the coating layer 170 After formation of the coating layer 170, that layer is dried and cured as described herein. Curing may be accomplished for example by exposure to a UV lamp 175. A coated layered su bstrate 180 is produced.
  • Figure 35 is a process flow chart schematically depicting a one pass method 200 in accordance with the present su bject matter.
  • the method comprises operations(s) of providing a layered assembly of a PSA and a carrier, shown as 210.
  • the method also comprises operation(s) of providing a layered assembly of a polymeric su bstrate and a carrier, depicted as 220.
  • the method 200 also comprises operation(s) involving contacting a face of the PSA with a face of the su bstrate to thereby adhere the two assemblies together and form an adhered layered assem bly. These operation(s) are shown as 230.
  • a carrier is removed to thereby expose a face of the su bstrate.
  • the removal of the carrier in operation 240 is generally performed after the two su bassem blies have been adhered to one another in operation 230.
  • the method 200 also comprises operation(s) 250 in which a coating material is applied to the exposed face of the su bstrate.
  • the coating material can be in the form of any of the coating materials described herein.
  • the method 200 also comprises one or more operation(s) 260 of drying and curing the applied coating.
  • the su bstrate is a polyurethane film.
  • the carrier associated with the PSA can be for example a PET carrier.
  • the coating material may comprise for example polyhydral oligomeric silsequioxanes, or a nanostructured organic- inorganic hybrid material as previously described herein.
  • the coating material may also comprise in addition, or instead, one or more UV curable acrylate monomer/oligomer(s), one or more photoinitiators, and carrier fluid(s).
  • the use of one or more co-solvents has several benefits.
  • the use of co-solvents controls the diffusion of solvent and other coating ingredients into the substrate. This is achieved by using one or more co-solvents having a different affinity with the substrate as compared to the primary solvent, e.g. MIBK solvent.
  • the use of one or more co-solvents with a higher evaporation rate minimizes the amount of residual solvent in the coated laminate.
  • isopropyl alcohol (IPA) has a higher vapor pressure than MIBK and evaporates much faster than the MIBK solvent.
  • the use of one or more co-solvents minimizes damage to some substrates, such as polypropylene, poly(methy methacrylate), and polycarbonate.
  • Those substrates can become brittle or even dissolve in the MIBK solvent.
  • the use of one or more co-solvents minimizes extraction of additives from the substrate.
  • plasticizers from a vinyl film can be extracted by the MIBK solvent and mixed into the coating liquid. The plasticizer extraction significantly reduces the flexibility of the vinyl film and reduces the curing of the liquid coating.
  • a wide array of co-solvents can be utilized such as ketones and particularly MEK, alcohols, ethers, alkyl acetates, and combinations thereof.
  • suitable alcohols include for example isopropyl alcohol.
  • an example of an alkyl acetate is ethyl acetate.
  • a PSA is typically used in the one pass process.
  • the properties of the PSA depend on the application. For exa mple, in forming coated films for automotive paint protective, the PSA should exhibit strong adhesion to the automotive paint. However, the present su bject matter includes the use of PSA's that exhibit relatively weak adhesion which is desired for applications such as those involving protective films for consumer electronics or other temporary applications.
  • an aliphatic or cyclo-aliphatic thermoplastic polyurethane can be used which exhibits good outdoor dura bility.
  • examples include Duraflex ® 3800A from Bayer Materials LLC and A GOTHAN E ® TPU from Argotec.
  • the components from the Sila-MaxTM composition diffuse into the polymeric, e.g. polyurethane, su bstrate.
  • the diffusion of Sila-MaxTM components may not extend into the PSA. However if a thinner PU film is used or if the process conditions are changed (such as for example increasing the temperature or diffusion time), the Sila-MaxTM components could diffuse through the PU.
  • diffusion into a PSA layer disposed along an opposite face of a PU film has been observed for a modified Sila-MaxTM formulation in which the components diffused through a 6 mil polyurethane film into the PSA layer.
  • the coating is then dried and cured.
  • curing can be accomplished by exposure to UV light.
  • Commercially availa ble mercury lamps are availa ble for such curing.
  • the thicknesses of protective films and the layers or regions constituting such films can vary depending upon the particular application.
  • a typical thickness for the PSA layer is 1-2 mils
  • a typical thickness for the polymeric, e.g. polyurethane, layer is 6-12 mils
  • the overall thickness of the protective film is 7-14 mils.
  • the present su bject matter also provides coatings comprising (i) one or more agents that include low surface energy components and (ii) one or more carrier fluid(s).
  • the coating undergoes, or more specifically, the coating components undergo, d iffusion in multiple directions and typically in opposite d irections.
  • related methods and protective coated films produced using these methods.
  • graded index interpenetrating networks of agents or components from the treatment compositions within the polymeric su bstrate are formed.
  • the coating is a solvent based, UV cura ble coating.
  • the coating includes one or more low surface energy component(s) that are dispersed or dissolved in one or more organic solvent(s).
  • the coating undertakes two-way d iffusion, typically in opposite directions, simultaneously, when applied to a polymeric su bstrate such as polyurethane.
  • the low surface energy component(s) diffuses to the top surface of the substrate which is driven by natural forces to minimize the surface energy; whereas other ingredients diffuse into the polymeric substrate, with the solvent serving as a carrier.
  • the low surface energy components include one or more fluorine groups, silicone groups, hydrocarbon groups, and/or combinations thereof.
  • UV curable acrylates comprising one or more, or a combination of these groups, can be used.
  • graded index interpenetrating networks of agents or components from the treatment compositions within the polymeric substrate are formed.
  • the coating formulations or treatment compositions for providing protective layer(s) on a diffusible polymeric substrate comprise at least one agent that is diffusible in the polymeric substrate of interest.
  • the formulation may include a low surface energy component selected from the group consisting of fluorine groups, silicone groups, hydrocarbon groups, and combinations thereof.
  • the coating formulations may also comprise one or more carrier fluids that are also diffusible in the polymeric substrate.
  • a layer of treatment materials is formed on the substrate with the concentration of the low surface energy component decreasing from the top surface to the interface.
  • at least a portion of the organic solvent(s) diffuse into the polymeric substrate. Typically, such diffusion is in a direction away from the layer of the low surface energy component(s) formed on the polymeric substrate.
  • graded interpenetrating networks of agents or components from the treatment compositions within the polymeric substrate are formed.
  • Figure 36 is a process flow chart schematically depicting a method 300 for forming a coated substrate with a protective layer that includes low surface energy component(s).
  • These methods generally comprise providing a polymeric substrate, and providing a coating formulation as described herein. These operations are shown as 310 and 320, respectively in Figure 36.
  • the coating formulation includes at least one agent having a low surface energy component such as previously described, and at least one carrier fluid.
  • the methods also comprise applying the coating formulation on the substrate to form a layer on the polymeric substrate. Typically the concentration of the low surface energy component(s) is greater along a top or outer surface than at the interface. This operation is shown as 330 in Figure 36.
  • the methods also comprise performing a drying operation and/or a curing operation of the layer on the substrate to thereby form a coated substrate having a protective layer thereon. These are shown as operation(s) 340.
  • the resulting protective coated films generally comprise a layer disposed on a face of the polymeric substrate.
  • the layer includes at least one agent having one or more low surface energy component(s) as noted herein.
  • the protective coated film also comprises a region of diffused components within the polymeric substrate which are generally spaced from the layer after diffusion through at least a portion of the substrate. In certain versions, graded index interpenetrating networks of agents or components from the treatment compositions within the polymeric substrate are formed.
  • low surface energy components are utilized in a coating formulation that undergoes diffusion in multiple directions, and particularly in such a manner that the low surface energy components or at least a majority proportion of these components, diffuse to the top surface or outer face of the substrate; while other components with relatively higher surface energy, i.e. better affinity with the polymeric substrate, diffuse into the substrate. Because of diffusion in multiple directions for a coating on a diffusible polymer substrate, the concentration of the low surface energy components on the top surface is greater than a concentration of such components in a corresponding layer produced on a non-diffusible substrate.
  • the present subject matter also provides strategies for selection of photoinitiators based upon optical absorption or transmission characteristics of a substrate.
  • the photoinitiator absorbs at wavelength regions in which the polymer film is at least partially transmissive.
  • the UV curing system for example UV lamps, needs to provide sufficient UV emissions at these wavelengths.
  • certain polyurethane films are partially transmissive at wavelengths around 260nm and absorb most of the emissions below 240nm and from about 275nm to about 400nm. If the UV photoinitiator absorbs at wavelengths below 240nm or between 275nm and 360nm, the coating materials that have diffused into the polymer film cannot be effectively reached and cured by the UV light.
  • Figures 32 and 33 illustrate optical properties of a commercially available polyurethane film (Figure 32) and absorption spectra of photoinitiators ( Figure 33). Specifically, Figure 32 illustrates UV spectra of a 6 mil A GOTEC polyurethane film. Percentage light transmission T%, is shown by the solid line. Absorption A%, is shown by the dashed line. Thus, that film is at least partially transmissive at a wavelength of around 260 nm. However, certain polymeric films are known which exhibit multiple transmission peaks in the UV wavelength range. And, these peaks may be centered at wavelengths different than 260 nm.
  • Figure 33 illustrates UV absorption spectra for two photoinitiators.
  • a conventional photoinitiator having the absorption spectra shown by the dashed line exhibits a single peak around 260 nm.
  • a photoinitiator having two peaks, e.g. at about 240 nm and 300 nm, is shown via its absorption spectra as a solid line.
  • the ARGOTEC film of Figure 32 is to receive a coating to form a protective film as described herein, that the conventional photoinitiator of Figure 33 having a peak absorbance at about 260 nm could be used.
  • a photoinitiator exhibiting absorbance peaks corresponding to the transmission peaks of the film should be used.
  • the present subject matter provides methods for selecting photoinitiators based upon the optical characteristics of a substrate.
  • the present subject matter selection technique for photoinitiators is unique.
  • the coating liquid and the photoinitiator used remain on or above the substrate. That is, the optical properties of the substrate have no effect on the selection of the photoinitiator.
  • the present subject matter methods ena ble diffusion of coating ingredients into the substrate.
  • the wavelengths of the light source of which the photoinitiator absorbs need to be able to pass through the su bstrate (at least partially), to reach the photoinitiator and become absorbed.
  • the substrate needs to be at least partially transparent to that wavelength region.
  • the present subject matter includes use and/or selection of a photoinitiator that exhibits multiple absorbance peaks.
  • a substrate for use with the photoinitiator should at least be partially transparent or light transmissive to at least one of the absorbance peaks.
  • the present subject matter provides methods for selecting one or more photoinitiators for use in a polymerizable composition that is applied to a polymeric substrate. These methods are particularly well suited for applications in which the compositions at least partially diffuse into the substrates.
  • the methods comprise identifying one or more spectral regions within which the polymeric substrate exhibits maximum transmission or at least substantial maximum transmission, of light.
  • the methods additionally comprise selecting a photoinitator that exhibits a maximum absorbance within the one or more spectral regions which the polymeric substrate exhibits maximum transmission.
  • the polymeric substrate exhibits a maximum transmission of light within a range of 100 nm to 400 nm, and particularly within a range of 200 nm to 300 nm.
  • the photoinitiator may for example be benzophenone and/or the substrate may be polyurethane.
  • the polymeric substrate may exhibit at least two spectral regions of maximum transmission of light. Therefore, the selection of photoinitiator is made with regard to a photoinitiator that exhibits at least two maximum absorbances, and particularly within the spectral regions of maximum light transmission exhibited by the substrate.
  • the photoinitiator is benzophenone (BP).
  • benzophenone (BP) has been identified as a preferred photoinitiator.
  • the BP photoinitiator has a very broad and strong absorption between 200 and 300nm wavelength range. This is the same wavelength range in which many polyurethane substrates are partially transparent. This allows the UV light (emitted from a UV curing lamp for example) to pass through the polyurethane substrate and effectively cure the Sila-MaxTM materials that have diffused into the polyurethane film.
  • Benzophenone is useful as a photoinitiator in a coating or composition which diffuses into a polymeric substrate and then cured.
  • the present subject matter includes the use of other photoinitiators such as I GACU E 184, IRGACURE 250, and IRGACURE 754, all commercially available from BASF.
  • the present subject matter also provides matte finish coatings and related methods for their formation.
  • the matte finish coatings can be formed by selection of coating components and substrate.
  • the extent or degree of gloss, or conversely the extent of a matte finish can be obtained and/or selectively adjusted by control of the size of particles and diffusability of liquid component(s) within a coating formulation. Selection of particulate size and diffusability of liquid components in the coating formulation has been discovered to lead to control of gloss or matte properties of the resulting coated substrate.
  • a protective film having a relatively low gloss or high matte finish can be prepared by formulating the coating to include particulates that are too large to diffuse into the polymeric substrate and one or more liquid components which can diffuse into the polymeric substrate. Upon applying the coating to the substrate, the particles are left along an outer face of the substrate while the liquid component has partially diffused into the substrate. After drying and curing, the outer surface of the thus formed protective film has a relatively low gloss or high matte finish.
  • a relatively higher gloss protective film can be formed using the same coating formulation if the polymeric substrate is such that neither the particulates nor the liquid components in the coating formulation diffuse, or substantially diffuse, into the polymeric substrate.
  • the resulting protective film will include a relatively higher gloss outer surface as compared to the previously described film formed from a coating including particulates that did not diffuse into the substrate and liquid components which diffused into the substrate.
  • FIG. 37 is a process flow chart schematically depicting such a process 400.
  • the method comprises selecting and providing a polymeric substrate. This is shown as operation 410.
  • the method comprises selecting and providing a coating material that includes one or more liquid components(s) and particulates dispersed in the liquid component(s).
  • the particulates have a size, i.e. diameter, effective diameter, or outer span, such that the particulates do not diffuse or substantially diffuse into the polymeric su bstrate.
  • the coating material is applied to the face(s) of the polymeric substrate, as depicted in operation 430.
  • the applied layer of coating material is then dried and cured as described herein to thereby form the coated su bstrate.
  • operation 440 Optical gloss of the coated substrate is reduced by selecting the polymeric su bstrate such that at least a majority proportion of the liquid component(s) diffuse into the polymeric substrate.
  • operation 450 Optical gloss of the coated substrate is increased by selecting the polymeric substrate such that at least a majority proportion of the liquid component(s) do not diffuse into the polymeric substrate.
  • operation 460 In both situations, after applying the coating material to one or more faces of the substrate, at least a majority proportion, i.e. greater than 50%, of the particulates remain on the face of the substrate and do not diffuse into the substrate.
  • the proportions of particulates that remain on the substrate face are significantly higher such as greater than 90%, 95%, 98%, 99%, and 99.9%.
  • this technique enables adjustment of gloss of a coated substrate by appropriate selection of substrate as opposed to changing or adjustment of the coating formulation.
  • substrates can be used such as polyurethane for example.
  • the particulates can be formed from numerous materials including for example polyamides. Typical size ranges of particulates in the coating materials can for example be in a range of 1 to 50 microns, and for many applications be about 5 microns.
  • Example 18 and Tables 29 and 30 illustrate the exemplary liquid treatment composition and the properties of the treated acrylic and polyurethane films.
  • the present subject matter also provides strategies for reducing coating defects by incorporating one or more surfactants into the coating formulation(s). Specifically, in certain embodiments, one or more surfactant(s) are incorporated into the Sila-MaxTM coating formulation to eliminate coating defects such as craters and/or pits.
  • a wide array of surfactants can be used in this aspect of the present subject matter. Generally, any fluorinated or silicone based surfactants are eligible so long as they are compatible with the coating formulation. Combinations of these surfactants can be used.
  • the surfactant includes reactive functional groups that promote chemical attachment to the coating matrix so that the surfactant does not migrate during application.
  • a compatible surfactant that contains unsaturated double bonds can attach to a UV cured coating matrix.
  • examples of commercially available surfactants that can be incorporated in the compositions described herein and which promote the reduction or elimination of craters and/or pits include TEGO 2250 from Evonik and FC-4430 from 3M.
  • the concentration of surfactant(s) in the compositions is from 0.1% to 1.0%.
  • the methods comprise incorporating or otherwise combining at least one surfactant in a coating material prior to application to a substrate.
  • the surfactant typically is a fluorinated surfactant, a silicone surfactant, or both types can be used.
  • fluorinated surfactant refers to a surfactant having one or more fluorine groups.
  • silicone surfactant refers to a surfactant having one or more silicone groups.
  • the surfactants can include one or more reactive functional groups that promote attachment or retention of the surfactant within the coating or layer and prevents migration or diffusion of the surfactant into the polymeric substrate.
  • Figure 38 is a process flow chart schematically depicting a method 500 for forming a coated substrate which reduces the potential of formation of surface defects.
  • the method comprises an operation 510 of providing a polymeric substrate.
  • the method also comprises an operation of providing coating materials that include liquid component(s), particulate(s), and one or more surfactants. This is shown as 520 in Figure 38.
  • a layer of the coating material is then formed on the substrate, depicted as operation 530.
  • the layer is then subjected to one or more drying and curing operations, shown as 540.
  • the present subject matter also provides strategies for selectively adjusting or altering surface properties of coated polymeric substrates by changing processing conditions.
  • these strategies can be undertaken without changing the coating composition or formulation. For example, residence time of a wet coating can be adjusted before drying. In addition, adjustment of drying temperatures can also alter diffusion and consequently, the surface properties of the treated plastic film.
  • the surface property of the coated polymeric substrate can be "tuned" by changing the processing conditions without changing the coating composition.
  • process conditions include for example, the residence time of the wet coating before entering the drying zones, and/or the drying temperatures and the residence time in the drying zones, etc.
  • the treatment liquid comprises low surface energy components
  • an easy and quick way to assess the surface property is to write on the surface of interest using a Sharpie marker or pen.
  • the coated surface is not writable and the ink can be wiped off easily using a paper or cloth.
  • the coating is writable and the ink cannot be wiped off with a paper or cloth.
  • the treatment liquid comprises electrically conducting materials
  • an easy and quick way to assess the surface property is to measure the surface conductivity using a Four-Point probe.
  • the treatment liquid comprises low surface energy components
  • diffusion of coating ingredients is promoted.
  • increased diffusion of coating ingredients into a polymeric substrate occurs at higher drying temperatures and/or longer residence times.
  • the amount of applied coating liquid and the kinetic or thermal energy of the coating liquid can affect one or more of the previously noted surface properties. Applying a greater amount of coating liquid will generally lead to increased amounts of coating materials remaining on or above the face of the polymeric substrate. Higher kinetic or thermal energy of the coating liquid will promote diffusion into the polymeric substrate. Increasing kinetic or thermal energy of the coating can be achieved by spraying the coating liquid at increased velocities through a nozzle or by pre-heating the liquid for example.
  • the present subject matter also provides coated polymeric films such as polyurethane films or substrates, with matte finishes and which can be extended or stretched.
  • the coated films are elastically extensible. This is unique because typically coated films with a matte finish are typically not stretchable or extensible because the matting agents include micron-sized particles and the coating cracks or otherwise fractures upon stretching.
  • the present subject matter also provides thermally curable compositions which are provided for surface treatment of polymeric films such as for example polyurethane substrates.
  • the present subject matter ena bles production of relatively high gloss surfaces using these thermally curable compositions.
  • new thermally curable liquid treatment compositions are provided for surface treatment of plastic films for application as protection films for automotive paint protection, consumer electronics, etc.
  • Particular focus is for flexible/conformable plastic films such as polyurethane that are hand stretchable and easily conformable to irregular surfaces.
  • the new treatment compositions can produce a surface that exhibits a relatively high gloss, and in certain versions, a 60 degree gloss of greater than 95, excellent optical clarity, and excellent dirt-repellent/anti-graffiti/stain resistance. These characteristics are demonstrated by Sharpie ink beading up nearly instantaneously and 100% dry ink removal using a cloth or paper along with a good mar/scratch resistance and more than 80% hand stretchability without cracking.
  • Protective films with high gloss/shiny surfaces, dirt-repellent/anti-graffiti/easy-cleaning properties, resistance to scratches/marring and stains, and easy conformability to irregular surfaces are key attributes for protecting articles against chemical and mechanical damages while providing a good aesthetic appearance.
  • the protective films treated with the treatment compositions described herein provide a unique combination of properties including surface gloss, dirt-repellent/anti-graffit/easy- cleaning, resistance to chemical/physical damages, and conformability to irregular surfaces.
  • FIG 39 schematically illustrates such a method shown as method 600.
  • the methods comprise providing a thermally curable coating composition including a liquid vehicle, and particulates dispersed in the vehicle. This is shown as operation 610.
  • the methods also comprise providing a polymeric substrate that defines one or more faces. This is shown as operation 620.
  • the coating composition is applied on the face of the polymeric substrate to form a layer of the coating composition. This is shown as operation 630.
  • the methods also comprise heating the layer of the coating composition and forming the coated polymeric substrate. This is shown as operation 640.
  • the coated substrate exhibits a 60 degree gloss of at least 95.
  • the 60 degree gloss is greater than 96, greater than 98, and in still other versions greater than 100.
  • Particular embodiments of the thermally cured coated substrates can also be stretched or extended such as to distances of at least 40% or even 80% beyond an initial dimension prior to such extension, without cracking or other fracturing occurring in the cured coating layer. This property is also referred to and described herein as % elongation.
  • curing is performed by heating to a temperature within a range of 280° F to 320°F and for a time period of from 1 minute to 10 minutes or more. In particular versions of the methods, heating is performed at a temperature of 300° F for a time period of 3 to 5 minutes.
  • Example 19 and Tables 31 and 32 illustrate evaluations of thermally cured, high gloss protective films.
  • the treated plastic film consists of a multilayered film of which at least one of the layers is a diffusion-enabled layer and is treated with a liquid treatment composition wherein the agents in the treatment liquid diffuse at least partially into the diffusion- enabled layer. Drying is applied to eliminate any carrier fluids and the treatment materials located both above and within the diffusion-enabled layer are cured to form an intermediate layer.
  • the intermediate layer can serve as a primer on which additional treatment layer(s) can be applied as illustrated in Figure 40A or as a bonding layer to bond a second coating layer or a plastic substrate to a first plastic substrate as illustrated in Figure 40B.
  • the intermediate layer may be located along the top surface of the treated plastic substrate which is subsequently attached to another plastic substrate to produce the final multilayered plastic film as illustrated in Figure 40C.
  • Figure 40A illustrates a multilayered film 700 in accordance with the present subject matter.
  • the film 700 includes a plastic substrate 702, a primer layer 704 disposed on a face 703 of the substrate 702, and an additional coating layer 706 disposed on the primer layer 704.
  • the coating layer 706 provides an outer surface 708.
  • Figure 40A illustrates diffusion of one or more components of the primer layer 704 into the plastic substrate 702 and past the face 703.
  • Figure 40B illustrates another multilayered film 710 in accordance with the present subject matter.
  • the film 710 includes a first plastic substrate 712, a second plastic substrate or coating layer 716, and a bonding layer 714 disposed between the substrates 712 and 716.
  • One or more components of the bonding layer diffuse past a face 713 and into the first plastic substrate 712 as shown in Figure 40B.
  • Figure 40C illustrates a multilayered film 720 in accordance with the present subject matter.
  • the film 720 includes a first plastic substrate 722, a second plastic substrate 724, a layer or region of an adhesive 725 disposed between the su bstrates 722 and 724, and a topcoat layer 726.
  • the topcoat layer 726 is disposed on a face 723 of the first plastic substrate 722.
  • FIG 40C also schematically depicts a method of forming the multilayered film 720 in accordance with the present subject matter.
  • an effective amount of the topcoat material is applied on the face 723 of the first plastic substrate 722.
  • the substrate 722 can include the adhesive layer 725 along an oppositely directed face.
  • the second substrate 724 is then obtained or otherwise provided and then contacted with an exposed face of the adhesive layer 725.
  • diffusion of the topcoat layer 726 into the first plastic substrate 722 can occur prior to mating with the second plastic substrate 724.
  • the present subject matter includes techniques in which the second plastic substrate 724 is mated to the adhesive layer 725 and the first substrate 722 before application of the topcoat layer 726 to the face 723; after application of the topcoat layer 726 to the face 723 but prior to or during diffusion of components in the topcoat layer 723 into the first plastic substrate 722; and after application of the top coat layer 726 to the face 723 and after diffusion of components in the topcoat layer 723 into the first plastic substrate 722.
  • the plastic film can be treated in discrete regions to produce a styling film with different visual appearances such as a high gloss region, a colored region, and/or a low gloss region as illustrated in Figure 41.
  • At least one of the treatment areas is produced by using a liquid treatment composition in which the agents from the treatment composition diffuse at least partially into the plastic film. After drying to eliminate a carrier fluid, the treatment materials located both above and within the plastic film are cured.
  • Figure 41 illustrates a multilayered film 800 in accordance with the present subject matter having one or more regions of different visual appearances.
  • the multilayered film 800 comprises a plastic substrate 802 defining a face 810.
  • the film 800 also comprises a high gloss region 804 on the su bstrate, a low gloss region 808 on the substrate, and a color region 806 on the substrate.
  • the regions 804, 806, and 808 are all disposed on the face 810 of the substrate 802.
  • one or more components from the composition forming the color region 806 diffuse past the face 810 and into the substrate 802.
  • the plastic film can be pre-treated prior to the treatment with a liquid composition by, for example, corona, plasma or flame surface treatment, heat treatment, mechanical stretching, embossing, exposure to irradiations, laser etching, etc. Combinations of the pre-treatments can be utilized.
  • a layered film produced from this process is illustrated in Figure 42.
  • Pre-treatment of the plastic substrate prior to application of the liquid treatment composition can promote interaction with and/or diffusion of the agents from the treatment liquid.
  • Figure 42 depicts another multilayered film 900 in accordance with the present subject matter.
  • the film 900 comprises a plastic substrate 902 defining a face 910. Prior to applying a topcoat layer 912, one or more treatment operations are applied to or performed upon the face 910.
  • one or more components of the composition constituting the topcoat layer diffuse past the face 910 and into the substrate 902.
  • textures can be created on the plastic film either before or after surface treatment by for example, printing or embossing techniques as illustrated in Figure 43A and Figure 43B, respectively. Textures, such as for example, produced by printing methods, are formed above the horizontal surface or face of the plastic film whereas those formed by embossing are located below the horizontal surface of the plastic film.
  • the liquid treatment composition is applied to the textured plastic substrate and the agents from the treatment composition diffuse at least partially into the plastic film. Drying is applied to eliminate the carrier fluid. Drying may also further enhance diffusion of the other treatment agents into the plastic substrate.
  • FIG 43A schematically illustrates a multilayered assembly 1000 in accordance with the present subject matter.
  • the assembly 1000 comprises a plastic substrate 1002 defining a face 1004 having a plurality of projections or outwardly extending members 1008.
  • the plurality of projections 1008 extend outward from the face 1004.
  • the projections 1008 can be formed using a variety of different techniques such as for example, by printing the projections 1008 on the face 1004.
  • a topcoat layer 1006 is applied on the face 1004 and on the projections 1008.
  • the distal tips or ends of the projections 1008, i.e. the regions of the projections 1008 farthest from the face 1004 can either extend beyond an outer surface 1007 of the topcoat layer 1006, or be submerged or disposed under the outer surface 1007.
  • the present subject matter includes a wide array of other arrangements and versions. Also, in the embodiment of Figure 43A, one or more components of the topcoat layer 1006 can diffuse past the face 1004 and into the substrate 1002.
  • Figure 43B illustrates another multilayered assembly 1100 in accordance with the present subject matter.
  • the multilayered assembly 1100 comprises a substrate 1102 defining a face 1104, and a topcoat or treatment composition layer 1106 disposed on the face 1104.
  • the face 1104 can define a plurality of depressions, recesses, or embossed regions generally denoted as item 1108 in Figure 43C.
  • the embossed regions 1108 can be in a wide array of shapes and sizes.
  • the overall visual appearance and/or texture of the resulting assembly 1100 can be selected by controlling the extent to which the embossed regions 1108 are "filled in” or occupied by the material of layer 1106. In the particular embodiment depicted in Figure 43B, one or more components of the material forming the layer 1106 diffuse past the face 1104 and into the substrate 1102.
  • textures can also be created on the plastic film surface by applying the liquid treatment materials and curing through a mask as illustrated in Figure 43C.
  • the method comprises applying the liquid treatment materials on the surface of the plastic film.
  • the method also comprises drying the treated plastic film to eliminate the carrier fluid.
  • the method further comprises curing through a mask to cure the areas exposed to the curing source.
  • the method also comprises heating the plastic su bstrate to a temperature higher than that employed in the drying step to allow the unexposed, uncured materials to diffuse into the plastic substrate, either partially or totally, and cure therein.
  • Figure 43 schematically depicts a process 1200 and various intermediate assemblies in forming a textured multilayer assembly 1250 in accordance with the present subject matter.
  • the process 1200 utilizes an intermediate assembly 1210 having a plastic substrate 1212 defining a face
  • the method 1200 comprises obtaining or providing a mask 1220.
  • the mask 1220 defines one or more regions 1222 that allow transmission of light or energy, or at least partially, and one or more regions 1224 that block or hinder transmission of light or energy.
  • the method 1200 includes an operation in which the mask 1200 is positioned on or generally over the topcoat layer 1216.
  • the masked topcoat is then su bjected to one or more curing operations such as by exposure to UV light or other energy.
  • the topcoat layer may be subjected to drying and/or heating operations for example to remove at least a portion of solvents, vehicles, carriers or other volatile components in the topcoat layer.
  • FIG. 43C The mask curing operation is schematically depicted in Figure 43C as operation A.
  • an intermediate assembly 1230 results having one or more regions in the topcoat layer 1216 that are cured as a result of light passing through mask regions 1222, and one or more regions in the topcoat layer
  • the method 1200 also comprises an operation B in which uncured portions of the topcoat layer 1216 diffuse or diffuse further into the substrate 1212, shown as diffused regions 1216B.
  • the remaining regions of the topcoat layer 1216 which were previously cured after mask curing, are shown as regions 1216A.
  • the intermediate assembly having diffused regions 1216B is depicted as assembly 1240. Diffusion or formation of the diffused regions 1216B can be promoted by heating the intermediate assembly 1230.
  • the assembly is subjected to additional curing, and typically without a mask.
  • This operation is denoted as operation C and referred to herein as flood curing.
  • Flood curing results in curing of the materials in diffused regions 1216B.
  • the resulting multilayered assembly 1250 comprises a plurality of outwardly extending cured regions 1216A and a plurality of cured diffused regions 1216B.
  • the method 1200 comprises a wide array of alternate versions and variations such as techniques in which the topcoat layer 1216 is only partially dried or partially cured in operations A and/or B, or prior thereto; and then further cured and/or dried in operation C, or afterwards.
  • Instron Measurement Unless otherwise stated, the measurement was performed on an lnstron-5542 instrument. Samples were cut into l"x 6" strips and a PET casting sheet peeled off before clamping to the sample holder. An initial gauge length of 4" was used. The specimen was elongated at a speed of 2 inch/min and stopped as soon as a change in the optical appearance, such as hazy/milky or cracking, appeared. The elongation % was recorded and named as the elongation % at deformation throughout the description herein. Three measurements were taken for each sample and the average values were reported.
  • Gloss Measurement Unless otherwise stated, the gloss at 60° incident angle was measured using a Micro-T I-gloss instrument (BYK Gardner) according to ASTM D-523 testing protocol. Unless otherwise stated, the test was performed by attaching the plastic film on the surface of a black color ACT automotive paint-test panel through the adhesive layer. At least three measurements were taken at different areas and the average values were reported.
  • Haze Measurement The measurement was performed using a Gardener Haze-Guard-Plus instrument (BYK Gardner). For a PU/PET film su bstrate, the measurement was made on the PU film by peeling off the PET carrier. When a PU/PSA/PET film substrate was used, the sample was mounted onto a glass panel via the PSA layer after peeling off the PET film. The optical transmission%, haze% and clarity% were recorded. At least three measurements were taken at different areas and the average value was reported.
  • Used Motor Oil Test This test is used to emulate resistance to staining by chemical agents. The test was performed by contacting a 2"x 4" test specimen to a used motor oil (Pennzoil, 10W- 30) at room temperature for 48 hours. After the test, the residual motor oil was removed from the sample surface; and the sample surface was thoroughly cleaned using a soap detergent, rinsed with water, and dried at room temperature.
  • Asphalt Stain Resistance Test This test is also used to emulate resistance to staining by chemical agents. The test was conducted using a mixture of kerosene and Roof Repair (Roofers Choice plastic roof cement 15) in a 1 to 1 ratio. The liquid was applied to the sample surface using a plastic pipette and kept in the laboratory environment for 48 hours. A Bug & Tar Remover fluid was applied over the tested area for about 2 minutes and removed using a clean cloth. The tested area was thoroughly cleaned using a general purpose automotive cleaner and dried at room temperature.
  • Impact Abrasion Resistance Test A modified ASTM D968-93 testing method was used. The treated plastic film samples were laminated to an aluminum (Al) panel through the PSA layer. The Al panel was firmly mounted on a heavy metal holder. Five pounds of a sand mixture with 3/8 to 1/2 inch in diameter particle size was used as the impact material. The sand mixture was poured from the top of a 3 meters long and 0.5 inch diameter stainless steel tube. The sand particles gained speed and upon exiting the tube, impacted on the sample carrying Al panel which was located at 3 inches from the bottom of the tube and positioned at a 45 degree angle. After all the sand mixture flowed out from the tube, the Al panel was removed from the heavy metal holder.
  • Permanent Marker Test This test is aimed to illustrate the anti-graffiti or easy cleaning properties. The test was performed using a black color MARKS-A-LOT FineMarkTM Permanent Marker. A straight line of about 2 inches in length was written onto the surface of the treated film. After 15 seconds dwell time, the ink was wiped off using a KLEENEX tissue. A rating of "1" to "10” was assigned to represent the amount of ink residue left. A rating "1" means that the ink could not be wiped off at all, and a rating "10” indicates that the ink could be wiped off cleanly.
  • Sharpie Performance Testing This test is aimed to illustrate the anti-graffiti or easy cleaning properties. The test was performed using a black color king size Sharpie pen. A straight line about 2 inches long was written onto the surface of the treated film. After 15 seconds dwell time, the ink was wiped off using a KLEENEX tissue. A rating "1" to “10” was assigned to represent the amount of the ink residue left. A rating "1” means that the ink could not be wiped off at all, and a rating "10” indicates that the ink could be wiped off cleanly.
  • UV Weathering Test The test was conducted using an Atlas Ci-5000 BH type Weather- ometer according to SAE J-1960 protocol to simulate extreme environmental conditioned encountered by a vehicle in outdoor environments.
  • the testing protocol consisted of repeating cycles of 120 minutes of light and 60 minutes of dark in the following sequences: a) 40 minutes of light; b) 20 minutes of light and front specimen spray; c) 60 minutes of light; and d) 60 minutes of dark with both front and back spray.
  • the dry bulk of the UV lamp had a temperature of 38°C ⁇ -2°C and relative humidity of the chamber was 95% ⁇ 5%.
  • the dry bulk temperature was maintained at 47°C ⁇ 2°C and the relative humidity in the chamber was maintained at 50% ⁇ -5%.
  • FT-IR Imaging This test method was developed to characterize diffusion of coating ingredients into the film substrate. FT-IR measurements were taken using a Perkin Elmer Spotlight 400 system. The samples were first cut cross-section in liquid nitrogen and FT-IR images were collected at different locations from the topcoat surface to the bulk of the PU film at a spatial resolution of about 1.56 ⁇ . The images were collected with spectral resolution of 4cm "1 . In total, 32 scans were collected and averaged at each location in order to obtain high quality spectra.
  • Coating Thickness Measurement The thickness of the treatment layer disposed above the plastic film was measured using optical microscopy. Samples were cross-sectioned under liquid nitrogen and the layer thickness was measured using an OLYMPUS BX60 optical microscope.
  • HPLC/GPC measurements Samples of about 150 mg were dissolved in 10 ml of tetra hydrofuran (THF) solvent and tumbled for about 3 hours. The solution was filtered through a 0.20 ⁇ PTFE filter and placed in an auto-sampler vial. A 0.2% acetic acid solution in THF was used as mobile phase which passed through the column at a flow rate of 1.0 mL/min. About 50 ⁇ of sample liquid was injected into the column of a Waters 2410. The molecular weight calibration standard was constructed by using polystyrene standards dissolved in THF solvent.
  • Sila-MaxTM U1006-40 treatment solution was obtained from Chisso Corp. (Osaka, Japan).
  • the solution contains a silicon-containing copolymer comprising POSS * moities, acrylate monomer/oligomers, and a photoinitiator mixed in methyl isobutyl ketone (MIBK) solvent with 40% solid.
  • MIBK methyl isobutyl ketone
  • the solution has a viscosity of about 2.8cps at 25°C as measured using a Brookfield Viscometer.
  • the silicon-containing copolymer contains low surface energy functional groups.
  • Polyurethane films of 150 ⁇ and 200 ⁇ in thickness extruded on a PET carrier were obtained from Deerfield Urethane (Dureflex ® ) and Argotec (second PU film), respectively.
  • the Sila-MaxTM treatment solution was applied to the PU film using an Automatic Film Applicator at different wet thicknesses.
  • the treated PU film was first dried in a thermal oven at 160°F for 3 to 5 minutes and cured by UV light at 206mJ/cm 2 .
  • the optical properties of the treated PU film were measured using a Haze-Guard Plus and a Micro-T I- gloss instrument, respectively.
  • the haze % measurements were taken after peeling off the PET carrier whereas for gloss measurements, the PU film remained on the PET carrier.
  • the results of haze measurements are shown in Table 1 and the gloss values are shown in Figure 3.
  • the gloss values are measured by placing the sample on a stack of white paper.
  • a 150 ⁇ thick PU film obtained from Argotec was first laminated to a PSA layer forming a PU/PSA/PET laminate and subsequently surface treated with a 5 ⁇ and a 15 ⁇ (wet thickness) thick Sila-MaxTM U1006 treatment solution disclosed herein.
  • the surface treated samples were dried in a thermal oven at about 80°C for about 3 to 5 minutes and further cured by UV irradiation using a mercury lamp with 206mJ/cm 2 irradiation energy, at a speed of 100 feet/min. After curing, the release liner was removed and the surface treated PU films were attached to aluminum (Al) plates via the PSA layer.
  • FIG. 4 illustrates measured b values of the samples on an L, a, b color scale after subjecting the samples to the aforementioned used motor oil test.
  • the listed samples represent 150 ⁇ PU film treated with the Sila-MaxTM U1006 treatment solution applied at the respective coat weights indicated.
  • the listed control sample was untreated.
  • the control PU films from Deerfield and Argotec show comparable b values of about 27 after the motor oil test.
  • the b values are significantly smaller for the PU films treated with the Sila-MaxTM solutions ( ⁇ 2.0).
  • the b values decrease slightly by increasing the wet thickness from 5 ⁇ to ⁇ , which has almost the same b value as the 15 ⁇ sample.
  • a treatment with 5 ⁇ applied wet thickness is sufficient to achieve excellent resistance to the used motor oil.
  • the PU film treated with the Sila-MaxTM U-1006 treatment solution also showed a significant reduction in the surface energy as illustrated in Table 3.
  • the surface energies from the existing commercial products (Product-1 and Product-2) were also included.
  • the surface energy was obtained through contact angle measurements conducted using D.I. water and tricresylphosphate (TCP) testing liquids, and calculated using the Geometric Mean Model.
  • the control PU (Argotec) film surface is hydrophilic with a water contact angle of about 75 degree and a total surface energy of about 40.1mN/m.
  • the surface becomes hydrophobic with a water contact angle of 103 degree and the total surface energy was reduced to about 22.1mN/m. The reduction is more pronounced for the polar component than for the non-polar component.
  • the existing products are both hydrophilic with water contact angle of below 90 degree and surface energy of about 38mN/m.
  • the reduction in the surface energy of the PU film treated with Sila-MaxTM U-1006 treatment solution is due to the presence of low surface energy component present in the treatment materials.
  • one of the properties of the Sila-MaxTM U-1006 treatment solution is that the treated surface exhibits a concentration gradient across the thickness for the silicon-containing copolymer which is derived from a silsesquinoxane compound and contains low surface energy functional groups, with more silicon-containing materials being located on the outermost surface than in the sub-surface. It is theorized that during the coating process, the silicon-containing materials migrate to the top surface prior to curing and are subsequently locked in place upon curing. The migration of the low surface energy components to the surface is well known to persons skilled in the art, and is associated with the natural force that has the tendency to minimize the surface energy. Table 3 - Surface Energys
  • the low surface energy of the PU film created by the surface treatments described herein provides an excellent release surface, which allows the treated film to be a self-wound, tape-like laminate comprising the surface treated plastic substrate and a PSA layer.
  • the release liner or backing sheet is not necessary and can be eliminated from the construction, e.g., shown in Figure 1. Accordingly, this both reduces the cost and eliminates the waste of a release liner or other like backing materials.
  • the treated film can also be used as a release film.
  • the low surface energy of the Sila-MaxTM treated plastic surface provides easy cleaning or anti-graffiti properties to the treated PU film surface. This effect is illustrated in the Sharpie performance test in which the surface was written upon using a black color king size Sharpie pen, kept for about 15 seconds, and wiped off using a KLEENEX tissue.
  • the change in the whiteness of the written area ( ⁇ ) was measured using a Colorimeter and shown in Table 4. For comparison, the changes from the two commercial products (Product-1 and Product-2) were also tested. As shown in Table 4, the change in ⁇ is significantly smaller for the Sila-MaxTM treated PU film than for the commercial products.
  • the flexibility/conformability of the film/laminate is very important. This is particularly true when the protective film/laminate is applied to an article having irregular surfaces, such as the body of an automobile, house appliance, PDAs, etc.
  • a 150 ⁇ thick Deerfield PU film having, on the bottom surface, a 50 ⁇ thick PSA layer was treated with 15 ⁇ wet thickness of the Sila- MaxTM U-1006 treatment solution. After treatment, the tensile stress at 100% elongation was measured using Instron equipment at an elongation speed of 300mm/min. For comparison, the tensile properties of the untreated PU film and commercial products were also measured and are plotted in Figure 6. The results for the commercial products are labeled as Product-1, Product-2, and Product-3.
  • the PU film treated with 15 ⁇ wet thickness of the Sila-MaxTM treatment solution exhibits a stress at 100% elongation of 7.3 MPa which is (i) comparable to that of the commercial Product-1, (ii) slightly lower than that of the commercial Product-2, and (iii) slightly higher than that of the commercial Product-3.
  • the protective film For application to the body of an article moving at high speeds such as the body of automobiles, trains, aircrafts, etc., the protective film needs to be capable of withstanding impact from particles, such as airborne debris, stones, sand particles, etc., which may hit the film surface at high speeds.
  • particles such as airborne debris, stones, sand particles, etc.
  • ASTM D968-93 testing method established by ASTM International, originally known as the American Society for Testing and Materials (ASTM). More specifically, samples were prepared and tested as follows.
  • the release liner of the laminate was first removed and the surface treated PU film was laminated to an Al panel through the PSA layer.
  • the Al panel was firmly mounted on a heavy metal holder. Five pounds of a sand mixture with 3/8 to 1/2 inch in diameter particle size was used as the impact material.
  • the sand mixture was poured from the top of a 3 meters long and 0.5 inch diameter stainless steel tube. The sand particles gained speed and upon exiting the tube, impacted on the sample carrying Al panel which was located at 3 inches from the bottom of the tube and positioned at a 45 degree angle. After all the sand mixture flowed out from the tu be, the Al panel was removed from the heavy metal holder.
  • UV Xenon weathering tests were performed on a 150 ⁇ thick sample of the Deerfield PU film treated with 15 ⁇ wet thickness of the Sila-MaxTM U-1006 treatment solution.
  • Commercial products i.e., Product-1, Product-2 and Product-3) were also tested along with an untreated sample for reference.
  • the changes in the b* values (Ab*) and in the total color ( ⁇ ) were measured before and after exposure to the testing. As shown in Figure 7, very little changes ( ⁇ 0.6) are observed for all the samples after 2000 hours. In fact, any color variation that is below 1.0 is nearly unperceivable if at all by naked human eyes.
  • a 150 ⁇ thick Argotec PU/PSA/PET laminate treated with the Sila-MaxTM U- 1006 treatment solution was mounted to white and black testing panels via the PSA layer and exposed to outdoor conditions in Florida and Arizona for one year along with and side by side two commercial products, e.g. Product-1 and Product-2.
  • Florida represents a high humidity testing environment while Arizona represents a high temperature testing environment.
  • the changes in color and gloss of the samples were measured and compared to the pristine samples.
  • the changes in the total color density E, the b value, and the 60° gloss are shown in Tables 5 and 6, respectively, for exposure in Florida and Arizona environments.
  • a negative Ab value indicates a color shift to blue whereas a positive Ab value indicates a color shift to yellow.
  • a positive change in AGIoss indicates a loss of gloss and a negative value indicates a gain in gloss.
  • a change in the total color of ⁇ >2.0 is considered noticeable by naked human eyes.
  • the protective film treated with the Sila-MaxTM U-1006 solution shows the least total color change ⁇ among the tested panels in both Florida and Arizona conditions, and for both white and black panels. In addition, all the panels show a negative Ab value after exposure, indicating a light shift to blue color.
  • the result of the gloss measurement indicates that the treated PU film marginally lost gloss after testing in Florida, slightly more than commercial Product-1 but much less than commercial Product-2.
  • the changes in gloss for the treated plastic film are much smaller in Arizona than in Florida environments, and much less than those from commercial Product-1 and Product-2.
  • the Sila-MaxTM U-1006 treatment solution leads to a hardcoat layer with 3H pencil hardness.
  • the Sila-MaxTM treatment solution was developed primarily as a hardcoat solution, which is not hand stretcha ble, for protection of flat display screens.
  • the first and second PU films are very soft, flexible and hand stretchable, having a pencil hardness of about 3B which is several grades lower than the aforementioned Sila-MaxTM coating. Yet, when the PU film was treated with the Sila-MaxTM treatment solution, the flexibility of the PU film was substantially retained and the treated film remains stretchable by hand.
  • Figure 8 compares the hardness and the stretchability of some commonly used plastic films with or without a hardcoat layer.
  • stretchability means that the plastic film can be elongated at room temperature by hand without failing.
  • failing refers to any changes in the appearance of the film/laminates such as hazy, cracking, etc.
  • stretchable plastic films such as PU, polyvinyl chloride, rubbers, and polyolefins all have very soft surfaces.
  • plastic films with harder surfaces such as acrylic and polycarbonate are not stretchable by hand.
  • the treated PU film in accordance with aspects of the present subject matter effectively combines a very hard surface with a very soft plastic core, which is a result of gradual transition from the soft PU to a very hard coating. That is, the penetration of the coating materials into the PU film creates a "composite" layer composed of coating materials and the PU materials. Due to the presence of a diffusion gradient, the composition and the properties of the composite layer gradually changes from the inner part (bulk) of the PU film to the upper surface. At the inner part of the film, the composition of the composite layer contains more PU and less coating materials whose properties are closer to those of pristine PU film. At the upper surface of the PU, the composition of the composite layer is dominated by the coating materials whose properties are closer to the coating layer. Therefore the composite layer originating from the diffusion process effectively bridges the treatment materials and the plastic film, e.g. the treated plastic film behaves like a single "entity".
  • a substantially less thick layer i.e., of about 0.5 ⁇
  • this is due to the significant migration or penetration of the treatment materials below the surface of the PU film in the latter example.
  • more than 90% of the coating ingredients have diffused into the PU film.
  • FTI imaging analyses were performed to further investigate the penetration, diffusion and/or migration of the Sila-MaxTM U-1006 treatment materials into the treated plastic films.
  • An ATR imaging system Perkin Elmer Spotlight 400
  • the FTIR images were collected with a spectral resolution of 4cm "1 and a spatial resolution of about 3 ⁇ . For 400 ⁇ 400 ⁇ 2 image dimension, 2 scans were averaged at each point, while for 25 ⁇ 85 ⁇ 2 image dimension, 32 scans were average at each point in order to obtain better quality spectra.
  • the IR absorption peak at 810cm "1 associated with the unreacted double bond from the Sila-MaxTM treatment solution is used as representative of the Sila-MaxTM coating materials.
  • the IR absorption peak at 779cm "1 associated with the C-H out of plane bending deformation is used to represent the PU materials.
  • the variation of the relative peak intensity of 810cm “1 to 779 cm “1 as a function of depth into the treated PU film is shown in Figure 11.
  • the relative peak intensity of 810cm "1 to 779 cm “1 falls off gradually with increased depth but remains visible up to at least 25 ⁇ . Accordingly, this indicates that the treatment solution penetrates, diffuses or migrates into the PU film to a depth of at least 25 ⁇ with a concentration that gradually decreases from the surface of the PU film to deeper within the PU film.
  • treated plastic films/laminates with various surface and bulk properties can be obtained from the same treatment solution by controlling the process conditions, i.e. the amount and/or depth of diffusion.
  • Typical process conditions include the web speed, the drying temperatures, the amount of applied coating materials, etc.
  • higher diffusion is obtained at high drying temperatures, which in turn leads to higher elongation and poor Sharpie performance for the treated plastic film.
  • Table 7 An example is shown in Table 7 wherein the Sila-MaxTM U-1006 treatment solution was applied on a pilot coater to a 150 ⁇ thick Argotec PU film laminated to a PSA layer (PU/PSA/PET).
  • the pilot coater contains two drying zones of 15 feet long in total length for solvent drying and a UV curing system for radiation curing.
  • the web speed was kept at 15 feet per minute.
  • the liquid was delivered by applying a positive pressure to the treatment solution. Higher pressure represents more coating liquids being applied to the PU film.
  • the treatment solution was dried at 120F and 165F in the first and second drying zones, respectively, and UV cured using a mercury lamp at about 0.30 J/cm 2 .
  • Table 7 The properties of thus treated PU films are shown in Table 7. It should be noted that the surface energy is determined merely by the top surface, typically less than lnm, and represents the contribution from the treatment materials alone.
  • the elongation % and modulus result from combined properties of the treatment materials and the PU film whose relative contributions depend on the applied coat weight and the amount of materials diffused into the PU film.
  • the resistance to the motor oil and the Sharpie performance are also related both to the treatment material and the PU films, but with more contribution from the treatment materials.
  • a reduction in the surface energy provided by the treatment materials impacts motor oil resistance and Sharpie performance.
  • the testing chemicals can leak through the treatment materials and into the plastic film and cannot be wiped off cleanly.
  • the untreated PU film has a modulus of about 29.0 MPa and an elongation % at deformation of about 450%.
  • This modulus value represents the PU film that has not been exposed to the high temperature in the treatment process during solvent drying and by UV curing. It is well known that PU film comprises hard and soft segments and exposure to high temperatures will soften the PU film, leading to a reduction in the modulus. For example, it was found that the modulus of untreated PU film decreases rapidly upon exposure to high temperatures, to 14.3MPa or 50% of its initial value after exposure to 150°F for 1 hour.
  • the PL film treatment with the Sila-MaxTM treatment material which is harder and more brittle, leads to higher modulus and smaller elongation % at deformation. Similar effects were obtained at fixed delivery pressure by changing the process conditions such as the drying temperatures. At higher drying temperatures, more ingredients diffuse into the PL ) leading to a higher elongation % at deformation but poor Sharpie performance.
  • PC-150 can be used as a new substrate and the treatment solution, which could be the same as used in the PC-150 or a new composition, can be applied to the surface of PC-150 in discontinuous fashion, such as by printing.
  • the unprinted areas which are composed of PC-150 provide extensive stretchability along with good stain resistance whereas the printed areas provide better scratch resistance.
  • a treatment composition with different surface energy, optical index, or colors new film/laminates with unique properties such as alternate hydrophilic-hydrophobic patterns, 3-D impressions, textures, colors, etc. can be produced.
  • a new radiation curable surface treatment solution was prepared by adding an acrylate oligomer CN2285 (Sartomer Company, Inc.) into the Sila-MaxTM U-1006 treatment solution. Without adding a new or additional photoinitiator, the new solution was UV curable at the same rate (i.e., at 100 feet/min. using a mercury lamp with 206mJ/cm 2 irradiation energy) with up to about 75 wt % of the CN2285 in the formulation. A 15 ⁇ wet coating thickness of the new treatment solution was used to surface treat a 200 ⁇ thick Deerfield PU film.
  • Figure 15 shows that the PU film treated with the new treatment solution comprising 25/75 weight ratio of CN2285/(Sila-MaxTM U-1006) has comparable tensile stress at 100% elongation as the untreated film. The tensile stress decreases with further increase in this ratio, due to the fact that CN2285 is a much softer material compared to Sila-MaxTM U-1006 treatment solution.
  • a further radiation curable treatment solution comprising an organic-inorganic hybrid material (POSS ® ) was obtained from Hybrid Plastics (Hattiesburg, MS) under the name of POSS ® Coat MA2310.
  • This treatment solution is solvent free and comprises a mixture of acrylated POSS ® compound, acrylate monomers or oligomers, and a photoinitiator.
  • a sample was prepared by surface treating a 200 ⁇ thick Deerfield PU film with a 15 ⁇ wet thickness coating of the foregoing solution and UV cured at 100 feet/min using a UV mercury lamp with 206mJ/cm 2 irradiation energy.
  • a further radiation curable treatment solution was prepared comprising a radiation curable Acrylo POSS ® MA0736 (Hybrid Plastics), an acrylate oligomer CN2285 (Sartomer Inc.), a benzophenone photoinitiator, and a MEK solvent (Table 8).
  • the treatment solution was applied to a 200 ⁇ thick Deerfield PU film at ⁇ wet thickness.
  • the coated PU film was dried at 80°C for 5 minutes and UV cured using a mercury lamp at 200mJ/cm 2 irradiation energy.
  • the thus treated PU film can be hand stretched to more than 100% elongation.
  • This result compared to the PU film treated with POSS ® Coat MA2310 described above, further suggests that the presence of an organic solvent is important for the coating ingredients to penetrate into and maintain the flexibility of the treated PU film.
  • the b value of the coated PU film after dipping in a used motor oil for 48 hours was 5.23, which is much better than that of commercial products as shown in Figure 4 but worse than that from the Sila-MaxTM U-1006 treatment solution.
  • a new radiation curable dispersion is prepared for making a protective film/laminate with low-gloss or matte finish.
  • the treatment dispersion comprises a 5 ⁇ polyamide matting agent (Orgasol ® 2001 UD Nat 2, Arkema Inc.); a radiation curable acrylate oligomer CN2285 (Sartomer Inc.); a radiation curable Acrylo POSS ® MA0736 (Hybrid Plastics Inc.); a benzophenone photoinitiator (Sigma-Aldrich), and a MEK solvent.
  • the composition of each component is listed in Table 9.
  • the coating dispersion was applied to a 2mil MelinexTM PET substrate and a 200 ⁇ Deerfield PU film with 15 ⁇ wet thickness, respectively, dried at 80°C for 5 minutes, and UV cured using a mercury lamp at 200mJ/cm 2 irradiation energy.
  • the 60° gloss and the stretchability of thus treated film samples were measured and listed in Table 10. Here the 60° gloss was measured by placing the sample on a stack of white paper.
  • the 60° gloss of the treated PU film is substantially lower than the treated PET substrate.
  • the treated PU film remains stretchable up to more than 300% without cracking. It is theorized that the lower gloss value from the treated PU film is associated with the migration of the treatment materials into the PU film.
  • the solvent and other smaller molecules such as POSS ® MA0736 and CN2285 quickly diffuse into the PU film.
  • the polyamide particle which is relatively large, is left behind. This leads to a coating layer with higher concentration of polyamide particles than in the starting coating composition.
  • the coating is applied to the PET film where little or no diffusion occurred, the coating layer remains uniform with the same concentration as the initial coating composition.
  • the treatment solution is “filtered” due to diffusion into the PU film with higher polyamide particle "concentrated” in the coating layer above the PU surface.
  • This "concentrating” or “filtering” effect enabled by a non-uniform, differentiated diffusion of different coating ingredients into the plastic film allows maximizing and/or tailoring of surface related coating properties such as abrasion resistance, low gloss, anti-glare, chemical resistance, etc.
  • a desired concentration of particles on the coating surface can be obtained using a coating formulation having a lower concentration of particles than on the coating surface. As a result, the amount of particles in the coating formulation can be reduced and the coating formulation can be made with a lower viscosity.
  • a non-reactive treatment solution was prepared with a 10% acrylic polymer (available under the designation Plexiglas V825 from Arkema Inc.) in l-methoxy-2-propanol solvent.
  • the solution was coated onto a 200 ⁇ thick Argotec PU film with 15 ⁇ wet thickness and dried at 80°C for 5 minutes.
  • the coated PL ) film thus obtained was optically clear.
  • the treated PU film becomes hazy and cracks instantaneously. It is theorized that, because of the large size of the acrylic polymer chain, the acrylic material was not able to diffuse into the PU film and consequently, the coating becomes hazy and cracks upon hand stretching.
  • Two-part (2K) thermally curable treatment compositions were obtained comprising as a first part, a resin solution with 10% solids in a co-solvent of MEK and IPA, and a curing agent as a second part.
  • Two resin solutions were obtained, the first having a viscosity of 0.90mPa.S and the second of 0.90mPa.S.
  • the corresponding curing agents are white solid powders for both resin solutions.
  • the thermally curable treatment solutions were prepared by mixing 0.5wt parts of the curing agent in lOOwt parts of the corresponding resin solution. To obtain a coating with high optical clarity, it is recommended that the dry thickness of the coating be less than ⁇ , as thicker coatings lead to a higher haze %.
  • Samples having a thickness of 150 ⁇ for the first and second exemplary films were treated with the thermally curable treatment solutions described above with a ⁇ wet coating thickness. The samples were then initially dried at about 60°C for about 3 to 5 minutes to eliminate the solvent, followed by thermal curing at about 120°C for about 1 minute. The surface treated films along with untreated control samples were evaluated for resistance to the used motor oil and for conformability. The results are shown in Table 11.
  • Thermally curable treatment compositions were made comprising a hydroxy-functional silicone modified polyacrylate BYK ® SIL-CLEAN ® 3700 (BYK CHEMIE), a modified polyisocyanate crosslinker Coronate HXLV (Nippon Polyurethane Industries, Japan), and a Methyl Ethyl Ketone (M EK) solvent (Table 12).
  • the composition has a viscosity of about 1.8cps as measured using a Brookfield viscometer and behaves like a Newtonian liquid whose viscosity remains unchanged irrespective of shear rate.
  • the BYK ® SIL-CLEAN ® 3700 is supplied as a colorless liquid with 25% solid in Metroxy Propyl Acetate (MPA) solvent. It has a hydroxyl (-OH) number of about 30 in mg KOH/g in the liquid form and of about 124 mg KOH/g on solids. This leads to an equivalent weight of about 452.4 g/eq. on solids.
  • the Coronate HXLV is HDI (hexamethylene diisocyanate) based modified polyisocyanates containing isocyanurate. It has a NCO content (%) of 22.7 to 23.9 (NCO equivalent weight average of 182), and is supplied as 100% solid with viscosity of 800-1500cps as measured at 25°C.
  • the Coronate HXLV has a specific gravity of 1.17g/cm 3 and contains ⁇ 0.2% monomeric HDI.
  • a stoichiometric (1:1) ratio of -NCO/-OH about 40g of Coronate HXLV polyisocyanate is needed for lOOg of the polyacrylate or 400g of the BYK ® SIL-CLEAN ® 3700 solution.
  • the weight ratio of polyisocyanate/polyacrylate of about 0.4 or the weight ratio of polyisocyanate/BYK ® SIL-CLEAN ® 3700 of about 0.1 is needed to attain a stoichiometric -NCO/-OH ratio.
  • thermally curable treatment compositions comprising different amounts of Coronate HXLV polyisocyanate, BYK ® SIL-CLEAN ® 3700, and MEK solvents were prepared as shown in Table 12.
  • Total solvent represents the total amounts (wt %) of MEK and MPA solvents, the latter being introduced from the BYK ® SIL-CLEAN ® 3700 solution.
  • Table 12 - Treatment Compositions
  • a 150 ⁇ thick Argotec PU film was first laminated to a PSA layer and the carrier PET layer was peeled off forming a PU/PSA/PET laminate.
  • the treatment compositions were applied to the exposed PU film surface using an Automatic Film Applicator at ⁇ applied wet thickness and dried/cured in a thermal oven at 260°F for 3 minutes, except for sample 8-12 which was dried at 300°F. These drying temperatures are significantly higher than the melting temperature (60 to 80°C) or the softening temperature (80 to 110°C) of the PU film.
  • the treated PU film exhibits an elongation of less than 10% and the writing ink from a Sharpie pen cannot be wiped off.
  • An elongation of more than 80% can be obtained with polyacrylate content between about 10 to about 85 wt %.
  • all treated PU films treated with the polyacrylate from 10 to 85 wt % exhibit excellent resistance to the motor oil with a total color change of ⁇ 2.0.
  • the exemplary treatment composition 8-7 was further tested on a pilot coater by applying the treatment composition to the top surface of a PU/PSA/PET substrate and dried/cured at different temperatures as indicated in Table 13.
  • the web speed was kept constant at 30 feet per minute.
  • the Pilot coater has three drying zones, each about 13 feet in length.
  • the coat weight (grams/m 2 or gsm) was first calibrated by applying the treatment composition onto a PET substrate.
  • the properties of thus treated PU films are shown in Table 13. For comparison, the properties of the untreated PU film were also reported.
  • the untreated PU film represents the PU/PSA/PET laminate that has not been treated by the exemplary 8-7 composition.
  • the sample labeled as xxxgsm-xxx-xxx-xxx represents the applied coat weight and the web drying temperatures for the three drying zones, respectively.
  • the "5gsm-250-250-300” represents a coat weight of 5gsm and the drying/curing temperatures at the film surface of 250°F, 250°F, and 300°F respectively, for the three drying zones. Again the drying temperatures are significantly higher than the melting temperature or the softening temperature of the PU film.
  • the untreated PU film shows a haze value of 4.15%, which is reduced to about 2.0 or less after treatment with the treatment composition. This effect is similar to what is reported with the first exemplary Sila-MaxTM treatment solution (Table 1) and can be explained by the smoothing effect of the rough PU surface by the treatment materials. In addition, all the treated films exhibit 60° gloss of above 90.
  • the untreated PU film shows elongation % at deformation of well above 300%. After treatment with the treatment composition, the PU films still maintain >80% elongation at deformation at all three coat weights: 3gsm, 5gsm, and 7gsm, and at various drying/curing conditions. The modulus of the PU films was increased after all treatments because the treatment material is substantially harder than the PU film. [00276] After testing in motor oil for 48 hours, the untreated PL ) film substantially yellowed as indicated by the pronounced increase in both the Ab (16.4) and ⁇ (16.5) values (Table 13). As discussed above, a ⁇ value of above 2.0 is considered noticeable by naked human eyes. In comparison, all treated PL ) films exhibit negative Ab values indicating a shift to blue color, and total color ( ⁇ ) well below 2.0, not noticeable by naked human eyes.
  • the writing ink When writing using a king size Sharpie pen which dispenses significantly more ink than an ordinary permanent marker, the writing ink also beads up instantly but trace amounts of residual ink remain observable (rating 7 or 8) after wiping off using a KLEENEX tissue. In general, better Sharpie performance is obtained for samples treated at higher curing temperatures and/or longer exposure times due to higher degree of curing or crosslinking.
  • FT-IR imaging was conducted on the 3gsm-215-300-300 and 7gsm-250-300-300 samples to check the depth of diffusion into the PU film.
  • the IR absorptions from 400 to 4000cm "1 were collected at an incremental step of 1.56 ⁇ . In total, 32 scans were taken and the accumulated spectra were reported at each incremental step.
  • the characteristic absorption peaks from different functional group are listed in Table 15.
  • the untreated PU film also exhibits absorptions at 1450 and 1523 cm “1 , assigned to -CH2 and -N-H bending mode, respectively.
  • the same amount of material applied to the PU substrate shows a layer thickness of about 0.5-0.9 ⁇ , which is about 1/3 of the theoretical thickness (2.6 ⁇ ).
  • the -NCO/-OH ratio of slightly above 1.0 is typically used in order to compensate for slight losses due to reaction with residual moisture and to fully convert the hydroxyl groups into urethane linkages.
  • part of the isocyanate crosslinker diffuses into the PU su bstrate, therefore even more excess amounts of polyisocyanate crosslinker are necessary to compensate for the extra loss incurred from the diffused polyisocyanate crosslinker.
  • the polyisocyanate crosslinker that has diffused into the PU film may further react with moisture or other compounds having reactive hydrogen atoms inside the PU film, leading to complex reactions and new functionalities.
  • the isocyanate crosslinker can also react with these groups to form amide and urethane linkages, respectively.
  • the polyisocyanate crosslinker can also react with the urethane group in the PU film to form allophanate structures.
  • a three dimensional reaction network may be enabled by the crosslinker which reacts both with the reactive components from the coating composition in the horizontal direction and with the functionalities present in the plastic film in the vertical direction.
  • the PU film treated with the exemplary treatment composition 8-7 was further tested for stability under different environments including high temperatures, high humidity, and outdoor sunlight.
  • the variation of elongation % is plotted after exposure to 70°C for 4 days and 8 days.
  • the elongation% decreased by about 20-30% after 4 days and become stable thereafter.
  • a high humidity environment such as 90% humidity
  • no change in the elongation% occurs as shown in Figure 19. It is theorized that the decrease in elongation% upon exposure to high temperature is due to continuous crosslinking reactions between the unreacted polyisocyanate and the polyacrylate.
  • Thermally curable formulations were prepared by adding a reaction catalyst FASCAT ® 2003 (Arkema Inc.) into the thermally curable treatment composition 8-7.
  • the use of a reaction catalyst is aimed to reduce the curing temperatures.
  • the FASTCAT ® 2003 is a pale yellow liquid consisting of 97 wt% of stannous octoate and 3 wt % of 2-ethylhexoic acid.
  • FASCAT ® 2003 catalyst is used extensively for producing urethanes from the reaction of isocyanates and polyols.
  • Two new compositions were prepared with different solid % as shown in Table 17. The composition with lower solid % is intended for treatment with smaller coat weight without changing the liquid delivery system and/or process conditions.
  • the PU/PSA/PET films were treated with the two treatment solutions at 2.6gsm and 1.3gsm dry coat weight on a pilot coater, respectively, and dried at various drying temperatures.
  • the properties of the treated PU films with both treatment compositions are summarized in Table 18.
  • Thermally curable treatment compositions were made by including a component (f) into the exemplary treatment composition 8-7.
  • the component (f) was a silicon-containing compound having hydroxyl groups, namely a phenyltrisilanol POSS ® material (S01458) available from Hybrid Plastics (Hattiesburg, MS) in the form of a white powder.
  • the S01458 is typically used as an additive for surface modification (dispersant), improving moisture resistance, and improving processabilty of plastic materials.
  • the S01458 contains hydroxyl groups which are capable of reacting with the polyisocyanate crosslinker and chemically attached to the coating matrix.
  • Table 19 The chemical composition of the newly prepared treatment compositions are shown in Table 19.
  • the treatment compositions were applied to the 150 ⁇ thick Argotec PU film (PU/PSA/PET) substrate using an Automatic Film Applicator at ⁇ coat weight and dried in a thermal oven at 260°F for 3 minutes.
  • the properties of thus treated PU films and their performance are shown in Ta ble 20.
  • the treatment composition 10-3 which comprises 14.29% S01458 in liquid composition exhibits a milky surface covered with the S01458 solid materials after drying.
  • the treatment composition 10-2 which contains 10.0% S01458 forms an optically clear coating, but becomes milky upon stretching to 40% elongation.
  • the appearance of milky surface for both the 10-2 and 10-3 treatment compositions suggests part of the POSS ® S01458 materials have not reacted with the polyisocyanate crosslinker and as a result, they are not chemically bonded to the matrix of the treatment materials and separate from this latter upon stretching.
  • the POSS ® S01458 in the treatment composition needs to be lower than about 5% in liquid composition or 32% based on the total solids.
  • Thermally curable treatment compositions were prepared by including colloidal silica nano-particles into the treatment composition of Example 8-7.
  • the colloidal silica was obtained from Nissan Chemical Industries, Ltd. (Houston, TX) under the trade name MIBK-ST. It is a pale yellow liquid with 31% amorphous silica dispersed in the MIBK solvent. So the new treatment compositions include three solvents: MEK, MPA, and MIBK.
  • the amorphous silica also contains hydroxyl functional groups on the particle surface.
  • the composition of the new treatment compositions comprising the colloidal silica is shown in Table 21.
  • Inorganic particles such as amorphous silica are widely used for increasing the hardness of the coating which leads to improved mar/scratch resistance.
  • the modulus of the treated PU film 40.0 MPa
  • the modulus of the treated PU film is considerably higher than that of untreated PU film (29.0 MPa). It is also much higher compared to the PU film treated with treatment compositions containing POSS ® S01458 nano-material (32.2 MPa, Table 20).
  • the modulus keeps increasing with the amount of silica loading.
  • a 150 ⁇ Argotec PU film on a PET carrier (PU/PET) was treated with 6.5gsm dry thickness of the first exemplary Sila-MaxTM U-1006 treatment composition.
  • the thus treated PU film was successfully embossed on a continuous embossing apparatus.
  • the embossing conditions and the depth of the embossed patterns are shown in Table 23.
  • a 150 ⁇ thick Argotec PU film laminated to a PSA was treated with the exemplary treatment composition 8-10.
  • the thus treated surface was embossed using a stationary heat press.
  • the top plate of the press was heated using an I source.
  • the treated surface was placed onto a Master shim with a retro-reflective cube pattern and embossed at a pressure of 90psi and an IR heating time of about 4 seconds.
  • a 150 ⁇ thick Argotec PU film laminated to a PSA was treated with the exemplary treatment composition 8-10.
  • a 1.7mil thick Trans-Kote ® PET/MR Laminating Film was obtained from Transilwrap Company Inc. (Franklin Park, IL).
  • the PET/MR Lamination Film was thermally laminated to the treated PU film surface on a laboratory scale thermal laminator (Cheminstruments, Fairfield, OH) at 250° F temperature, 2cm/sec lamination speed, and 40psi pressure.
  • the PET lamination layer sticks firmly to the treated PU surface and yet can be peeled off easily and cleanly.
  • a 150 ⁇ thick black color Polyvinyl chloride) (PVC) film laminated to a PSA layer and a PET release layer (PVC/PSA/PET) was obtained from Avery Dennison Corporation.
  • the PVC film was treated using an exemplary treatment composition 15-1 shown in Table 24 at 20 ⁇ applied wet thickness and cured in a thermal oven at 220°F for 3 minutes. The properties of thus treated PVC film are shown in Table 25.
  • the untreated PVC film exhibits an elongation of about 500% and a 60° gloss of 30.1. Upon writing using a Sharpie pen, the writing ink does not contract and only trace amounts of the ink can be wiped off (rating 1).
  • the 60° gloss of the PVC surface was increased to 91.6 while the flexibility/stretchability was substantially maintained as shown by an elongation at deformation of 151.5%.
  • the writing ink contracts instantly and a significant amount of the writing ink can be wiped off (rating 7).
  • Cross-hatch tape peel using 3M 810 * tape showed no delamination of the treatment materials from the PVC film.
  • Table 26 lists various coating treatment formulations.
  • the solvent MEK is methyl ethyl ketone.
  • the solvent MPA is metroxy propyl acetate. Unless noted otherwise, the values set forth in Table 26 are parts by weight.
  • All treatment compositions except for ARC-36 contained a commercially available polyisocyanate component designated as Desmodur ® N3300A from Bayer Material Sciences. It is also contemplated that Coronate HXLV from Nippon Polyurethane could also be used.
  • a polyacrylate based polyol component was also used in each of the treatment compositions. Specifically, a polyol (i.e. having hydroxyl groups) with a polyacrylate backbone is preferably used.
  • An example of such an agent is BYK3700 available from BYK Chemie USA.
  • This agent contains 25% hydroxyl-functional silicone modified polyacrylate and 75% MPA solvent.
  • the isocyanate groups in the polyisocyanate react with the hydroxyl groups in the polyol to produce a cross-linked polyurethane coating.
  • the ARC-36 treatment compositions utilized only polyol and so the resulting coating is not cross-linked and is 100% polyacrylate polyol compound.
  • the ARC-34 compositions utilized a colloidal silica.
  • a commercially available colloidal silica product was used, designated as MIBK-ST and available from Nissan Chemicals.
  • the MIBK-ST product contains 31% colloidal silica in methyl isobutyl ketone (MIBK) solvent.
  • MIBK methyl isobutyl ketone
  • Elongation % at deformation was determined by ASTM D-2370, using an Instron device at a rate of 2 inches/min, using 1 inch by 6 inch strips and 4 inch in gauge length. Visual observations were used for assessing any change in appearance. Long term durability was evaluated in accordance with SAE J-1960 for 2,000 hours, and/or 2 years testing in Florida and Arizona.
  • Table 27 further includes two comparative samples, a commercially available paint protection film product from Avery Dennison referred to as NANO-FUSION ® .
  • the other comparative sample is a conventional polyurethane film.
  • each formulation was applied at several different coat weights and dried at various web temperatures for further evaluations.
  • the previously described labeling nomenclature was used, i.e. xxxgsm-xxx-xxx-xxx where "xxxgsm" represents the applied coat weight and the following values represent the web drying temperatures for three drying zones.
  • a prefix is also typically used herein to refer to the sample identifier.
  • Figure 22 illustrates various elongation% values and Young's modulus values obtained from numerous samples summarized in Table 27.
  • Figure 23 illustrates changes in elongation% after thermal aging at 80°C for 48 hours.
  • Figure 24 illustrates variation in Young's modulus after thermal aging at 80°C for 48 hours.
  • Figure 25 illustrates change in elongation% after humidity aging at 40°C and 90%RH for 48 hours.
  • Figure 26 illustrates change in Young's modulus after humidity aging at 40°C and 90%RH for 48 hours.
  • Figure 27 illustrates additional testing results relating to release and adhesion to a painted panel.
  • Adhesion was evaluated by a 180° peel test using PU/PSA/white painted panel (ADT), an Instron device at a peel rate of 12 inches/minute.
  • the painted panel is a commercially available testing panel designated as APR52956 Testing Panel from ACT Test Panels, LLC. The panel is 4 inches wide and 12 inches long. The panel was cut into 2 inch by 5 inch pieces and cleaned with isopropyl alcohol solvent. The treated film was attached to the 2 inch by 5 inch pieces via a PSA layer and dwelled for 20 minutes prior to adhesion testing. Release was evaluated at 90° peeling angle on a peel terse.
  • the sample was attached to an aluminum holder on the peel tester by a double-sided tape from the exposed PL ) surface and the PET layer was peeled off at 90° at a rate of 300 inches/minute.
  • release force is generally not affected by surface treatments.
  • adhesion to the painted panels increased by use of the surface treatments.
  • Cytotoxicity testing was performed in accordance with ISO-10993-10 "Biological Evaluation of Medical Devices". Generally, a collection of wells were provided containing a sub-confluent monolayer of L-929 mouse fibroblast cells.
  • the growth medium used included Single Strength Minimum Essential Growth Medium supplemented with 5% fetal bovine serum, 2% antibiotics (100 units/mL penicillin, 100 ⁇ g/mL streptomycin, and 2 ⁇ g/mL asmphotericin B) and 1% (2mM) L-glutamine.
  • Triplicate wells were dosed with Icmxlxm test article or sample, a high density polyethylene (HDPE) negative control, and a late positive control. Each article was placed in direct contact with the L-929 cells for 24-26 hrs. Visual checks under lOOx optical microscope were performed for abnormal cell morphology and cell lysis in proximity to the articles.
  • HDPE high density polyethylene
  • Results of this testing included Primary Irritation Scores and Primary Irritation Index values. These were determined as follows. Animals were observed daily for general health. Changes in body weights were recorded for each animal. Dermal observations for erythema and edema were recorded at 1, 24, 48, and 72 hours after patch removal. The erythema and edema scores obtained at 24, 48, and 72 hours interval were added and divided by the total number of observations. Primary Irritation Scores were obtained by subtracting the scores of the control sample from the scores of testing article. Primary Irritation Index was calculated by averaging the Primary Irritation Scores among the 3 Rabbits.
  • films having a transition region and thus free of a distinct interface can be formed, such as samples 2, 9 and 10 in Table 28.
  • films having a distinct interface can be formed, such as samples 1 and 3-8 in Table 28.
  • Liquid treatment compositions were prepared by blending by blending 5 ⁇ polyamide particles with the Sila-MaxTM U-1006-40 treatment liquid [Table 29].
  • a matte finish coating was obtained by applying the treatment compositions on 6mil thick Argothane ® PL ) , 8mil thick Dureflex ® PL ) A3800, and 5mil thick ohaglas ® acrylic substrates (Evonik Degussa, NJ), respectively. After drying at 80°C for 3 to 5 minutes, the treatment materials were cured using a belt UV curing system at s dosage of about 200mJ/cm 2 .
  • the 60deg gloss of the coated film was measured and used as an indication of the matting effect. The measurement was taken by placing the sample on a stack of white paper. To evaluate the surface energy, which is usually about 22mN/m for the pure Sila-MaxTM coating solution, the coating surface was written upon using a Sharpie pen. The treated PL ) films were also tested for flexibility by hand stretch. The results are summarized in Table 30.
  • the control acrylic film exhibits a 60 degree gloss of about 140 which is gradually reduced by increasing the wt% of the polyamide particles.
  • the 60 degree gloss was reduced to about 45 at 20 wt% of the polyamide particles (J-11-02-1) and further down to 12 at 38.5 % loading (J-10-27-3).
  • the treated acrylic film exhibits excellent coating quality and the surface is not writable, i.e. the writing ink from a Sharpie pen beads up.
  • the beading up of the writing ink indicates that the treated acrylic film has a low surface energy which is associated with the low surface energy component in the Sila-MaxTM treatment liquid.
  • both the 60 degree gloss and the ink writability do not change noticeably when the applied liquid coating thickness is increased from 10 to 20 ⁇ .
  • the wt% of the polyamide particles is 100%, i.e., with no Sila Max ® treatment liquid, the coated film shows poor coating quality and can be wiped off easily with a Kleenex paper.
  • the control PU films exhibit lower 60 degree gloss values (108 for Dureflex ® PU and 110 for Argotec ® PU).
  • the lower gloss value suggests a higher surface roughness for the PU than for the acrylic film.
  • the 60 degree gloss of the PU films is also significantly reduced by treating with the above liquid treatment compositions, and the effect is much more pronounced compared to the acrylic film.
  • the 60 degree gloss of the treated PU A3800 is reduced to 12 at 20 wt% of polyamide particle (J-ll-02-1) loading and further down to 2.3 at 38.5 wt% of polyamide particle (J-ll-02-1).
  • the Sharpie test indicates that the treated PU film, which is not writable when treated with the pure Sila-MaxTM treatment liquid as discussed above, is writable with all the treatment compositions, even with a polyamide particle loading as low as 11.6%. In comparison, the treated acrylic film remains not writable even at polyamide particle loading of up to 38.5%.
  • the low surface energy component(s) was not able to diffuse to the top surface on the treated PU film, which is most probably caused by a rapid increase in the viscosity of the coated liquid due to a quick diffusion of the carrier fluid and other liquid ingredients into the PU film.
  • the surface of the treated PU film contains larger wt% of polyamide particles with higher surface energy and is writable using the Sharpie pen, accompanied with a lower 60 degree gloss. All treated PU films remain hand stretchable.
  • the difference between the coating on the acrylic substrate and PU substrate is due to the diffusion of the Sila-MaxTM ingredients into the PU film. Because the polyamide particles are too large, they cannot diffuse into the PU substrate and consequently, are left above the PU substrate. The diffusion of the Sila-MaxTM ingredients leads to a coating layer more concentrated with the polyamide particles. This leads to more light diffusion or lower gloss. Conversely, the coating applied on the acrylic substrate exhibits no or very limited diffusion of the Sila-MaxTM ingredients into the acrylic substrate and consequently, the coating is uniformly coated on the top surface of the acrylic substrate with a relatively lower wt% of the polyamide particles.
  • New liquid treatment compositions were prepared in an effort to improve the glossy appearance of the treated plastic films (Table 31). Such materials can be obtained by treating the plastic film with a liquid composition comprising high optical index compounds.
  • the new treatment compositions shown in Table 31 use an aliphatic and cyclic adduct of polyisocyanate prepoklymer: TakenateTM D-110N and TakenateTM D-120N, both available from Mitsui Chemical Inc.
  • the TakenateTM D-110N has an optical index of about 1.54 and TakenateTM D-120N has an optical index of about 1.48.
  • a HDI (Hexamethylene diisocyanate) based aliphatic polyisocyanate such as Desmodur® products (HDI trimers) has an optical index of about 1.45.
  • the TakenateTM D-110N is an aliphatic polyisocyanate adduct prepolymer used mainly for gravure and screen printing ink applications and metal and plastics coating such as electrical appliances, automotive interior parts.
  • the as-received TakenateTM D-110N contains 75% solid in ethyl acetate solvent with a viscosity of 100-900mPas and NCO content of 11-12%.
  • the TakenateTM D-120N is an aliphatic polyisocyanate adduct based on hydrogenated xylylene diisocyanate (H6XDI).
  • the as- received TakanateTM D-120N contains 75% solid in ethyl acetate solvent with a viscosity of 1500 to 1900mPas and NCO content of 10.5 to 11.5%.
  • the PU films treated with the liquid composition using a Desmodur® N-3300 polyisocyanate are also tested and represented as HG-11 and HG-12 in the Table 32.
  • nano-sized particles can be used that exhibit a higher optical index such as Zr0 2 , ZnS, etc.
  • most organic materials exhibit optical indices within a range of 1.4 to 1.6.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un traitement de surface pour un film en plastique protecteur et/ou un stratifié. Dans certaines versions, le traitement de surface comprend le revêtement d'une surface principale du film en plastique ou du stratifié avec une formulation de revêtement durcissable dans laquelle un ou plusieurs des ingrédients du revêtement sont diffusés ou migrés au moins partiellement dans le film en plastique ou le stratifié en plastique. La migration des ingrédients de revêtement crée une couche de transition progressive du film en plastique à la couche de revêtement et génère des propriétés uniques. Dans d'autres versions, la diffusion n'intervient pas et une interface relativement aiguë est définie entre la formulation du revêtement et le film en plastique. En option, le film en plastique traité en surface est stratifié sur un papier doublure revêtu d'un adhésif sensible à la pression (PSA) pour former le stratifié susmentionné.
PCT/US2013/029016 2012-04-09 2013-03-05 Film et/ou stratifié traité en surface WO2013154695A2 (fr)

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PCT/US2012/032746 WO2012141994A2 (fr) 2011-04-15 2012-04-09 Film et/ou stratifié traité en surface
PCT/US2012/048124 WO2013133862A1 (fr) 2012-03-07 2012-07-25 Film et/ou stratifié traité en surface
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3421525A1 (fr) * 2017-06-26 2019-01-02 Essilor International Procédés de préparation de films optiques fonctionnels
WO2020194136A1 (fr) * 2019-03-25 2020-10-01 3M Innovative Properties Company Film décoratif et encre pour jet d'encre durcissable par rayonnement
US10933608B2 (en) 2016-08-19 2021-03-02 Wilsonart Llc Surfacing materials and method of manufacture
US11020948B2 (en) 2017-09-28 2021-06-01 Wilsonart Llc High pressure decorative laminate having a top layer of energy cured acrylated urethane polymer
US11077639B2 (en) 2016-08-19 2021-08-03 Wilsonart Llc Surfacing materials and method of manufacture
US11123968B2 (en) 2014-01-09 2021-09-21 Wilsonart Llc Decorative laminates having a textured surface exhibiting superhydrophobicity, self-cleaning and low adhesion
US11130324B2 (en) 2014-01-09 2021-09-28 Wilsonart Llc Decorative laminates having a textured surface exhibiting a fingerprint proof surface
US11504955B2 (en) 2016-08-19 2022-11-22 Wilsonart Llc Decorative laminate with matte finish and method of manufacture
US11662708B2 (en) * 2018-09-25 2023-05-30 Scott Hinkel Method of forming a two-dimensional image over a model
US11745475B2 (en) 2016-08-19 2023-09-05 Wilsonart Llc Surfacing materials and method of manufacture

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US5453464A (en) 1993-05-24 1995-09-26 Eastman Chemical Company Thermosetting coating compositions
US5804612A (en) 1995-06-08 1998-09-08 Arkwright, Incorporated Transparent anti-fog coating
US6383644B2 (en) 1998-11-11 2002-05-07 3M Innovative Properties Company Multi-layer sheet comprising a protective polyurethane layer
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US6316531B1 (en) 2000-11-15 2001-11-13 Shashikant B Garware Process for dyeing UV stabilized polyester film
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11123968B2 (en) 2014-01-09 2021-09-21 Wilsonart Llc Decorative laminates having a textured surface exhibiting superhydrophobicity, self-cleaning and low adhesion
US11130324B2 (en) 2014-01-09 2021-09-28 Wilsonart Llc Decorative laminates having a textured surface exhibiting a fingerprint proof surface
US10933608B2 (en) 2016-08-19 2021-03-02 Wilsonart Llc Surfacing materials and method of manufacture
US11077639B2 (en) 2016-08-19 2021-08-03 Wilsonart Llc Surfacing materials and method of manufacture
US11504955B2 (en) 2016-08-19 2022-11-22 Wilsonart Llc Decorative laminate with matte finish and method of manufacture
US11745475B2 (en) 2016-08-19 2023-09-05 Wilsonart Llc Surfacing materials and method of manufacture
EP3421525A1 (fr) * 2017-06-26 2019-01-02 Essilor International Procédés de préparation de films optiques fonctionnels
WO2019002220A1 (fr) * 2017-06-26 2019-01-03 Essilor International Procédés de préparation de films optiques fonctionnels
US11648742B2 (en) 2017-06-26 2023-05-16 Essilor International Methods for preparing functional optical films
US11020948B2 (en) 2017-09-28 2021-06-01 Wilsonart Llc High pressure decorative laminate having a top layer of energy cured acrylated urethane polymer
US11662708B2 (en) * 2018-09-25 2023-05-30 Scott Hinkel Method of forming a two-dimensional image over a model
WO2020194136A1 (fr) * 2019-03-25 2020-10-01 3M Innovative Properties Company Film décoratif et encre pour jet d'encre durcissable par rayonnement

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