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    • 专利摘要:
    Surface treated film and / or laminate A surface treatment for a protective plastic and / or laminate is disclosed. suitably, the surface treatment includes coating a main surface of the plastics or laminate film with a curable coating formulation wherein one or more of the coating ingredients are diffused or at least partially migrating in the plastic film or plastic laminate. Migration of coating ingredients creates a gradual transition layer from the plastic film to the coating layer and leads to unique properties. optionally, the surface treated plastic film is laminated to a release liner with a pressure sensitive adhesive (psa) to form the aforementioned laminate.
    公开号:BR112012029399A2
    申请号:R112012029399
    申请日:2011-04-15
    公开日:2019-08-06
    发明作者:Dinescu Liviu；Kun Shi Ming；Akhter Sohail
    申请人:Avery Dennison Corp；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for FILM AND / OR
    LAMINATED WITH TREATED SURFACE.
    REFERENCES TO RELATED ORDERS
    This order claims priority over US Order Serial No. 12 / 784,160 filed on May 20, 2010, which claims priority over US Provisional Order No. Serial 61 / 179,872 filed on May 20, 2009.
    FIELD OF THE INVENTION
    The subject of the present invention relates, in general, to the field of protective films and / or laminates. Particular relevance is found with regard to adhesive films useful for protecting various surfaces to which adhesive films are applied, for example, such as the surfaces of automotive bodies, consumer electronics, windmill blades, household items and, consequently , this descriptive report makes specific reference to them. However, it will be appreciated that aspects of the subject of the present invention are also equally amenable to others of such applications.
    BACKGROUND
    Protective films and / or laminates of various types are generally known. For example, U.S. Patent No. 6,383,644 to Fuchs discloses one of such multi-layered films. In addition, McGuire's Published U.S. Patent Application (Pub No. A1 A1 2008/0286576) also describes a multilayered protective film. Both of the above references are hereby incorporated by reference in their entirety.
    Despite previous attempts to develop protective films and / or laminates, there remains a desire for a protective film and / or laminate that performs adequately in accordance with one or more evaluation criteria, for example, such as good chemical resistance, good scratch and impact resistance, non-stick and anti-wetting properties, good stain resistance, anti-graffiti and anti-fouling properties, good resistance to weather conditions, a low degree of yellowing over time, good optical clarity for application
    2/85 transparent sections, a high degree of flexibility to conform to non-planar surfaces, etc.
    In Pub. US No. 2010 / 0297376A1, which is hereby incorporated by reference in its entirety, the present authors disclose a new protective film / laminate with treated surface comprising, in sequence, a treated plastic film 10 with an outer surface 16 , a pressure sensitive layer (PSA) 14 and a releaseable coating 12 (see Figure 1 of publication '376). The treated plastic film 10 is obtained by treating a plastic film with a liquid treatment composition, in which one or more ingredients of the treatment composition diffuse into the plastic film. The liquid composition was conceived as an irradiation-curable hard protective coating that exhibits 3H pencil hardness. In addition, when an optically transparent polyurethane (PU) film was treated with such a liquid, the polyurethane film greatly retains its flexibility / stretching ability, an effect associated with the diffusion of ingredients from the treatment composition to the PU film. In an exemplary embodiment, as much as 90% of the ingredients of the treatment composition diffuse into the PU film, with a diffusion depth of as much as 25 pm in the PU film. Diffusion of a liquid or coating ingredients onto a macroscopically porous substrate, such as paper, foam or other porous media, is known and can be promoted by the capillary effect.
    The diffusion of ingredients from the treatment composition to the plastic film effectively eliminates the sharp limit typically present in a conventional coating process and forms, instead, an interfacial transition layer under the plastic film together with an ultra thin coating layer arranged by on top of the plastic film. With a composition and physical properties residing between the treatment materials and the plastic film, the transition layer leads to a gradual transition in the properties of the plastic film to the treatment layer arranged above the plastic film, which produces several benefits. First, it leads to excellent adhesion between the treatment layer and the plastic film
    3/85 by physical interlock. It also significantly retains the intrinsic properties of the plastic film, such as the stretch / flexibility of the PU film. A protective film / laminate manufactured from such a treatment process effectively combines the support surface properties conferred by the top coat layer, such as stain resistance, anti-graffiti characteristics, chemical / scratch resistance and the unique properties in mass of the plastic film, such as elasticity, flexibility, etc. In application, the releasable coating 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 away from it. For example, the film is optionally applied in this way to an automotive body surface or another of such a surface that it is desired to protect.
    Once the stretch, flexibility and / or extensibility of the plastic film is substantially maintained, the film 10 shown in Figure 1 can be readily and easily applied to complex geometries and / or otherwise curved surfaces. Optionally, alternative means can be used to glue or otherwise adhere the film 10 to a desired surface.
    Although the subject described in US Publication No. 2010 / 0297376A1 is useful and is expected to find wide application, there remains a need for a treated film and / or laminate that includes a macroscopically non-porous solid plastic film and particularly including a layer or layer. interfacial transition region.
    SUMMARY OF THE INVENTION
    The present invention provides new liquid treatment compositions that are thermally curable for the treatment of plastic films / laminates in which one or more ingredients of the treatment composition diffuse into the plastic film. The new treatment compositions may contain components with hydrophobic functionality, such as silicone or fluorinated functional groups, to impart low surface energy to the treated plastic film. Treatment compositions can
    4/85 further include inorganic, organic or organic-inorganic hybrid particles / materials to impart special properties to the treated plastic / laminate film, such as extensibility, hardness, chemical / scratch resistance, etc. When applied to the surface of a plastic / laminate film, the ingredients of the treatment compositions diffuse substantially to the plastic / laminate film. The diffusion creates an interfacial transition layer beneath the top surface of the plastic film consisting of a mixture of the coating materials and the plastic film and leaves a very thin layer consisting of coating materials arranged above the plastic film. The formation of the transition layer eliminates the sharp boundary between the treatment layer and the plastic film, which is typical in conventional coating processes and minimizes or completely eliminates the mismatch in properties between the treatment layer and the plastic film. This treatment process leads to excellent adhesion between the treatment layer and the plastic film and effectively combines the surface properties conferred by the treatment layer and the mass properties conferred by the plastic film.
    According to one embodiment, a new thermally curable composition comprises at least one compound carrying hydroxyl groups, at least one cross-linking agent capable of reacting with the hydroxyl groups and optionally at least one carrier fluid. The crosslinking agent reacts with the hydroxyl groups to produce a crosslinked structure upon application of heat. The reticulated structure provides chemical / scratch resistance to the treated plastic film and the article under protection.
    According to yet another embodiment, the new thermally curable composition comprises at least one compound carrying hydroxyl groups, at least one cross-linking agent capable of reacting with hydroxyl groups, at least one reaction catalyst and optionally at least one carrier fluid. The crosslinking agent reacts with the hydroxyl groups to produce a crosslinked structure upon application of heat. The reaction catalyst is designed to accelerate the curing reaction.
    5/85
    According to yet another embodiment, the new thermally curable composition comprises at least one compound bringing hydroxyl groups, at least one cross-linking agent capable of reacting with hydroxyl groups, at least one particle / organic, inorganic or organic-inorganic material and optionally at least least one carrier fluid. Preferably, the organic, inorganic or organic-inorganic hybrid particle / material also contains reactive functional groups capable of reacting with the crosslinking agent, so that the particle / material is chemically bonded to the treatment material matrix when applying heat. . The use of such a particle / material can increase the chemical / scratch resistance and long-term durability of the treated plastic film and / or confer other optical properties.
    According to yet another embodiment, the treatment composition comprises a matting agent. The matting agent imparts low gloss, anti-reflective properties to the treated plastic or laminated film.
    According to yet another embodiment, the treatment composition comprises a colorant. The colorant diffuses to and is protected by the plastic film. The colorant gives aesthetic characteristics to the treated plastic / laminate film.
    During the treatment process, one or more ingredients of the treatment compositions diffuse in the plastic film. The diffusion of treatment materials in the plastic film substantially modifies the mechanical, optical, chemical resistance and / or surface properties of the film. For example, when one or more of the components in the above thermally curable treatment compositions contain low surface energy groups, such as silicone or fluorine groups, a low surface energy treated surface film / laminate can be obtained. The low surface energy makes the treated plastic / laminate film easy to clean and anti-graffiti. When the film substrate is soft and flexible, the diffusion of the treatment materials substantially intensifies the hardness and reduces the flexibility / stretching capacity of the fil6 / 85 m and plastic or vice versa. Changes in surface and / or physical properties, in turn, lead to changes in the chemical properties of the plastic film, such as stain resistance or other chemical damage.
    According to yet another modality, a protective film or laminate with discontinuously treated surface is provided.
    According to yet another modality, a protective film or laminate with a textured surface or surface topography is provided.
    According to yet another modality, a protective film or laminate with a treated, thermoformed surface is provided.
    According to yet another modality, the film with treated surface comprises films with multiple layers, of which the upper layer has the treated surface.
    According to yet another modality, a protective film or laminate with a surface is provided.
    According to yet another modality, a method for surface treatment of a protective film or laminate is provided.
    Numerous advantages and benefits of the subject of the invention disclosed here will become evident to those skilled in the field when reading and understanding this specification.
    BRIEF DESCRIPTION OF THE DRAWINGS
    The subject of the invention disclosed here can take shape in various components and component configurations and in various stages and configuration of stages. The drawings are for illustration purposes only and should not be construed as limiting. Also, it will be appreciated that the drawings may not be scaled.
    Figure 1 is a schematic illustration showing an exemplary construction of a film and / or laminate with a surface treated according to aspects of the subject of the present invention.
    Figure 2 is a schematic illustration showing another exemplary construction of a film and / or laminate with a surface treated according to aspects of the subject of the present invention.
    Figure 3 is a graph showing measured values of brightness at
    7/85 degrees for each of several sample films tested with an exemplary treatment composition prepared in accordance with the subject of the present invention and comparative examples.
    Figure 4 is a graph showing b measured values for each of several sample films tested treated with an exemplary treatment composition prepared in accordance with the subject of the present invention and comparative examples after exposure to a test with used motor oil.
    Figure 5 is a graph showing b measured values for each of several tested sample films treated with an exemplary treatment composition prepared according to the subject of the present invention and comparative examples after exposure to a test with used motor oil.
    Figure 6 is a graph showing the tensile stress measured at 100% elongation for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the subject of the present invention and comparative examples.
    Figure 7 is a graph showing delta b and delta E values measured for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the subject of the present invention and comparative examples after exposure to testing under weather conditions. .
    Figure 8 is a graph showing the pencil hardness and the ability to manually stretch different plastic films with and without a hard coating.
    Figure 9 is a photomicrograph showing a comparative sample film treated with an exemplary treatment composition prepared in accordance with the subject of the present invention.
    Figure 10 is a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition prepared in accordance with the subject of the present invention.
    Figure 11 is a graph showing the relative intensity of
    8/85 an IR spectral analysis peak associated with an exemplary radiation curable treatment composition prepared in accordance with the subject of the present invention as a function of depth in an exemplary film receiving the treatment.
    Figure 12 is a 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 a photomicrograph showing an exemplary sample film treated with an exemplary treatment composition, in which all treatment materials have diffused into the film.
    Figure 14 is a graph showing b measured values for each of several tested sample films treated with another exemplary treatment composition prepared according to the subject of the present invention and comparative examples after exposure to a test with used motor oil .
    Figure 15 is a graph showing the tensile stress measured at 100% elongation for each of several tested sample films treated with an exemplary treatment composition prepared in accordance with the subject of the present invention and comparative examples.
    Figure 16 includes graphs showing the% elongation variation as a function of polyacrylate [% by weight] in a treatment composition (Figure 16a) and the polyisocyanate / polyacrylate weight ratio (Figure 16b).
    Figure 17 is a graph showing the variation of IR spectra as a function of depth in the film treated with an exemplary treatment composition.
    Figure 18 is a graph showing the% elongation variation when exposed to high temperature for the film treated with an exemplary treatment composition.
    Figure 19 is a graph showing the% elongation variation after exposure to high humidity for the film treated with an exemplary 9/85 treatment position.
    Figure 20 is a graph showing changes in b values and total color for sample films treated with an exemplary treatment composition after exposure to a UV accelerated weather test.
    Figure 21 is a graph showing changes in% elongation for sample films treated with an exemplary treatment composition after exposure to a UV accelerated weather test.
    DETAILED DESCRIPTION OF THE INVENTION
    For reasons of clarity and simplicity, the present specification refers to structural and / or functional elements, standards and / or relevant protocols and other components that are commonly known in the art without further explanation of their configuration or operation, except until the point where they have been modified or altered in accordance with and / or to accommodate the preferred mode (s) shown here.
    Before paying attention to the details and aspects of the present invention and its preferred embodiments, it is instructive to define several terms used here.
    The term region for surface treatment, as used herein, refers to a region of material with no clear boundary. The surface treatment region typically includes a coating and extends over a region of an adjacent substrate containing both coating material and substrate material, into which the coating penetrates, diffuses or migrates at least partially. The term surface treatment refers to the treatment of a surface, such as a substrate surface, by applying a coating which results in no clear boundary between the coating and the substrate.
    The term% elongation to deformation refers to the% elongation at which a plastic film begins to change its appearance, such as turbidity, fracture, etc. Unless otherwise indicated, the term alon10 / 85%% used herein refers to elongation% to deformation.
    The term modulus represents Young's modulus.
    The useful life refers to the period of time for which the liquid treatment composition can be used. Typically, the end of life is reached when the viscosity of the liquid treatment composition has been doubled.
    The term nanomaterials refers to materials with particle size ranging from a few nanometers to 1.0 pm.
    The term used engine oil refers to automotive engine oil after about 5000 miles of use under normal driving conditions.
    The term carrier fluid refers to a low molecular weight compound, such as an organic solvent or water, which is used to dissolve or transport a higher molecular weight compound.
    The term residence time refers to the length of time that a sample of film is exposed to a treatment agent, such as a solvent, temperature, etc.
    The term hydrophobically modified compound refers to a compound having hydrophobic functional groups, such as hydrocarbon, silicone, fluorinated groups, etc. For example, a hydrophobically modified silica refers to a particle of silica comprising hydrophobic groups on the surface.
    The term solid film refers to a film that does not contain interconnected or closed voids that are present in a porous or spongy medium.
    In general, this specification discloses a new protective film or laminate that has at least one main 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 property of the intact plastic substrate, such as flexibility and / or extensibility. In particular, the surface treatment proposed here differs from a top coat otherwise
    11/85 conventional by the fact that a substantial portion of the material applied during the surface treatment does not, in the end, extend over or disposed over or above the upper surface of the underlying film or laminate thus treated. That is, instead of forming a layer with a clearly defined, highly distinct boundary above the underlying film or laminate, the coating material applied during the surface treatment significantly penetrates the underlying film / laminate matrix and / or fills valleys or depressions on the rough surface of the underlying film / laminate. The coating material used for surface treatment generally includes a liquid coating solution or dispersion. The coating solution is typically a clear liquid, in which the coating ingredients are totally soluble in an organic solvent or water or their dimension is less than the wavelength of visible light and, therefore, the coating ingredients they do not scatter light. 15 Nano-sized particles generally fall into the latter category. A coating dispersion refers to a coating liquid that appears cloudy because the coating ingredients are not fully soluble in or miscible with an organic solvent or water or their dimension is greater than the wavelength of visible light and the distance between them. Persian light.
    Figure 1 illustrates a suitable construction according to aspects of the subject of the present invention. In the illustrated embodiment, a plastic film 10 is laminated to a release-able coating 12 coated with a pressure sensitive adhesive (Pressure Sensitive Adhesive - PSA) 25 14. As shown, reference numeral 16 identifies a surface created by treatment surface area of the plastic film 10 with the coating material as disclosed here. Suitably, as discussed above, film 10 is optionally a PU film. As can be seen from Figure 1, suitably, the surface treatment of the film 10 creates a surface 16, which is not a distinct layer in relation to the film 10. That is, there is no strictly defined boundary between the surface 16 and film 10, which separates the two in other ways
    12/85 distinct. Before, the surface 16 is formed through a chemical treatment of the film 10, so that the material composition performs a gradual transition from one material to the next.
    The diffusion and formation of a gradual transition layer of the treatment materials on the plastic film substrate contribute greatly to retaining the flexibility / extensibility of the film. This is particularly the case when the treatment material is of a hard protective coating composition, as illustrated in one of the embodiments here. Several mechanisms can contribute to the diffusion and formation of a gradual transition. First, the coating solvent is selected to have good compatibility with the PU film. Consequently, the solvent swells the PU film and transports the solid coating materials from the surface treatment into the PU film matrix. The inclusion of coating solids from the treatment in the PU film matrix increases the density of the sub-surface. Second, 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 the penetration of coating ingredients. Third, the outer surface of the PU film, like all plastic materials, is generally rough under a nanometer scale. When treating with the coating material, the valley areas are filled with the coating materials, which also beneficially leads to a smoother surface. In any case, at least in part because of these effects, as seen under magnification, the thickness and / or quantity of the coating material from the treatment which remains above or above the upper 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 modalities, it may even be imperceptible.
    The ability of a coating ingredient to diffuse or migrate to a plastic film depends on many factors, such as the physical size of the coating ingredient, compatibility with the film
    13/85 plastic, 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. Diffusion is, in general, more pronounced for a lower viscosity composition, at higher drying temperatures and / or longer residence time. By properly controlling the viscosity of the treatment composition and / or other process conditions, protective films / laminates with different mechanical and surface properties can be obtained.
    It is reasonable to assume that an ingredient that is smaller in size and / or has a good affinity for plastic wrap diffuses more quickly than an ingredient that is larger and / or has poor affinity. Since a typical coating formulation contains several ingredients that are of different sizes and / or affinity / compatibility with the plastic film, the composition of the coating materials that has diffused / migrated to the plastic film can be substantially different from the composition of the formulation initial. This, in turn, leads to a new composition for the coating layer that remains above the plastic film, different from the composition of the initial coating formulation as well.
    In practice, 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 in order to facilitate the penetration of one or more coating ingredients into the film or substrate. Suitably, the solvent is selected to be compatible with the film or substrate material chosen in this way and the coating materials are chosen in the same way, for example, based on physical size and / or other suitable properties, to obtain the desired penetration in view of the selected film material and solvent. Preferably, in addition to the solvent, the coating materials used in the surface treatment include one or more of the following ingredients: monomers and oligomers, such as radiation-curable monomers and oligomers (electron beam, gamma or ultraviolet radiation, including free radicals or cationic) or thermally curable, additives such as surfactant and antifoam and small
    14/85 particles of organic compounds, inorganic compounds or hybrid organic-inorganic compounds. These materials are small in size and easily penetrate the plastic or laminate film matrix. Preferably, the monomer or oligomer or particle size is less than 10 pm, more preferably less than 5 pm, and even more preferably less than 1 pm.
    The temperature during the treatment process has significant effects on the diffusion of treatment ingredients in the plastic film. In one aspect, the viscosity of the coating ingredients, such as monomers or oligomers, decreases with increasing temperature. In another aspect, the free volume of the plastic film substrate increases with temperature. Therefore, the diffusion of coating ingredients can be significantly enhanced simply by increasing the processing temperature and, in some cases, the presence of an organic solvent may not be necessary, that is, the diffusion can also occur from a composition solvent-free or 100% solid treatment.
    In one embodiment, a PU film of about 150 to 200 pm thick is particularly suitable for such applications. For example, polyurethane films made by Deerfield Urethane, Inc. (Whately, Massachusetts) and sold under the trademark Dureflex® (periodically referred to here as a first sample or exemplary film material) and polyurethane films made by Argotec, Inc. (Greenfield, Massachusetts) and sold under the trademark ARGOTHANE® (periodically referred to here as a second sample or exemplary film material) are acceptable. Notably, the elastic property of the PU film also provides additional cushioning that benefits the impact resistance of the final film or laminate. These PU films are extruded on a PET vehicle (PU / PET). Compared with Dureflex® film, ARGOTHANE® film has greater optical clarity and is more attractive for applications that require transparency properties. 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 an elevation rate of 5 ° C / min. According
    15/85 shown in the examples, the treatment composition is applied and cured at temperatures substantially higher than the melting or softening temperatures, which is beneficial for the diffusion of treatment ingredients in the plastic film.
    In a particularly suitable embodiment, the coating material used in the surface treatment comprises POSS® (polyhedral oligomeric silsesquioxanes) or other similar hybrid organic-inorganic nanostructured material. For example, suitable silsesquioxane derivatives are disclosed in U.S. Patent No. 7,235,619 issued on June 26, 2007 to Morimoto etal. 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).
    In one embodiment, the surface treatment solution is a solvent-based UV (ultraviolet) curable solution comprising a POSS® material applied to the underlying substrate or film. More specifically, according to a treatment material of a preferred embodiment, this treatment solution contains a silsesquioxane compound dissolved in an organic solvent. One of such suitable solutions is available from Chisso Corporation (Osaka, Japan) and is sold under the trademark Sila-Max ™ U1006-40. Sila-Max ™ U1006-40 contains about 40% solids dissolved in an organic solvent. In addition to the POSS® material, other ingredients in the Sila-Max ™ U1006-40 treatment solution include UV-curable acrylate monomers / oligomers and a photoinitiator mixed in an organic solvent.
    The film surface treated with an exemplary treatment solution exhibits a low surface energy (for example, approximately 21.8 mN / m), which leads to good chemical resistance, while providing additional properties, such as anti-stick and anti-wetting properties, anti-graffiti characteristics, anti-fouling properties, easy cleaning, water and oil resistance and anti-stain properties and a low friction coefficient, which
    16/85 also contributes to good scratch and impact resistance. The preferred treatment material also has excellent optical clarity, for example, with less than approximately 1% turbidity, which is advantageous for applications that require transparency properties. For example, when coated with a low porosity film, such as polyester or polycarbonate, the treatment material in a preferred embodiment also has a high surface hardness (for example, a pencil hardness of around 3H), which makes it highly resistant to impact and well adapted for protecting surfaces, for example, automotive bodies, 10 consumer electronics and other products.
    When a suitable extensible polymeric film has the surface treated as described herein (for example, using the treatment material mentioned in the preferred embodiment), such as by means of engraving, spraying, flexography, 15-groove matrix coating, coating with roll or other suitable methods, the surface, physical and chemical properties of the film or laminate are substantially increased. The modulus of elasticity of the film is substantially increased. The elongation of the film, although reduced, is largely retained. And the optical clarity is greatly improved by virtue of the smoothing 20 of the film surface by the treatment materials. It will be appreciated that, due to the fact that most of the treatment materials have migrated to the plastic film, changes in the mechanical properties of the treated plastic film are caused mainly by the materials diffused in the plastic film and, to a much lesser extent, by presence of an ultra thin treatment layer arranged over the plastic film. For example, the modulus of a 150 qm Argotec PU film treated with the first treatment solution has been increased from about 29MPa to above 50MPa and the elongation to deformation has been reduced from> 200% to about 150%, by the same time that no treatment layer could even be detected by means of optical microscopy, that is, all treatment materials diffused into the PU film. Along with changes in mechanical properties, the surface energy of the PU film thus treated 17/85 was reduced from about 40.1 mN / m to about 24.9 mN / m and the color changes after exposure to used engine have been reduced by
    16.5 to 1.71.
    Along with changes in surface and mechanical properties, dramatic improvements are seen in chemical resistance, for example, such as resistance to used engine oil, asphalt oil and chemicals used for automotive body cleaning. These properties make the treated film and / or laminate very attractive for applications in which the film or laminate is applied to objects having curved surfaces and / or other complex geometries (i.e., non-flat surfaces). For example, when the film or laminate with a treated surface is used as a protective film applied on the surface of an automotive body (for example, to protect the paint or finish on it from scratches and stains), a more pleasant and / or other benefits are generally obtained when the film or laminate conforms to the contour of the automotive body. In an alternative embodiment, other coating materials, for example, as described herein, can also optionally be used for surface treatment.
    The Sila-Max ™ treatment solution can be further modified to configure special properties or to reduce the cost. In one embodiment, the Sila-Max ™ coating solution is diluted using common organic solvents, such as alcohol, ketones, ethers, acetates, etc. Dilution is particularly beneficial for treatment with low coating weight, as it allows more precise control of the thickness of the wet coating. Dilution is also beneficial for promoting diffusion of coating materials on the substrate. In a preferred embodiment, the Sila-Max ™ solution was diluted to 35% solids by adding ethyl acetate, methyl ethyl ketone (MEK) or isopropanol to the initial solution. In another preferred embodiment, the Sila-Max ™ solution was diluted to about 30% solids using ethyl acetate solvent.
    In one embodiment, UV-curable acrylate monomer (s) or oligomer (s) are added to the Sila-Max ™ coating solution. In
    18/85 a preferred embodiment, an aliphatic urethane acrylate is added to the Sila-Max ™ coating solution to increase the solids content, that is,% solids and / or reduce the cost. Higher% solids is advantageous for coating a thick film. Although any known acrylate monomers and oligomers that are compatible with the Sila-Max ™ treatment solution can be used, aliphatic urethane acrylate (s) are particularly attractive for their high flexibility and long-term environmental stability. An exemplary urethane acrylate is available from Sartomer Company, Inc. (Exton, PA) and sold under the product designation CN2285. With a 120% elongation at break, CN2285 is an acrylic oligomer. CN2285 was specially developed for UV / EB curing thermoforming applications, where high elongation is desired. Without the addition of a new or additional photoinitiator, the mixture of the Sila-Max ™ treatment solution and the preceding urethane acrylate can be UV cured at the same rate (that is, at 100 feet / min using a powered mercury lamp 206 mJ / cm 2 ) with up to about 75% by weight of urethane acrylate in the formulation. Suitably, the curing agent contained in the Sila-Max ™ treatment solution is sufficient to cure the compound. Additional photoinitiator can be added upon further increase in the urethane acrylate content in order to maintain an appropriate cure rate. Preferably, the% by weight of urethane acrylate with respect to the Sila-Max ™ treatment solution is less than 75% by weight and, more preferably, less than 40% by weight.
    Again, diffusion within the plastic film and smoothing the surface of the plastic film described above leads, at least in part, to the relatively thin thickness of the surface treatment material that remains above the upper surface of the underlying substrate. Consequently, this relatively thin thickness, together with the gradual transition nature, contribute to the fact that the flexibility and / or extensibility of the treated film or laminate is greatly retained, although the treatment materials (for example, such as Sila- Max ™) are only more generally known for rigid surface applications because of their hardness
    Relatively high surface 19/85. For example, in one embodiment, the treated film or laminate described here supports at least 20% elongation without fail (i.e., crack, fracture, turbidity, etc.). In yet another embodiment, the treated film or laminate described here supports at least minus 50% elongation without fail. And in yet another embodiment, the treated film or laminate described here supports at least 80% elongation without fail. However, depending on the weight of the coating of the material used for the surface treatment, the amount and / or type of cure, the composition of the underlying base film and other factors, elongations of up to about 150% or even 300% can obtained without failure of the treated film / laminate. In general, less weight of the coating and / or greater penetration into the plastic film leads to greater extensibility. As used in this regard, failure refers to the onset of loss of clarity and / or increased turbidity, for example, as exhibited by fracture, turbidity or bleaching.
    In yet another example, a matte finish stretch protective film / laminate is made by treatment with a solvent-based composition comprising a matting agent. In an exemplary treatment dispersion, the matting agent comprises an ultra-fine polyamide powder having an average particle size of 5 qm (available under the designation Orgasol® 2001 Nat UD 2 from Arkema Inc). This polyamide particle is widely used as a matting agent to impart low gloss and smooth surfaces. The treatment composition was made up of the polyamide particle, a UV-curable aliphatic urethane acrylate (i.e., CN2285 available from Sartomer Inc.); a UV-curable POSS® material (ie Acrylo POSS® Cage Mixture (MA0736) obtained from Hybrid Plastics Inc.) and benzophenone (available from Sigma-Aldrich) as a photoinitiator. Preferably, the loading of the polyamide particle into the coating composition is less than 20% by weight, more preferably less than 15% by weight. A matte coating surface with a 60 ° gloss of less than 10 can be obtained at a wet coating thickness of about 10 μπι.
    When the composition is applied to a PU substrate, the
    20/85 coating substrates diffuse in the PU film, even more so for the other coating ingredients, except the polyamide particle. This non-uniform diffusion leads to a higher concentration of the polyamide particle in the coating layer above the PU surface. Because of such a filtration effect, a much more efficient low gloss or anti-reflective effect can be achieved with less particle loading in the composition. Reduced particle loading is very advantageous because it reduces the dispersion effort and the viscosity of the composition.
    Suitably, once the treatment ingredients diffuse into the underlying PU or other film 10, it is desirable that the plastic film is at least partially transparent to curing radiation for treatment with a radiation curing composition, so that the material diffused in the film receives and / that is, otherwise, exposed to curing radiation.
    In yet another embodiment, the surface of the PU film has been treated with treatment compositions that are thermally curable. In one embodiment, two treatment compositions were made, each containing two parts, namely, a part of resin solution and a part of curing agent. The thermally curable treatment compositions were prepared by mixing 0.5 parts by weight of the curing agent in 100 parts by weight of the resin solution. To obtain a coating with high optical clarity, it is recommended that the thickness of the dry coating be less than 1 pm, since thicker coatings lead to greater turbidity%. PU films treated with such thermally curable treatment compositions exhibit excellent optical clarity, more than 100% elongation to deformation, excellent stain resistance by used motor oil and a surface energy of about 21.8 mN / m.
    In yet another exemplary embodiment, the thermally curable treatment composition comprises at least one compound bringing hydroxyl functional groups and at least one cross-linking agent capable of reacting with the hydroxyl groups. Exemplary hydroxyl-containing compounds include various polyols, such as polyether polyol, polyester poly
    21/85 ol, polycaprolactone polyols, polyol based on castor oil, acrylic polyol, polyurethane polyol and mixtures or copolymers thereof. Hydroxyl-containing compounds may also contain additional functionality, such as silicone, fluorine, amino, carboxylic acid, urethane, urea, etc. and with or without unsaturated double bonds. A hydrophobically modified compound, such as modified silicone or fluorinated compound, is particularly attractive because it imparts low surface energy to the treated plastic film which, in turn, imparts anti-graffiti characteristics, anti-fouling properties and easy surface cleaning. . Exemplary modified silicone compounds with hydroxyl functionalities include modified hydroxy-functional silicone polyacrylates available from BYK Chemie (Wallingford, CT) under the trademark BYK-CLEAN SIL 3700, 3710 and 3720. Exemplary fluorinated compounds having hydroxyl functionalities include available Lumiflon® compounds of Asahi Glass Co. Ltda. (Exton, PA) and Polyfox ™ compounds available from Omnova Solutions Inc. (Mogadore, OH).
    BYK SIL-CLEAN 3700 is a light yellow color solution from BYK Chemie USA comprising 25% modified hydroxy-functional silicone poiliacrylate in methoxypropyl acetate (MPA) solvent. Polyacrylate is a solid polyacrylate material modified from hydroxyl-functional silicone in the SIL-CLEAN BYK 3700 solution.
    The cross-linking agent reacts with the hydroxyl functional groups in the compound bringing hydroxy, leading to a cross-linked structure. When silicone or fluorine groups are present in the compound with hydroxyl, the treated film exhibits low surface energy, which confers hydrophobic and oleophobic properties. Any crosslinking agents that are capable of reacting with hydroxyl groups can be used including, but not limited to, aminoplastic resins, diacetal crosslinking agents, such as 2,2'-diacetyl-bisacetoacetates and bis (beta-ketoesters), as described in US 5,453,464, crosslinking agents containing aluminum having hydroxyl functionalities, as disclosed in US 5,804,612 and blocked and unblocked isocyanate compounds and their reaction products. Particular preference is given to a retention agent
    22/85 cation based on aliphatic or cycloaliphatic isocyanate consisting of an average of 2 to 5 isocyanate groups per compound and their mixtures. Such a compound is typically used as a crosslinking agent for compounds containing hydroxyl groups, especially polyesters and polyacrylic polyols, to prepare two-component polyurethane coatings and varnishes. Such coating and varnishes have excellent durability outdoors and mechanical properties together with resistance to solvents, abrasion, chemicals and UV weather conditions. A hydrophobically modified crosslinking agent, such as one containing silicone or fluorinated groups, is particularly attractive for imparting low surface energy to the treated film.
    Preferably, the aliphatic or cycloaliphatic isocyanate-functional crosslinking agent is a modified polyisocyanate or polyisocyanate, such as aliphatic, cycloaliphatic or mixtures thereof with a low amount of monomeric isocyanates. Examples of aliphatic polyisocyanates are available from Bayer Materials under the trademark Desmodur® N, such as N-3300A, N-3600 and N-3900. Modified aliphatic polyisocyanates are available from Nippon Polyurethane Industry Co. (Tokyo, Japan) under the trademark of Coronate HXLV and HXR. These products have a% NCO content ranging from 21.5 to 23.9 and the residual HDI monomer is typically <0.2% (by weight). Additional features can be introduced in the isocyanate crosslinking agents. A hydrophobically modified polyisocyanate, such as those containing silicone or fluorinated groups, is particularly attractive for imparting low surface energy to the treated film.
    In some cases, the at least one compound containing hydroxy and the at least one cross-linking agent can be mixed and used as is, particularly when one or more of these components have low viscosities, such as low molecular weight or are supplied as a solution in one or more vehicle fluids. In other cases, at least one (additional) carrier fluid can be added to the composition to obtain appropriate viscosities and / or to promote the diffusion of the ingredients into the plastic substrate, which has been found to be essential for maintaining the
    23/85 high flexibility / stretching capacity of the treated plastic film. In addition, the use of an additional carrier fluid with higher vapor pressure can also facilitate the evaporation of the carrier fluid (s) during the drying process. Those skilled in the field can appreciate that the carrier fluid should act as a solvent with respect to the compound bringing hydroxy and the crosslinking agent and, in the case where these components already contain a carrier fluid, the additional carrier fluid must also be compatible with the existing vehicle fluid. Preferably, the additional carrier fluid is a polar organic solvent. Most preferably, the additional carrier fluid is a polar aliphatic solvent or a polar aromatic solvent. Even more preferably, the additional carrier fluid is a ketone, ester, acetate, aprotic amide or mixtures thereof. Examples of carrier fluids include water, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), amyl acetate, ethylene glycol butyl ether-ethyl acetate, ethyl acetate, propylene acetate monomethyl ether glycol, etc.
    In a particular exemplary embodiment, the thermally curable treatment composition comprises: (a) a hydroxy-functional silicone modified polyacrylate solution available from BYK Chemie under the brand name 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. BYK SIL-CLEAN 3700 has a hydroxyl number (-OH) of about 30 mg KOH / g in the liquid form provided and about 124 mg KOH / g in solid form. This leads to an equivalent weight of 1870 g / eq. for the BYK SIL-CLEAN 3700 solution and 452.4 g / eq. for the polyacrylate solid. 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 resistance to the paint or coating, so that it does not crack during drying or handling . The BYK SIL-CLEAN 3700 additive is recommended to be included in the following binder systems: two-component polyurethanes (2K), alkyd-melamine, polyester melamine, melamine acrylate and phenolic epoxy resins. Typically,
    24/85
    BYK SIL-CLEAN 3700 is added to such a paint or coating formulation at 3-6% by weight, based on the total formulation. During the coating process, the polyacrylate migrates to the upper surface, where the silicone groups impart low surface energy to impart anti-graffiti characteristics or ease of surface cleaning to the paint or coating and the polyacrylate is reticulated in the ink system or coating via hydroxyl groups to provide long-term durability. For example, WO 2003 / 05776A1 describes the use of a hydroxy-functionalized silicone modified polyacrylate additive in a coating composition comprising a UV absorber, a polyacrylate binder and a methanol propanol solvent. The coating is intended to reduce the adhesion of contaminants to a polymeric substrate. However, when BYK SILCLEAN 3700 is used in the present invention, a polymeric binding agent was not required because the coating ingredients diffuse on the plastic film substrate and the coating layer and the PU substrate behave as a single entity. That is, the diffusion of coating ingredients creates a smooth and gradual transition layer beneath and adjacent to the surface of the PU film, leaving a very thin coating layer on the PU film. Thus, there is no clear interface or boundary between the coating layer and the plastic substrate, the coating layer and the PU substrate are effectively linked together and behave as a single entity.
    Coronate HXLV polyisocyanate is known for producing polyurethane paints that do not yellow with superior performance to biuret or types of adduct hardeners. Coronate HXLV is resistant to high heat, has a high solubility in solvents and has good compatibility with polyol materials. Coronate HXLV has an NCO content of 22.5 to 23.9%. At an NCO content of 23.5%, Coronate HXLV has an equivalent weight of 182 g / eq. Thus, to achieve a stoichiometric ratio of isocyanate to hydroxyl groups, the weight ratio of Coronate HXLV to polyacrylate must be 0.40.
    The use of MEK solvent reduces the viscosity of the
    25/85 treatment which, in turn, promotes the diffusion of ingredients in the plastic film substrate. Diffusion in the plastic film has been found to be essential to obtain an acceptable flexibility / stretchability of the treated plastic film.
    Suitably, the polyacrylates or component (a) ranges from about 10% by weight to about 85% by weight based on the total solids in the treatment composition and the polyisocyanate or component (b) varies between about 90% by weight to about 15% by weight in the composition. This corresponds to a weight ratio of polyisocyanate to polyacrylate of about 0.2 to 10. When BYK SIL-CLEAN 3700 is coated by itself in the PU film, that is, the polyisocyanate / polyacrylate ratio is equal to zero, the surface of the PU coated film can be written using a permanent marker or a Sharpie King Size and the ink cannot be rubbed using KLEENEX paper, fabric or cloth. This is probably due to the presence of hydroxyl functionalities, which have a high surface energy and compromise the low surface energy effect of the silicone groups. In addition, the coated PU film easily cracks when manually stretched. On the other hand, when the crosslinking agent Coronoate HXLV is coated on the PU film alone or the polyacrylate / polyisocyanate ratio is equal to zero, the surface of the coated PU film remains sticky after drying. When the amount of polyacrylate in the treatment composition is greater than 85% by weight or the ratio of polyisocyanate to polyacrylate is less than 0.2, Sharpie's performance is very poor, meaning that writing inks contract from slowly and cannot be cleaned by rubbing. On the other hand, when the polyacrylate in the treatment composition is less than 10% by weight or the ratio of polyisocyanate to polyacrylate is more than 10, the coating could be sticky, exhibit very poor chemical / scratch resistance and / or have very poor Sharpie performance.
    The MEK solvent (c) is preferably present in the coating composition in an amount from 0% by weight to 80% by weight, more preferably in an amount from 4% by weight to 70% by weight.
    26/85
    It should be noted that a non-stick coating can be obtained on a PU substrate from treatment compositions with 10 to 85% by weight of polyacrylate based on the total solids. However, an adherent coating can be obtained on aluminum (Al) or PET substrates when the% by weight of polyacrylate in total solids is less than about 40% or the weight ratio of polyisocyanate / polyacrylate is greater than 1.2 (ie 3 times the stoichiometric proportion of 0.4 based on equivalent weight). The formation of an adherent surface on Al or PET substrate is due to the presence of an excessive amount of polyisocyanate, which is not able to diffuse on these substrates, in contrast to the PU substrate. This result suggests that more polyisocyanate has migrated to the PU substrate compared to the polyacrylate, that is, the diffusion of the coating ingredients is not uniform and not all components migrate to the PU substrate proportionally. Due to this non-uniform diffusion, greater amounts of polyisocyanate are required for coating on the PU film in order to maximize the reaction with the hydroxyl groups present in the coating composition. HPLC measurements indicate that Coronate HXLV has a main component with a molecular weight of about 631. This compares to the molecular weight of about 17000 for the polyacrylate. Therefore, the greater diffusion of Coronate HXLV in relation to polyacrylate can be attributed to its smaller size.
    In another exemplary embodiment, the thermally curable treatment composition comprises: (a) BYK SIL-Clean 3700; (b) Coronate HXLV crosslinking agent; (c) MEK solvent; and (d) at least one aliphatic or cycloaliphatic compound bringing additional hydroxyl. Additional examples of compounds containing hydroxy include ethylene glycol, propylene glycol, glycerol, BYK SIL-CLEAN 3720, etc. The use of compounds with additional hydroxy can accelerate the reaction speed and / or give more flexibility / stretching capacity to the treated plastic film. Preferably, the amount of additional compound carrying hydroxyl is 10 to 85% by weight based on the total solids in the compositions or from 0 to 100% based on the materials bringing hydroxy.
    27/85
    An optional reaction catalyst can be included in the above thermally curable treatment compositions to enhance the curing reactions. Suitable reaction catalysts include known polyurethane catalysts and / or mixtures thereof, for example, organic compounds, such as tertiary amine, including triethylamine, pyridine, methyl pyridine, Ν, Ν-dimethylamino, cyclohexane, N-methylpiperidine, pentamethyl diethylene amine and Ν, Ν'-dimethyl piperazine; metal salts, such as iron chloride, zinc chloride and organic metal compounds, such as zinc-2 ethyl caproate, tin tin caproate, tin dibutyl dilaurate and molybdenum glycolate. Such catalysts can be used alone or in combinations. Examples of organic tin compound catalysts are available from Arkema Inc. under the trade name Fascat®.
    In an exemplary embodiment, the reaction catalyst consists of FASCAT® 2003, which consists of tin octoate or tin 2-ethylhexanoate (referred to here as component (e)). FASCAT® 2003 is a solvent-free liquid that can be easily incorporated into a coating solution and has been widely used in polyisocyanate and hydroxy compound reactions. The FASCAT® 2003 catalyst does not require long or strict handling conditions and can be loaded at any time during the reaction. Preferably, the catalyst is used from 0 to 0.3% by weight in the composition, more preferably from 0 to 0.2% by weight in the coating composition. Under such conditions, the coating formulation has a service life of several hours.
    The above thermally curable treatment compositions may further contain inorganic particles, hybrid inorganic-organic particles, polymeric particles and / or their mixture. Suitable inorganic particles include, for example, calcium carbonate, titanium dioxide, silica, alumina, zinc sulfate, zinc oxide, antimony oxide, barium sulfate, etc .; Suitable organic-inorganic particles include materials derived from silsesquinoxane compounds. For example, many hybrid organic-inorganic particles of polyhydric oligomeric silsesquinoxane (POSS®) materials with a wide range of functionality are
    28/85 commercially available from Hybrid Plastics (Hattiesburg, Mississippi). Suitable organic particles include, for example, particles of polyamide, polyolefin, polyester and polyurethane. These particles can be used alone or in combinations. Of particular interest are nanoparticles or compounds that can confer special properties without impairing the optical transparency of the treated plastic film. For example, particles of aluminum oxide and silicon dioxide provide surface hardness and scratch resistance; particles of zinc oxide and titanium dioxide provide light / UV stability and anti-microbial properties; particles of indium / antimony oxide and tin provide anti-static and infrared absorption properties; photocatalytic titanium dioxide nanoparticles provide self-cleaning, anti-microbial, superhydrophilicity and light / UV stability properties; copper and silver oxide nanoparticles confer anti-microbial property; iron oxide provides stability to light / UV and magnetism; cerium oxide particles provide light / UV stability and mechanical properties; bismuth oxide particles for attenuation of X-rays, etc. Those skilled in the field can appreciate that different functionalities can be introduced on the surface of these particles to make them hydrophilic or hydrophobic and reactive or nonreactive with the other components in the treatment compositions.
    In a particular embodiment, the thermally curable surface treatment composition described above further includes at least one compound or nanoparticle containing silicone (referred to here as component (f)), for example, such as a hybrid organic-inorganic or similar material that is derived from silsesquinoxane compounds (POSSO). Due to the fact that the properties of a POSS® material are intermediate between an organic and inorganic material, the use of POSS® material can confer properties between organic and inorganic materials. POSS® material can contain hydrogen or several carbon moieties, such as hydrocarbon, hydroxyl, acid, amine and epoxy groups, some of which may be able to react with the crosslinking agent. In addition, POSS® material can be bonded to a monomer or oligomer as side groups
    29/85 or as a segment of the main part of a copolymer. In an exemplary embodiment, component (f) consists of a POSS® triphenyl silanol available from Hybrid Plastics (Hattiesburg, Ml) under the trade name POSS® SO1458. Preferably, the amount of POSS® SO1458 in the dry coating ranges from 0 to 40% by weight, more preferably from 5 to 30% by weight, based on the total solids in the treatment composition.
    In yet another exemplary embodiment, the thermally curable treatment solution optionally comprises (a), (b) and at least one inorganic nanoparticle containing reactive groups (g). One such inorganic nanoparticle consists of colloidal silica available from Nissan America (Houston, TX) under the trademark MIBK-ST. Preferably, the amount of silica, based on the total solids in the treatment solution, ranges from 0-30% by weight, more preferably from 0 to 20% by weight and, even more preferably, from 0 to 10% by weight. It should be noted that the use of nanoparticles can intensify the hardness of the coating, which is beneficial for scratch resistance. However, the elongation decreases with the increase in weight% of silica.
    The plastic / laminate film thus treated by the above thermally curable treatment compositions has a hydrophobic surface (for example, with a surface energy of about 21.8 dynes / cm), which is resistant to writing by permanent markers / Sharpie, it has excellent optical clarity, excellent resistance to stains and scratches and can be stretched for more than 100% elongation without breaking. Here, the word failure refers to any significant changes in the appearance of the treated film / laminate. Typical failure mechanisms include cloudy appearance and cracks that are associated with delamination or cracks in the coating. Optionally, the treated surface plastic film is laminated with a release-able coating coated with a pressure sensitive adhesive (PSA) to form the aforementioned laminate (Figure 1). Notably, Sharpie's performance of surface-treated PU film tends to improve further during storage due to post-curing reactions with moisture.
    30/85
    Significantly, it is notable that the thermally curable treatment compositions mentioned above achieve the desired results without the addition of materials containing halogen or fluorine and the aforementioned surface energy remains less than more conventional silicone release coatings. Also, in addition to other than the aforementioned components, the formulation contains no additional binder and, as such, behaves as a surface treatment as opposed to a conventional paint or coating.
    Those skilled in the field may appreciate that the diffusion of coating ingredients, particularly the crosslinking agent, into the plastic film can cause additional reactions with the residual functional groups or reactive moieties present in the plastic film. For example, the isocyanate crosslinking agent is known to react with urethane functionalities in a PU film to form allophanate functionalities. The isocyanate crosslinking agent also reacts with residual hydroxyl or carboxyl functionalities possibly present in a polyurethane film. Thus, the cross-linking agent not only reacts with the reactive component in the coating composition, but also possibly reacts with the plastic substrate, on the surface and inside the plastic film due to the aforementioned diffusion - thus providing reactions of three-dimensional (3D) curing. The reaction of isocyanate with urethane or urea that forms allophanate functionalities is known in the field and a combination of zinc or copper compound with a tertiary amine catalyst has been particularly effective, as illustrated in U.S. Patent 6,228,472. The use of a reaction catalyst will accelerate the reaction or reduce the curing temperature,
    Preferably, the viscosity of the above treatment compositions is less than 1000 cps, more preferably less than 100 cps, and even more preferably less than 50 cps, as measured using a Brookfield viscometer or rotational rheometer.
    Suitably, the thickness of the dry coating, as measured by coating on a PET substrate, varies from 0.1 μπι
    31/85 to 25 pm, more preferably from 0.5 pm to 15 pm and, even more preferably, from 0.5 pm to 10 pm. In general, the% elongation to deformation decreases with increasing coating thickness. On the other hand, at low coating thickness, ink from a permanent marker or Sharpie pen or other chemicals can leak through the coating and stain the PU substrate underneath, both causing changes in the optical properties of the film or protective laminate.
    Additional agents, such as surfactants, wetting agents, dispersing agents, defoamers, thermal stabilizers, UV absorbers, hindered amine stabilizers, thickeners, etc., can be incorporated into the above thermally and radiation curable treatment compositions.
    Optionally, treatment can include thermal and radiation curing, including curing agents in the coating composition. For example, radiation curable acrylate monomers or oligomers with or without hydroxyl groups and a radiation curing initiator can be added to the thermally curable formulations mentioned above for curing by an irradiation source. Alternatively, the thermally curable components in the above thermally curable compositions can be added to a UV curable and thermally cured composition. In both cases, healing can be started in sequence or simultaneously.
    The coating can be applied to the plastic film by any means including, but not limited to, grooved matrix, flexography, wire bar coating, shovel coating, engraving coating, spray coating, dip coating, curtain coating, roller coating, flexography or other suitable methods. The coating solution can also be applied by means of digital printing, such as through UV or solvent inkjet printing.
    The diffusion of ingredients from the treatment compositions to the plastic film leads to a substantial reduction in the thickness of the layer that is placed on top of the plastic film. Preferably, the layer formed
    32/85 on and / or above the surface of the PU film is less than 10 μιη, more preferably less than 5 pm. Typically, excellent performance
    Sharpie and elongation up to 100% can be achieved with a thickness of less than 5 pm above the surface of the PU film.
    According to an exemplary embodiment, it is appropriate for the surface treatment to penetrate, diffuse or migrate as much as 5 pm in the film. In yet another suitable modality, the surface treatment penetrates, diffuses or migrates as much as 10 pm in the film. In yet another suitable modality, the surface treatment penetrates, diffuses or migrates as much as 20 pm in the film. In yet another suitable modality, the surface treatment penetrates, diffuses or migrates as much as 50 pm in the film. Suitably, the treatment solution migrates or penetrates the film so that it has a gradient of concentration 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. For example, the modulus of a 150 pm thick Argotec PU film has been increased from 29.0 MPa to 51.5 MPa and the% elongation has decreased from more than 300% to 175% after treatment with the treatment solution of a preferred mode, in which all the treatment materials are diffused in the PU film. The modulus of elasticity was increased to 121.2 MPa and the elongation% decreased to 47.1% when more treatment material was applied and a thin layer of treatment materials was formed on the PU film.
    Along with diffusion in the plastic film, the low surface energy component present in the mentioned treatment compositions also diffuses to the upper surface simultaneously and leads to the low surface energy of the treated plastic film. This simultaneous bidirectional diffusion leads to a highly stretch protective film / laminate with desired low surface energy properties.
    Optionally, the surface treatment described above can be applied to any suitable substrates, for example, including
    33/85 flexible and rigid or extensible substrates. Examples of such substrates include, but are not limited to, plastics, glass, metal, ceramics, wood, composites, etc. However, for application as a protective film to be applied to complex geometries, curved surfaces and / or other applications that generally benefit from high conformability (for example, such as a protective film for an automotive vehicle body surface), a flexible plastic film substrate is advantageous. Such plastic films include, but are not limited to, for example, polyurethanes, polyvinyl chloride, polyolefins, polyesters, polyamides, polyacrylates, poly silicones, etc. For rigid and non-stretchable substrates, the surface treatment described above is beneficial to obtain strong adhesion between the treatment layer and the substrate. It reduces the stress on the treatment layer and on the substrate and minimizes the mismatch in properties between the treatment layer and the substrate, which often leads to delamination, cracks 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 hard protective coating.
    Optionally, the above treatment compositions can be applied to the plastic substrate discontinuously, for example, in different areas which can be random or regular patterns. By controlling the pattern of discrete areas and / or the amount of coating ingredients diffused in the PU, many interesting properties can be obtained. For example, a soft touch property of the intact PU film can be preserved, a matte PU surface can be obtained having excellent resistance to chemicals / stains and / or a stretch plastic film having optical properties that change when stretch can be obtained, etc.
    Treatments in different areas can be done using conventional coating methods including, but not limited to, printing patterns using flexography, gravure printing or digital printing, such as inkjet printing. In addition, localized heating can be applied to a plastic web to adjust the amount of diffusion, such as through IR, lasers or through a mask to create coatings with variable properties in different local areas. In heated areas, more coating ingredients will penetrate the plastic substrate and the treated plastic / laminate film will have a higher% elongation to deformation. For areas that are not heated or exposed to low temperatures, less coating material will penetrate the plastic substrate and better mechanical or chemical resistance can be achieved.
    Alternatively, a plastic substrate with different treatment areas can also be obtained by first treating the plastic substrate over the entire surface area, followed by embossing using IR or thermal heating sources. Alternatively, plastic substrates with different treatment areas can be obtained first by embossing the plastic substrate, followed by surface treatment, in which the treatment materials partially fill the embossed plastic / laminate film valleys.
    Optionally, sequential treatments can be carried out on the plastic substrate. For example, a first treatment can be processed at high temperatures for enhanced diffusion and longer elongation. A second treatment can be coated in a pattern on the first coating layer. The coating ingredients of the second treatment will reside above the surface of the first treatment layer and will provide better chemical and mechanical properties.
    Optionally, textures can be created on the plastic film, either before or after the surface treatment, for example, using printing or embossing techniques. The textured surface, in particular those that imitate natural species, can give special properties to the treated films. Examples of such a textured surface include an anti-reflection surface like a moth's eye, a surface with reduced friction like a shark skin, an ultra-hydrophobic surface like lotus leaves, etc. Alternatively, a textured surface also
    35/85 is also useful to provide a retro-reflective surface for traffic signs, graphics and digital printing properties. The textures created on the surfaces of the film can be random or regular patterns, with varying depth and above or below 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 separating the embossing tool. On the other hand, embossing can be conducted first, followed by printing of the treatment composition, in which the treatment materials partially fill the valley areas to preserve the characteristics of the embossing.
    Optionally, the treated plastic / laminate film 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 liner, before embossing to produce a three-dimensional component that can be handled easily without breaking.
    Colors can be introduced by adding a colorant, such as dyes or pigments, to the treatment compositions to obtain an aesthetic effect or for self-protection. During the treatment process, the colorant diffuses into the plastic film substrate. The diffusion depth can be tuned by varying the process conditions which lead to different optical effects or an aesthetic appearance. Due to the diffusion in the plastic film, the colorant is also protected by the plastic film against environmental degradation.
    Those skilled in the field can appreciate that the plastic film can be a film with multiple layers, of which the upper layer has the treated surface. A multilayer film can be made using 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. First, as discussed above, the ability to diffuse coating ingredients in a
    36/85 plastic substrate depends on many factors and no or minimal diffusion can occur for many substrates. In other cases, a suitable organic solvent may not be readily available to promote the diffusion process. For example, a PVC film becomes brittle when exposed to the MEK solvent. In order to solve such a problem, a thin layer of PU or other materials can first be attached to such a plastic substrate using one of the means discussed above before applying the treatment. The coating ingredients will diffuse into the PU layer.
    Referring now to Figure 1, in use, the release liner 12 is removed from the construction and the PSA layer 14 is used to adhere the treated film 10 to the surface of a desired object with the treated surface 16 of film 10 facing out. For example, the film is optionally applied in this way to the surface of an automotive body or other similar surface to be protected. Significantly, by virtue of the fact that the ability to stretch, flexibility and / or extensibility is maintained, film 10 can be easily and smoothly applied to complex geometries and / or an otherwise curved surface. Optionally, alternative means can be used to glue or otherwise adhere the film 10 to a desired surface. For example, in an alternative embodiment, a functional layer optionally free of adhesive may be employed. In particular, a layer of silicone material with poor cohesion and / or low surface tension (i.e., excellent wetting capacity) can be used. Consequently, the functional layer spreads and / or conforms easily to the surface of the object to which it is applied and, as air is expelled between the functional layer and the surface of the object, a vacuum is created between them. This vacuum and / or external air pressure acts to keep the film 10 on the object's surface. Of course, other non-adhesive options known in the art can also be employed, for example, as a functional gecko-mimetic material.
    The laminate shown in Figure 1 can be manufactured differently
    37/85 other ways. In one embodiment, a 150 pm thick PU film extruded on a 2 mm thick polyester backing is obtained from Argotec Inc. The PU film has the first and second main surfaces. The first main surface is exposed and the second main surface is attached to the polyester vehicle. A pressure sensitive layer (PSA) was coated on the first main surface of the PU film and the PSA-coated PU film was subsequently laminated to a release-capable polyester coating 12, as shown in Figure 1, the polyester vehicle being delaminated. The second main surface of the PU film is now exposed. The treatment composition described above is applied to the second main surface, dried at high temperatures to eliminate the solvent and initiate curing reactions for a thermally curable composition and subsequently cured using a UV mercury lamp when a radiation curable composition is used.
    Alternatively, the laminate shown in Figure 1 may further comprise a protective layer on the upper surface of the treated film / laminate to protect the laminate from contamination or physical damage prior to application (Figure 2). The laminate comprises a new protective layer 28, a PU film 20, a layer of PSA 24 and a release PET layer 22. The new laminate can be manufactured in several ways. In one embodiment, a 150 pm thick PU film 20 extruded over a 2 mm thick polyester vehicle is obtained from Argotec Inc. The PU film has the first and second main surfaces. The first main surface is exposed and the second main surface is attached to the polyester vehicle. A pressure sensitive layer (PSA) 24 was coated on the first main surface of the PU film and the PSA-coated PU film was subsequently laminated to a release-capable polyester coating 22, as shown in Figure 2, the polyester being delaminated. The second main surface of the PU film is now exposed. The treatment composition described above is applied to the second main surface, dried in
    38/85 elevated temperatures to eliminate the solvent and initiate curing reactions for thermally curable compositions and subsequently cured using a UV mercury lamp when a radiation curable composition is used. Finally, the protective layer 28 is applied to the upper surface treated by thermal lamination or adhesive. Alternatively, the PSA layer 24 was first applied to a releaseable polyester coating 22 and subsequently laminated to a first main surface of the PU film 20. The polyester vehicle on a second surface of the PU film is delaminated thereby exposing , the second main surface for receiving the irradiation or thermally curable treatment compositions. After curing the treatment composition, the treated PU surface is laminated to the protective layer 28 through lamination or via an adhesive. Alternatively, the treatment composition described above is applied first to the first main surface of the PU film, dried at elevated temperatures to eliminate the solvent and initiate curing reactions for thermally curable compositions and subsequently cured using a UV mercury lamp when a curable composition radiation 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 over a release-capable polyester coating 22, as shown in Figure 2, and subsequently laminated to the second PU surface after delamination of the polyester vehicle. Examples
    Several investigations have been carried out to better evaluate and test various modalities and aspects of the present invention. Several methods have been carried out in the examples presented below. These methods are as follows.
    Testing Methods
    Instron measurement: Unless otherwise indicated, the measurement was performed on an lnstron-5542 instrument. The samples were cut into 1 x 6 strips and a delaminated molten PET film before fixing to the sample holder. An initial measurement length of 4 was
    39/85 used. The specimen was stretched at a speed of 2 inches / min and stopped as soon as a change in optical appearance, such as turbidity / milky appearance or cracks, appeared. The% elongation has been recorded and referred to as% elongation to deformation throughout the description here. Three measurements were taken for each sample and the average values were reported.
    Brightness Measurement: Unless otherwise indicated, brightness at an incidence angle of 60 ° was measured using a Micro-TRI-gloss instrument (BYK Gardner) according to the ASTM D-523 test protocol. At least three measurements were taken in different areas and the average values were reported.
    Turbidity Measurement: The measurement was performed using a Gardener Haze-Guard-Plus (BYK Gardner) instrument. For a PU / PET film substrate, the measurement was made on the PU film delaminating the PET vehicle. When a PU / PSA / PET film substrate was used, the sample was mounted on a glass plate via the PSA layer after delamination of the PET film. Optical transmission%, turbidity% and clarity% were recorded. At least three measurements were made in different areas and the average value was reported.
    Used Engine Oil Test: The test was performed by contacting a 2 x 4 test sample with used engine oil (Pennzoil, 10W30) 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 with a detergent, rinsed with water and dried at room temperature.
    Asphalt Stain Resistance Test: The test was conducted using a mixture of kerosene and Roof Repair (plastic roof cement Roofers Choice 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 40/85 and dried at room temperature.
    Color Measurement: Measurement was performed using a Colorimeter
    SpetroEye ™ (GregtagMacbeth ™). The sample was placed on a stack of white paper. Three measurements were made in different areas and the average value was reported.
    Impact Abrasion Resistance Test: A modified ASTM D968-93 testing method was used. The treated plastic film samples were laminated to an aluminum panel (Al) through the PSA layer. Al's panel was firmly mounted on a heavy metal support. Five pounds of a sand mix with 3/8 to 1/2 inches of particle diameter size was used as the impact material. The sand mixture was spilled from the top of a stainless steel tube 3 meters long and 0.5 inches in diameter. The sand particles picked up speed and, when leaving the tube, collided with Al's panel, bringing the sample that was located 3 inches from the bottom of the tube and positioned at a 45 degree angle. After all the sand mixture flowed out of the tube, the Al panel was removed from the heavy metal support. After blowing out any loose dust and / or other particles, the area that collided with the sample was visually checked for damage. An additional test was performed following the SAE J400 Test for Chip Resistance of Surface Coatings testing protocol. After the test, the Chip Count representing the number and size of the damaged areas within a predetermined surface area was measured.
    Permanent Marker Test: The test was performed using a MARKS-A-LOT FineMark ™ black permanent marker. A straight line about 2 cm long was written on the surface of the treated film. After a waiting time of 15 seconds, the ink was wiped off using a Kleenex tissue. A rating of 1 to 10 has been assigned to represent the amount of paint residue left. A rating of 1 means that the ink cannot be thoroughly cleaned and a rating of 10 indicates that the ink can be thoroughly cleaned.
    Sharpie Performance Test: The test was performed using
    41/85 a black Sharpie king size pen. A straight line about 2 cm long was written on the surface of the treated film. After waiting for 15 seconds, the ink was cleaned using a Kleenex tissue. A rating of 1 to 10 has been assigned to represent the amount of paint residue left. A rating of 1 means that the ink cannot be thoroughly cleaned and a rating of 10 indicates that the ink can be thoroughly cleaned.
    UV Weather Conditions Test: The test was conducted using an Atlas Ci-5000 Type BH Weather-Ometer according to the SAE J-1960 protocol to simulate extreme environmental conditions encountered by a vehicle in outdoor environments. The test protocol consisted of repeated cycles of 120 minutes of light and 60 minutes of darkness in the following sequences: a) 40 minutes of light; b) 20 minutes of light and spraying from the front of the specimen; c) 60 minutes of light; and d) 60 minutes of darkness with spraying on the front and back. During the darkness cycle, the UV lamp had an overall temperature of 38 ° C ± 2 ° C and the relative humidity of the chamber was 95% ± 5%. During the light cycle, the global temperature was maintained at 47 ° C ± 2 ° C and the relative humidity in the chamber was maintained at 50% ± 5%.
    Measurement of Surface Energy: Measurement of the contact angle was conducted on an NRL Contact Angle Goniometer using water D.l. and tricresylphosphate (TCP) as a test liquid. At least three measurements were taken in different areas and the average values were calculated. The surface energy values were calculated using the Geometric Average Model.
    FT-IR measurements: FT-IR measurements were made using a Perkin Elmer 400 Spotlight system. For FT-IR imaging, the samples were first cut transversely in liquid nitrogen and FT-IR images were collected at different locations, from the top coating surface to most of the PU film in a spatial resolution of about 1.56 pm. The images were collected with a spectral resolution of 4 cm 1 . In total, 32 scans were collected and averaged at each location in order to obtain high quality spectra.
    42/85
    Measurement of Coating Thickness: The thickness of the treatment layer arranged over the plastic film was measured using optical microscopy. The 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 tetrahydrofuran solvent (THF) and stirred for about 3 hours. The solution was filtered through a 0.20 μιτι PTFE filter and placed in an autosampler vial. A 0.2% solution of acetic acid in THF was used as the mobile phase, which was passed through the column at a flow rate of 1.0 mL / min. About 50 μί of sample liquid was injected into a Waters 2410 column. The molecular weight calibration standard was calculated using polystyrene dissolved in THF standards.
    Example 1
    Sila-Max ™ solution U1006-40 was obtained from Chisso Corporation (Osaka, Japan). The solution contains a silicon-containing copolymer comprising POSS® portions, acrylate monomers / oligomers and a photoinitiator mixed in methyl isobutyl ketone solvent (MIBK) with 40% solids. The solution has a viscosity of about 2.8 cps at 25 ° C, measured using a Brookfield viscometer. The silicon-containing copolymer contains low surface energy functional groups. Polyurethane films 150 μιτι and 200 μΓη thick on an extruded PET vehicle (first PU film) were obtained from Deerfield Urethane (Dureflex®) and Argotec (second PU film), respectively. The Sila-Max ™ treatment solution was applied to the PU film using an Automatic Film Applicator in 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 206 mJ / cm 2 . The optical properties of the treated PU film were measured using a Plus Haze Guard and Micro-TRI-gloss instrument, respectively. Turbidity measurements% were taken after delamination of the PET vehicle while, for brightness measurements, the PU film remained in the
    43/85 PET vehicle. The results of the turbidity measurements are shown in Table 1 and the brightness values are shown in Figure 3. Here, the brightness values are measured by placing the sample on a stack of white paper.
    Table 1 - Turbidity Measurement Results
    Samples Turbidity% First PU control 2.77 First PU film treated with Sila-Max ™ solution in a wet thickness of 5 pm 2.03 First PU film treated with Sila-Max ™ solution in a wet thickness of 10 pm 1.91 Second PU control 1.70 Second PU film treated with Sila-Max ™ solution in a wet thickness of 10 pm 1.59
    Both the sharpness and brightness of PU films are enhanced by surface treatments, as illustrated by a reduction in turbidity% (Table 1) and an increase in the brightness value at 60 ° (Figure 3). Such improvements are due to the diffusion of coating ingredients into and partially filling the valleys or depressions on the rough surface of the underlying PU film. The aforementioned diffusion and formation of a gradual transition layer also acts to harden the surface which, in turn, can help to eliminate the appearance of the orange peel effect often seen in flexible films.
    In addition, several tests have been carried out to assess the stain resistance of film and / or laminate samples treated according to one or more of the modalities presented here. These tests included subjecting the samples to materials and / or conditions that stain and / or cause fouling, for example, such as engine oil, HCI, roof tar, carpet stain mixes, etc., to simulate
    44/85 exposure to engine oil and dust in the air by the driving environment and test the resistance to cleaning detergents.
    In an exemplary experiment, a 150 pm thick PU film obtained from Argotec was first laminated to a PSA layer, forming a PU / PSA / PET laminate and subsequently the surface was treated with a Sila-Max ™ treatment solution. U1006 at a thickness of 5 pm and 15 pm (wet thickness) disclosed herein. The surface of the treated samples was 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 an irradiation energy of 206 mJ / cm 2 , in a speed of 100 feet / min. After curing, the release liner was removed and the PU films with treated surface were attached to the aluminum (Al) plates via the PSA layer. Al plates containing the prepared samples were dipped in used motor oil (Pennzoil, 10W30) for 48 hours together with commercial products currently available for comparison. After the 48 hour test period, the samples were removed from the used engine oil and thoroughly cleaned with detergent and water. The film samples with treated surface were examined and compared with the present commercial products to evaluate the changes in color (yellowing) as a result of the test using engine oil. Figure 4 illustrates the b measured values of the samples on a color scale L, a, b after subjecting the samples to the test with used motor oil mentioned above. The listed samples represent a 150 pm PU film treated with the Sila-Max ™ U1006 treatment solution applied at the respective coating weights indicated. The control sample listed was not treated. Also listed are commercially available automotive paint protection film products marked Product 1, Product 2 and Product 3 for comparison. While pronounced color change (ie yellowing and / or staining), as indicated by a significant increase in b values, has been observed for all commercial products and untreated PU film (> 20), very little color change was observed for the treated PU film (<2), even with a 5 pm wet thickness of 5 pm applied.
    In another experiment, 150 pm thick PU film samples from Deerfield and Argotec were laminated to a PSA layer, forming a PU / PSA / PET laminate and subsequently treated with the Sila-Max ™ U-1006 treatment solution. , applied with wet thicknesses ranging from 15 pm to 5 pm. The samples were then dried at about 80 ° C for about 3 to 5 minutes and further cured by UV using a mercury lamp with 206 mJ / cm 2 irradiation energy, at a speed of 100 feet / min. The treated samples were tested again in the engine oil used with the same procedure. The b values for the control and treated PU samples are shown in Figure 5. The Deerfield and Argotec control PU films show comparable values of about 27 after the engine oil test. The b values are significantly lower for PU films treated with Sila-Max ™ solutions (<2.0). The b values decrease slightly as the wet thickness increases from 5 pm to 10 pm, which has almost the same b value as the 15 pm sample. Clearly, a treatment with a wet thickness of 5 pm applied is sufficient to achieve excellent resistance to used engine oil.
    Asphalt oil resistance was tested at 23 ° C for 48 hours and resistance to ceiling tar liquid was tested at 70 ° C for 12 hours. The variations of the b value (Áb) and the total color (Δ após) after both tests are shown in Table 2 for a PU film (Argotec) treated with SilaMax ™ in a wet applied thickness of 15 pm. For comparison, two commercial products called Product 1 and Product 2 were also tested under the same conditions. As shown in Table 2, changes in both b (Ab) and total color ΔΕ values are below 1.0 for the PU film treated with Sila-Max ™ solutions, which are not visible to the naked eye. In comparison, pronounced changes that lead to yellowing were observed for both commercial products.
    46/85
    Table 2 - Changes in Values b and E
    Tests Procedures Changes PU film treated with Sila-Max ™ Product 1 Product 2 OilAb á 2.0 0.50 49.1 39.9 asphalt 23 ° C / 48 hours ΔΕ <3.0 0.67 48.2 39.3 TarAb £ 2.0 0.76 16.7 68.2 ceiling 70 ° C / 12 hours ΔΕ <3.0 0.84 17.2 69.2
    The PU film treated with the Sila-Max ™ treatment solution
    U-1006 also showed a significant reduction in surface energy, as shown in Table 3. For comparison, the surface energies of existing commercial products (Product 1 and Product 2) were also included. The surface energy was obtained by measuring the contact angles conducted using test liquids, water Dl and tricresylphosphate (TCP) and calculated using the Geometric Average Model. The surface of the control PU film (Argotec) is hydrophilic, with an angle of contact with water of about 75 degrees and a total surface energy of about 40.1 mN / m. After treatment with the Sila-Max ™ U1006 treatment solution, the surface becomes hydrophobic, with a water contact angle of 103 ° and the total surface energy has been reduced to about 22.1 mN / m. The reduction is more pronounced for the polar component than for the non-polar component. In comparison, the existing products are both hydrophilic, with an angle of contact with water below 90 degrees and a surface energy of about 38 mN / m.
    The reduction in the surface energy of the PU film treated with Sila-Max ™ U-1006 treatment solution is due to the presence of the low surface energy component present in the treatment materials. In fact, one of the properties of the SilaMax ™ 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 energy functional groups. surface, with materials containing more silicon being Io47 / 85 set on the outermost surface than on the sub-surface. It is assumed that, during the coating process, materials containing silicon migrate to the upper surface before curing and are subsequently kept in place when curing. The migration of low-energy components from the surface to the surface is well known to those skilled in the field and is associated with the natural force that tends to minimize surface energy.
    Table 3 - Surface Energies
    Total surface energy [mN / m] Polar component [mN / m] Non-polar component [mN / m] 150 pm Argotec PU(Control) 40.1 34.6 5.5 150 pm Argotec PU treated with SilaMax ™ solution in a 10 pm wet thickness 22.1 21.0 1.1 Product 1 38.5 32.3 6.2 Product 2 37.7 29.1 8.6
    The low surface energy of the PU film created by the surface treatments described here provides excellent surface release, which allows the treated film to be a self-releasing tape-type laminate comprising the treated surface plastic substrate and a layer of PSA. In this way, the release liner or liner sheet is not required and can be eliminated from the construction, for example, as shown in Figure 1. Consequently, this reduces the cost and eliminates the waste of a release liner or other materials. similar coatings. Alternatively, the treated film can also be used as a releaseable film.
    The low surface energy of the plastic surface treated with
    Sila-Max ™ provides easy cleaning or anti-graffiti properties when
    48/85 PU film with treated surface. This effect is illustrated in the Sharpie performance test, in which the surface was written using a Sharpie black king size pen, held for about 15 seconds and cleaned using a Kleenex handkerchief. The change in whiteness of the written area (ΔΙ_) was measured using a Colorimeter and is shown in Table 4. For comparison purposes, the changes in the two commercial products (Product 1 and Product 2) were also tested. As shown in Table 4, the change in AL is significantly less for PU film treated with SilaMax ™ than for commercial products.
    Table 4 - Change in Whiteness
    Tests PU film treated with Sila-Max ™ in a wet thickness of 15 pm Product 1 Product 2 AL 9.1 34.7 44.5
    For application as a protective film / laminate, the flexibility / forming capacity of the film / laminate is very important. This is particularly true when the protective film / laminate is applied to an article that has uneven surfaces, such as the body of an automobile, household items, PDAs, etc. To assess the flexibility / conformability of the PU film with treated surface, a 150 pm thick PU Deerfield film having a 50 pm thick PSA layer on the bottom surface was treated with a thickness of 15 pm wet of the Sila-Max ™ U-1006 treatment solution. After treatment, 100% elongation tensile strength was measured using an Instron equipment at an elongation speed of 300 mm / min. For comparison purposes, the stress properties of untreated PU films and commercial products were also measured and are represented graphically in Figure 6. The results for commercial products are marked as Product 1, Product 2 and Product 3.
    As shown in Figure 6, the PU film treated with a wet thickness of 15 pm from the Sila-Max ™ treatment solution exhibits a 100% elongation stress of 7.3 MPa, which is (i) comparable with that Commercial Product 1, (ii) slightly lower than that of
    49/85
    Commercial Product 2 and (iii) slightly higher than that of Commercial Product 3.
    For application to the body of an article that moves at high speeds, such as the body of cars, trains, airplanes, etc., the protective film must be able to withstand the impact of particles, such as debris in the air, stones , sand particles, etc., which can reach the film surface at high speeds. To assess impact resistance, a 150 pm thick PU Deerfield film having a PSA layer on the bottom surface was treated with the Sila-Max ™ U10 1006 treatment solution and the impact resistance was assessed using a testing method ASTM D968-93 modified established by ASTM International, originally known as the American Society for Testing and Materials (ASTM). More specifically, the samples were prepared and tested as follows. The release liner of the laminate was first removed and the PU film with treated surface was laminated to an Al panel through the PSA layer. To simulate exposure to airborne stones and debris in the driving environment, the Al panel was firmly mounted on a heavy metal support. Five pounds of a sand mix with a particle size of 3/8 to 1/2 inches in diameter of 20 meters was used as the impact material. The sand mixture was spilled from the top of a stainless steel tube 3 meters long and 0.5 inches in diameter. The sand particles picked up speed and, when leaving the tube, collided with the panel bringing Al of sample that was located 3 inches from the bottom of the tube and placed at a 45 degree angle. After all the sand mixture left the tube, the Al panel was removed from the heavy metal support. After blowing loosely bound powder and / or other particles, the impact area of the sample was examined and compared with a currently available commercial product that had been subjected to the same test. The results suggest that the impact resistance of the sample with treated surface is comparable to that of the commercially available product.
    Additional tests were conducted following the test protocol
    50/85 tage SAE J400 Test for Chip Resistance of Surface Coatings. The film and / or laminate samples that had the surface treated the Sila-Max ™ U-1006 treatment solutions disclosed here were tested together with commercial products. After the test, the Chip Count, which represents the number and size of the damage areas within a predetermined surface area, was measured. The results indicate that there are less than nine areas with chips of 3-6 mm in diameter when treatment material at a weight of 7 gsm was applied and less than four areas with chips when a coating with a weight of 10 gsm was applied. These results are comparable to those of commercial products and have passed the test requirement. It seems that the impact resistance of the protective film is determined, to a large extent, by the PU film, which can absorb the impacts.
    In addition, to simulate exposure to sunlight and different weather conditions, UV Xenon weather tests were performed on a 150 pm thick sample of the Deerfield PU film treated with a 15 pm wet thickness of the solution treatment system Sila-Max ™ U-1006. Commercial products (ie Product 1, Product 2 and Product 3) were also tested, along with an untreated sample as a reference. Variations in b * value (Ab *) and total color (ΔΕ) were measured before and after exposure for testing. As shown in Figure 7, very few changes (<0.6) are observed for all samples after 2000 hours. In fact, any color variation that is below 1.0 is almost imperceptible, if at all, to the naked human eye.
    In addition, a 150 pm thick Argotec PU / PSA / PET laminate treated with the Sila-Max ™ U-1006 treatment solution was mounted on white and black test panels via the PSA layer and exposed to outdoor conditions in the Florida and Arizona for one year, together with and side by side with two commercial products, for example, Product 1 and Product 2. Florida represents a high humidity testing environment, while Arizona represents a high temperature testing environment . After one year, changes in the color and brightness of the samples
    51/85 were measured and compared with the intact samples. Changes in total color density Ε, b value and brightness at 60 ° are shown in Tables 5 and 6, respectively, for exposure in Florida and Arizona environments. It should be noted that a negative Ab value indicates a shift from color 5 to blue, while a positive Ab value indicates a shift from color to yellow. Likewise, a positive change in ABrilho indicates a loss of brightness and a negative value indicates a gain in brightness. A change in total color of ΔΕ> 2.0 is considered to be noticeable to the naked human eye.
    Table 5 - Changes After Exposure in Florida
    Samples Panel color ΔΕ Ab Open Florida Exhibition PU treated with Sila-Max ™ White 0.41 -0.10 5.7 Product 1 1.62 0.64 3.0 Product 2 3.02 1.01 12.7 PU treated with Sila-Max ™ black 0.58 -0.12 4.0 Product 1 1.27 -0.04 3.3 Product 2 1.00 -0.03 5.3
    Table 6 - Changes After Exposure in Arizona
    Samples Panel color ΔΕ Ab Open Arizona Exhibition PU treated with Sila-Max ™ White 0.49 -, 36 * -1.0 Product 1 0.98 0.04 2.3 Product 2 1.5 0.35 25.3 PU treated with Sila-Max ™ black 0.71 -0.68 2.3 Product 1 1.04 -0.66 5.7 Product 2 1.21 -0.66 22.0 ___
    * Actually shows an increase in brightness
    As shown in Tables 5 and 6, the protective film treated with the Sila-Max ™ U-1006 solution shows the total color change ΔΕ between the panels tested in Florida and Arizona conditions and for the 15 white and black panels. In addition, all panels show a negative Ab value52 / 85 vo after exposure, indicating a shift of light to a blue color. The gloss measurement result indicates that the marginally treated PU film lost its luster after testing in Florida, slightly more than Commercial Product 1, but much less than Commercial Product 2. The 5 changes in gloss for plastic film treated are much smaller in Arizona than in Florida and much smaller than those of Commercial Product 1 and Commercial Product 2.
    It should be noted that when applied to a rigid plastic substrate, such as glass or metal, the Sila-Max ™ U10 1006 treatment solution leads to a hard coating layer with a pencil hardness of 3H.
    The Sila-Max ™ treatment solution was developed primarily as a hard coating solution, which is not manually stretchable, for protecting monitor screens. The first and second PU films, on the other hand, are very soft and flexible, having a pencil hardness of about 15 of 3B, which is several degrees lower than that of the SilaMax ™ coating mentioned above. However, when the PU film was treated with the Sila-Max ™ treatment solution, the flexibility of the PU film was substantially retained and the treated film remains manually stretchable. Such contradictory properties are largely unexpected and / or unforeseen in the prior art. For example, Figure 8 compares the hardness and stretchability of commonly used plastic films with or without a hard coating layer. Here, the term stretch capacity means that the plastic film can be stretched at room temperature manually without failure. Here, the term failure refers to any change in the appearance of the film / laminates, such as turbidity, breakage, etc. Commercially available stretch plastic films, such as PU, polyvinyl chloride, rubbers and polyolefins, have very smooth surfaces. On the other hand, plastic films with hard surfaces, such as acrylic and polycarbonate, are not manually stretchable. The PU film treated according to 30 aspects of the subject of the present invention effectively combines a very hard surface with a very soft plastic core, which is a result of the gradual transition from soft PU to a very hard coating. That is, the
    53/85 penetration of the coating materials in the PU film creates a composite layer composed of coating materials and PU materials. Due to the presence of a diffusion gradient, the composition and properties of the composite layer gradually change from the inner (dense) part of PU film to the upper surface. Inside the film, the composite layer composition contains more PU and less coating materials whose properties are closer to those of the intact PU film. On the upper surface of PU, the composition of the composite layer is dominated by the coating materials, with properties closer to the coating layer. Therefore, the composite layer originating from the diffusion process effectively binds the treatment materials and the plastic film, for example, the treated plastic film behaves as a single entity.
    The penetration of the coating materials into the plastic film or laminates also leads to other desired benefits, such as strong adhesion. Adhesion is particularly important when the coated film is subjected to bending and / or stretching when applied to uneven surfaces.
    With reference to Figures 9 and 10, a cross-sectional optical microscopy was performed to investigate the interface formed by treating a 150 µm thick PET Melinex ™ substrate and an Argotec PU film substrate and the layer thickness of treatment arranged over the substrates. Here, the same amount of Sila-Max ™ U-1006 treatment solution was applied to a PU film and a PET Melinex ™ film. As shown in Figure 9, a well-defined interface was formed when treating the PET substrate (Figure 9), while no distinct interface was formed when treating the PU film (Figure 10). In addition, a significant distinct layer (i.e., about 7 pm) forms on / above the surface of the PET film, where none or an insignificant amount of diffusion has occurred. In comparison, as shown in Figure 10, a layer of substantially less thickness (i.e., about 0.5 pm) is thus formed on and / or
    54/85 above the surface of the PU film. As can be appreciated, this is due to the migration or significant penetration of the treatment materials below the surface of the PU film in the last example. Here, more than
    90% of the coating ingredients (calculated based on the thickness of the coating) migrated to the PU film.
    FTIR imaging analyzes were performed to further investigate the penetration, diffusion and / or migration of the Sila-Max ™ U-1006 treatment materials in the treated plastic films. An ATR imaging system (Perkin Elmer Spotlight 400) was used and the IR spectra were obtained in an incremental step or pixel size of 1.56 pm. FTIR images were collected with a spectral resolution of 4 cm ' 1 and a spatial resolution of about 3 pm. For an image dimension of 400 x 400 pm 2 , the average of 2 scans was calculated for each point, while an image dimension of 25 x 85 pm 2 , the average of 32 scans was calculated for each point, in order to obtain better quality spectra. The IR absorption peak at 810 cm ' 1 associated with the unreacted double bond by the Sila-Max ™ treatment solution is used as representative of the Sila-Max ™ coating materials. The IR absorption peak at 779 cm 1 associated with the CH outside the flexural strain plane is used to represent PU materials. The variation in the relative peak intensity from 810 cm ' 1 to 779 cm' 1 , as a function of the depth in the treated PU film, is shown in Figure 11.0 The relative intensity peak from 810 cm ' 1 to 779 cm' 1 falls gradually with greater depth, but remains visible until at least 25 pm. consequently, this indicates that the treatment solution penetrates, diffuses or migrates to the PU film at a depth of at least 25 pm with a concentration that gradually decreases, from the surface of the PU film to deeper into the PU film.
    It will be appreciated that, due to the diffusion of coating materials for the treated plastic film, plastic / laminated films treated with various surface and mass properties can be obtained from the same treatment solution by controlling the process conditions. , that is, the amount and / or depth of diffusion. Typical process conditions include weft speed, drying temperatures, the amount of coating materials applied, etc. In general, greater diffusion is obtained at high drying temperatures which, in turn, leads to greater elongation and poor Sharpie performance for the treated plastic film. An example is shown in Table 7 where the Sila-Max ™ U-1006 treatment solution was applied on a pilot coating device to a 150 pm thick Argotec PU film laminated with the PSA layer (PU / PSA / PET). The pilot coating apparatus 10 contains two drying zones of 15 feet in total length for drying solvents and a UV curing system for radiation curing.
    The weft speed was maintained at 15 feet per minute. The liquid was distributed by applying positive pressure to the treatment solution. Higher pressure represents more coating liquids being applied to the PU film. The treatment solution was dried at 120 ° F and 165 ° F in the first and second drying zones, respectively, and UV cured with a mercury lamp of about 0.30 J / cm 2 . The properties of the PU films thus treated are shown in Table 7. It should be noted that the surface energy is determined only by the upper surface, typically less than 1 nm, and represents the contribution of the treatment materials. The% and modulus elongation, on the other hand, results from the combined properties of the treatment materials and the PU film, with more contribution from the PU film. Engine oil resistance and Sharpie's performance, on the other hand, are also related to both treatment material and PU films, but with more input from treatment materials. A reduction in the surface energy provided by the treatment materials has an impact on Sharpie's engine oil resistance and performance. However, if an insufficient amount of treatment materials is applied and / or too much diffusion has occurred, the test chemicals can leak from the treatment materials and into the plastic film and cannot be disposed of cleanly.
    56/85
    Sharpie σ) CD - x— Test with engine oil [ΔΕ] 1.20 'Φ 1.71 16.5 Test with engine oilJAb] 'ΦT "τ— 'Φ• y ~ 1.64 16.4 Module [MPa] 121.2 95.4 51.5 29.0 Stretching[%] it 70.4 217.2 > 300 EnergyPolar[mN / m] CXI τ— CMx— x—X— LOLD Dispersive energy [mN / m] 20.6 20.6 23.8 34.6 Surface energy [mN / m] 21.8 21.8 24.9 40.1 Hi cotoω i—.p ’cdcl a in Ox— 0.5Samples PC-148 PC-149 PC-150 150 pm Argotec control PU
    57/85
    As shown in Table 7, the untreated PU film has an elastic modulus of 29.0 MPa and an elongation% to deformation above 300%. This value represents the modulus of elasticity of the PU film that was not exposed to high temperature in the treatment process during solvent drying and UV curing. It is well known that a PU film comprises hard and soft segments and exposure to high temperatures softens the PU film, which leads to a reduction in the modulus of elasticity. For example, it has been found that the elastic modulus of untreated PU film rapidly decreases after exposure to elevated temperatures, to 14.3 MPa or 50% of its initial value after exposure to 150 ° F for 1 hour. After treatment with the Sila-Max ™ solution, however, all PU films show a significant change in mechanical properties, as characterized by a marked increase in Young's modulus. The increase is even more pronounced when one considers the reduction in the elastic modulus of the PU film after exposure to high temperatures during the treatment process. Although the% elongation is significantly reduced for PC-148, it is substantially retained for PC-149 and PC-150. In addition, the PC-148 and PC-149 films treated with the Sila-Max ™ solution distributed at 1.5 and 1.0 psi, respectively, show a surface energy of 21.8 mN / m, which it is much lower than that for PC-150, which was treated with the solution distributed at 0.5 psi (24.9 mN / m). Since the surface energy is determined by the few angstroms on the upper surface, these results indicate that most of the treatment materials on the PC-150 have migrated to the PU film and the surface of the treated PU film in question is, in fact, composed of a mixture of treatment materials and PU, which has a substantially higher surface energy (40.1 mN / m).
    The total diffusion of treatment materials for the PC-150 was also confirmed by means of optical microscopy of cross section. At
    In Figure 12 and in Figure 13, the cross-sectional light microscopy of PC-148 and PC-150 is shown. PC-148 exhibits a continuous transition of the treatment material from the PU film with a treatment layer of about
    58/85 of 5.8 pm arranged over the PU film. On the other hand, the PC-150 does not show any treatment layer above the surface of the PU film, that is, all treatment materials have migrated to the PU film. The absence of treatment materials above the PU film is consistent with the smallest increase in modulus and the greatest% elongation to deformation for the PC-150 compared to the PC-148 and PC-149 samples. These results confirm that the diffusion of treatment materials to the film results in significant changes in the mechanical properties of the film.
    Resistance to used engine oil and Sharpie's performance both decrease with reduced liquid delivery pressure. For PC-148 and PC-149 where the treatment solution was distributed at a distribution pressure of 1.0 psi or higher, the surface of the treated PU film is completely covered with the treatment material, as shown by an energy surface area of 21.8m N / m. However, for PC-149, the thickness of the treatment materials placed above the PU film seems insufficient to completely stop the diffusion of the engine oil and Sharpie paint in the PU film and, consequently, leading to poor Sharpie performance compared to the PC-148 sample. As expected, Sharpie's worst performance is achieved by the PC-150, where all treatment fluids have migrated to the PU film. All samples showed excellent resistance to used motor oil.
    As shown in Table 7, treatment of the PU film with the treatment material Sila-Max ™, which is harder and more brittle, leads to greater modulus and less elongation% to deformation. Similar effects were obtained at a fixed distribution pressure by changing the process conditions, such as drying temperatures. At high drying temperatures, more ingredients diffuse in the PU, leading to greater elongation% to deformation, but poor Sharpie performance.
    The excellent resistance to engine oil and long% elongation demonstrated by the PC-150 sample are very attractive for making new protective films / laminates with improved properties. For example, PC-150 can be used as a new substrate and the solution of
    59/85 treatment, which could be the same as that used in PC150 or a new composition, can be applied to the surface of PC-150, in a discontinuous way, for example, by means of printing. The unprinted areas which are made up of PC-150 confer stretch capacity together with good resistance to the formation of stains, while the printed areas confer better resistance to scratching. Using a different surface energy treatment composition, the optical index, or colors, of the new film / laminates with unique properties, such as alternating hydrophilic-hydrophobic patterns, 3-D prints, textures, colors, etc., can be produced .
    Example 2
    A new radiation-curable surface treatment solution was prepared by adding an aliphatic urethane acrylate CN2285 (Sartomer Company, Inc.) to the Sila-Max ™ U-1006 treatment solution. Without the addition of a new or additional photoinitiator, the new solution was UV curable at the same rate (ie 100 feet / min using a mercury lamp with 206 mJ / cm 2 irradiation energy) with up to about 75 % by weight of CN2285 in the formulation. A wet coating thickness of 15 pm from the new treatment solution was used for the treatment of a 200 pm thick PU Deerfield surface. The samples were. Then, dried at about 80 ° C for about 3-5 minutes, followed by UV curing at about 100 feet / min using a mercury lamp with an irradiation energy of about 206 mJ / cm 2 . The resistance to used engine oil and the tensile strength to elongation at 100% (elongated at a speed of 300 mm / min) were evaluated and are shown in Figure 14 and Figure 15, respectively. An untreated sample (ie, the control) was also tested and the results are reported here in the same way.
    As shown in Figure 14, excellent resistance to staining was achieved with up to 50% CN2285 (weight / weight) in the composition formulation, far from the performance of all commercial products, as shown in Figure 4. Performance, however , became worse
    60/85 with additional increases in the CN2285 component.
    Figure 15 shows that the PU film treated with the new treatment solution comprising a 25/75 weight ratio of CN2285 / (Sila-Max ™ U-1006) has 100% elongation tensile strength comparable to non-film treated. The tensile strength decreases with an additional increase in this proportion due to the fact that CN2285 is a much softer material compared to the SilaMax ™ U-1006 treatment solution.
    Example 3
    Another radiation curable treatment solution comprising an organic-inorganic hybrid material (POSS®) was obtained from Hybrid Plastics (Hattiesburg, MS) under the name POSS® Coat MA2310. This treatment solution is solvent-free and comprises a mixture of acrylated POSS® compound, acrylate monomers or oligomers and a photoinitiator. Again, a sample was prepared by surface treatment of a 200 pm thick PU Deerfield film with a wet coating thickness of 15 pm from the previous solution and UV cured at 100 feet / min, using a UV mercury with 206 mJ / cm 2 irradiation energy The resistance to used motor oil of the PU film thus treated was measured and showed a b value of 8.2, which is comparable to that of a commercial product (Figure 4) and significantly better than untreated PU film (see, for example, Figure 5). However, the treated PU film cracked when stretching manually due to probably no or insufficient diffusion of the treatment materials to the PU film.
    Example 4
    Another radiation curable treatment solution was prepared comprising a radiation curable Acrylo POSS® MA0736 (Hybrid Plastics), a CN2285 urethane acrylate (Sartomer Inc.), a benzophenone photoinitiator and a MEK solvent (Table 8). The treatment solution was applied at a thickness of 200 pm on a PU film Deerfield with a wet thickness of 10 pm. The coated PU film was dried
    61/85
    80 ° C for 5 minutes and UV cured using a mercury lamp with an irradiation energy of 200 mJ / cm 2 .
    Table 8 - Treatment Solution
    Components % MEK 46.5 CN2285 46.5 MA 0736 4.6 Benzophenone 2.4 Total 100
    The PU film thus treated can be manually stretched to more than 100% elongation. This result, compared to the POSS® Coat MA2310-treated PU film 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 immersion 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 of the solution treatment system Sila-Max ™ U-1006.
    Example 5
    A new radiation-curable dispersion is prepared to produce a protective film / laminate with a low gloss or matte finish. The treatment dispersion comprises a 5 pm polyamide matting agent (Orgasol® 2001 UD Nat 2, Arkema Inc.), a radiation-curable aliphatic urethane acrylate 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.
    62/85
    Table 9 - Treatment Dispersion
    Components % MEK 41.0 Aliphatic urethane acrylate 41.0 Ultra-fine polyamide powder 11.8 POSS®-containing material 4.1 Benzophenone 2.1 Total 100
    The coating dispersion was applied to a PET substrate
    2 mm Melinex ™ and a 200 gm Deerfield PU film with a wet thickness of 15 pm, respectively, dried at 80 ° C for 5 minutes and UV cured using a mercury lamp with an irradiation energy of 200 mJ / cm 2 . The 60 ° brightness and the stretch capacity of the film samples thus treated were measured and listed in Table 10. Here, the 60 ° brightness was measured by placing the sample on a stack of white paper.
    Table 10 - Brightness and Stretch Capacity of Treated Samples
    PU PET Brightness at 60 ° Stretch capacity Brightness at 60 ° Stretch capacity 4.3 > 300% 13 Non-stretch
    The 60 ° gloss of the treated PU film is substantially less than the treated PET substrate. In addition, the treated PU film remains stretchable up to more than 300%, without cracking. It is assumed that the lower the brightness value of the treated PU film is associated with the migration of the treatment materials to the PU film. When the treatment dispersion is applied to the PU film, the solvent and other smaller molecules, such as
    63/85
    POSS® MA0736 and CN2285, diffuse quickly to PU film. The polyamide particle, which is relatively large, is left behind. This leads to a coating with a higher concentration of polyamide particles than in the initial coating composition. On the other hand, when the coating is applied to the PET film where little or no diffusion has occurred, the coating layer remains uniform, with the same concentration as the initial coating composition. Thus, the treatment solution is filtered due to the diffusion to the PU film with more polyamide particles concentrated in the coating layer above the PU surface. This concentration or filtration effect allowed by a non-uniform diffusion, differentiated from the different plastic film coating ingredients allows maximization and / or configuration of surface-related coating properties, such as abrasion resistance, low gloss, anti-reflection, resistance chemistry, etc. On the other hand, a desired concentration of particles on the coating surface can be obtained using a coating formulation with 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.
    Example 6
    The non-reactive treatment solution was prepared with 10% acrylic polymer (available under the name Plexiglas V825 from Arkema Inc.) in solvent 1-methoxy-2-propanol. The solution was coated on a 200 μίτι Argotec PU film with a wet thickness of 15 μπΊ and dried at 80 ° C for 5 minutes. The coated PU film thus obtained was optically transparent. However, when manually stretched, the treated PU film turns and cracks instantly. It is assumed that, due to the large size of the acrylic polymer chain, the acrylic material was not able to diffuse inside the PU film and, consequently, the coating becomes cloudy and cracks when manually stretched.
    64/85
    Example 7
    Two part (2K) thermally curable treatment compositions were obtained comprising, as a first part, a 10% solids resin solution in a MEK and IPA co-solvent and a curing agent as a second part. Two resin solutions were obtained, the first having a viscosity of 0.90 mPa.S and the second 0.90 mPa.S. The corresponding curing agents are white solid powders for both resin solutions. The thermally curable treatment solutions were prepared by mixing 0.5 parts by weight of the curing agent with 100 parts by weight of the corresponding resin solution. To obtain a coating with high optical clarity, it is recommended that the dry coating thickness is less than 1 pm, as thicker coatings lead to greater turbidity%.
    Samples with a thickness of 150 pm for the first and second exemplary films were treated with the thermally curable treatment solutions described above with a wet coating thickness of 10 pm. The samples were then initially dried at about 60 ° C for about 3 to 5 minutes to remove the solvent, followed by thermal curing at about 120 ° C for about 1 minute. Films with the treated surface together with untreated control samples were evaluated for resistance to used engine oil and forming capacity. The results are shown in Table 11.
    Table 11 - Characteristics of films with the treated surface
    Samples Stretch resistance to 100% [N / mm 2 ] Appearance to 100% elongation b value (after testing withused motor oil) First untreated example film (Control) 9.4 Transparent 26.0 First example film treated with first thermally curable treatment solution 6.0 Transparent 4.7
    65/85
    Samples Stretch resistance to 100% [N / mm 2 ] Appearance to 100% elongation b value (after testing with used engine oil) First exemplary film treated with second thermally curable treatment solution 5.9 Transparent 13.0 Second untreated example film (Control) 10.2 Transparent 26.0 Second exemplary film treated with first thermally curable treatment solution 6.2 Transparent 1.4 Second exemplary film treated with second thermally curable treatment solution 5.6 Transparent 2.1
    As shown in Table 11, the tensile strength to elongation of 100% (measured at an elongation rate of 300 mm / min) is significantly reduced by treatment with both thermally curable treatment solutions, which leads to an improvement5 conformation capacity. No change in optical clarity was noticeable after 100% elongation. The resistance to stain formation, as evidenced by its performance in the test with used motor oil, for both exemplary films, is significantly improved after treatment with the two thermally curable treatment solutions, more for the second exemplificative film than for the first example film.
    Example 8
    Thermally curable treatment compositions have been made comprising a hydroxy-functional silicone modified polyacrylate BYK 15 SIL-CLEAN 3700 (BYK Chemie), a modified isocyanate crosslinking agent Coronate HXLV (Nippon Polyurethane Industries, Japan) and a methyl ethyl ketone solvent (MEK) (Table 12). The composition has a
    66/85 viscosity of about 1.8 cps, as measured using a Brookfield viscometer and behaves like a Newtonian liquid, whose viscosity remains unchanged regardless of the shear rate. BYK SIL-CLEAN 3700 is supplied as a colorless liquid with 25% solids in methoxy propyl acetate (MPA) solvent. It has a hydroxyl group number (-OH) of about 30 in mg of KOH / g in liquid form and about 124 mg of KOH / g in solid form. This leads to an equivalent weight of about 452.4 g / eq. on solids. Coronate HXLV is isocyanurate containing modified polyisocyanates based on HDI (hexamethylene diisocyanate). It has an NCO content (%) of 22.7-23.9 (NCO equivalent weight average of 182) and is supplied as 100% solids with a viscosity of 800-1500 cps, as measured at 25 ° C . Coronate HXLV has a specific gravity of 1.17 g / cm 3 and contains <0.2% monomeric HDI. To achieve a stoichiometric ratio (1: 1) of -NCO / -OH, about 40 g of Coronate HXLV polyisocyanate is required for 100 g of polyacrylate or 400 g of BYK SIL-CLEAN 3700 solution. In other words, the a polyisocyanate / polyacrylate weight ratio of about 0.4 or a polyisocyanate / BYK SIL-CLEAN 3700 weight ratio of about 0.1 is required to achieve a stoichiometric ratio of -NCO / -OH.
    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. Here, the total solvent represents the total values (% by weight) of MEK solvents and MPA, the latter being introduced from the BYK SIL-CLEAN 3700 solution.
    67/85
    Table 12 - Treatment Compositions
    Coronate HXLV / Polyacrylate [weight / weight] O O 20 itX— OX-- m 2.4 CO 0.8 0.6 0.4 0.2 AT % by weight of Coronate HXLV onsolids 100 97.56 95.24 93.02 90.91 CD CDCD00 70.59 61.54 44.44 37.50 28.57 The CD ooX— O % by weight of polyacrylate on solids O 2.44 CD 6.98 9.09 CD coX- 29.41 38.46 55.56 62.50 71.43 O00 o o o 'o x— % solids 23J 16.80 47.73 46.74 45.83 ct> CD o “CM 23.61 22.41 20.45 18.60 16.67 14.88 8.33 Net composition [% by weight] ___________________ % CoronateHXLV 23.1 0.41 45.45 COCO CD tfx— 16.67 13.79 9.09 6.98 4.76 2.72 0.00 % polyacrylate O 16.39 CN c T 3.26 X— OJ and CT) cd 8.62 11.36 11.63 11.90 12.16 8.33 % solventstotals 76.9 83.20 4773 53.26 54.17 CD σί 76.39 77.59 79.55 O00 83.33 85.12 91.67 LU£ 2 76.9 81.97 45.45 43.48 41.67 the ocTCD 55.56 51.72 45.45 46.51 47.62 48.64 66.67 Examples 8-1 * | 8-2 * 8-3 * 8-4 * 8-5 CD00 oò I8-8 8-9 8-10 X "00 8-12 8-13
    68/85
    A 150 µm thick Argotec PU film was first laminated to a PSA layer and the supporting PET layer was delaminated, forming a PU / PSA / PET laminate. The treatment compositions were applied to the exposed surface of the PU film using a 5 Automatic Film Applicator in a wet applied thickness of 10 pm 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 properties of the PU films thus treated were evaluated in terms of optical clarity, elongation% to deformation, Young's modulus, resistance to staining by used motor oil, clean removal of Sharpie inks, etc. In Figure 16, an elongation% to deformation of the treated PU film is plotted as a function of the polyacrylate weight% (Figure 16a) and as a function of the polyisocyanate / polyacrylate weight ratio (Figure 16b). When the amount of polyacrylate (% by weight) in the treatment composition is less than about 10% by weight or the polyisocyanate / polyacrylate ratio is greater than 15, the surface of the treated PU film remains sticky due to the presence of an excessive amount of polyisocyanate compound. On the other hand, when polyacrylate is used alone (8-13), the treated PU film exhibits an elongation of less than 10% and the ink written with a Sharpie pen cannot be erased. An elongation of more than 80% can be obtained with the polyacrylate content between about 10 to about 85% by weight. In addition, all PU films treated with 10-85% by weight polyacrylate exhibit excellent resistance to motor oil, with a total color change of <2.0.
    The exemplary treatment composition 8-7 was further tested in a pilot coating apparatus by applying the treatment composition 30 to the upper surface of a PU / PSA / PET substrate and dried / cured at different temperatures, as indicated in Table 13. The weft speed was kept constant at 30 feet per minute. The device
    The 69/85 pilot jacket has three drying zones, each about 13 feet long. The coating weight (grams / m 2 or gsm) was first calibrated by applying the treatment composition to a PET substrate. The properties of the PU films thus treated are shown in Table 5. For comparison purposes, the properties of the untreated PU film have also been reported.
    70/85
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    71/85
    The untreated PU film has a turbidity value of 4.15%, which is reduced to about 2.0 or less after treatment with the treatment composition. This effect is similar to that reported with the first exemplary treatment solution Sila-Max ™ (Table 1) and can be explained by the leveling effect of the rough PU surface by the treatment materials. In addition, all treated films exhibit a 60 ° gloss greater than 90 °.
    The untreated PU film shows a% elongation to deformation well over 300%. After treatment with the treatment composition, the PU films still maintain elongation at> 80% deformation in all three coating weights: 3 gsm, 5 gsm and 7 gsm and in various drying / curing conditions. The elastic modulus of PU films was increased after all treatments because the treatment material is substantially harder than PU film.
    After testing in engine oil for 48 hours, the untreated PU film yellowed substantially, as indicated by the pronounced increase in the values of Ab (16.4) and ΔΕ (16.5) (Table 13). As discussed above, a ΔΕ value above 2.0 is considered perceptible to the naked human eye. In comparison, all treated PU films exhibit negative Ab values, indicating a blue and full color shift (ΔΕ) well below 2.0 and not noticeable to the naked human eye.
    When writing using a permanent marker or a Sharpie king-size pen, the ink written on the untreated PU film does not contract (agglomerate) and the written ink cannot be completely erased using a Kleenex tissue or cloth without damaging the film. When the PU film is treated with the treatment composition, however, the ink from a permanent marker agglomerates instantly and can be completely cleaned. This property is associated with the low surface energy of the treated PU film conferred by the silicone functionalities in the polyacrylate component, as discussed above. When writing using a king size Sharpie pen that distributes ink significantly more than an ordinary permanent marker, the written ink also agglomerates instantly, but traces of residual ink remain observable (rating 7 or 8) after cleaning using a handkerchief. Kleenex paper. In general, better Sharpie performance is obtained for samples treated at high cure temperatures and / or longer exposure times due to a higher degree of polymerization or crosslinking.
    The contact angle of the PU film treated with water testing liquids D.l. and tricresylphosphate (TCP) was measured using a goniometer and the surface energy was calculated using the Geometric Average Model. The result is reported in Table 14 for PU films treated with treatment materials at 3 gsm and 7 gsm, respectively and dried / cured at 215 ° F (zone 1), 300 ° F (zone 2) film surface temperatures ) and 300 ° F (Zone 3). Both treated films show a surface energy of 21.8 mN / m, which is in the low range between the silicone materials. As expected, surface treatment leads to a significant decrease in the polar component and an increase in the non-polar component, the latter being by far the largest contributor to total surface energy. The low surface energy is due to the presence of silicone groups from the polyacrylate component and is responsible for the agglomeration of the ink when writing with a Sharpie pen or permanent marker. In addition, low surface energy is also beneficial for chemical resistance.
    Table 14 - Surface Energies
    Samples Total surface energy [mN / m] ComponentPolar [mN / m] Non-polar component [mN / m] PU (Control) 40.1 34.6 5.5 3 gsm-215-300-300 21.8 1.2 20.6 7 gsm-250-300-300 21.8 1.2 20.6
    FT-IR imaging was performed on the samples of 3 gsm-215-300-300 and 7 gsm-250-300-300 to verify the diffusion depth for the PU film. IR absorptions from 400 to 4000 cm ' 1 were
    73/85 collected in an incremental step of 1.56 µm. In total, 32 foam scans taken and the accumulated spectra were reported in each incremental step. The absorption peaks characteristic of the different functional groups are listed in Table 15.
    Table 15 - Absorption peaks
    Frequency (cm ' 1 ) 2270 1720 1683 1523 1450 Assignments -NCO'spolyisocietyborn -C = O of polyacrylate and polyurethane -C = O of polyurethane and polyisocyanate -N-H dopolyurethane -CH 2 of polyurethane, polyisocyanate and polyacrylate
    The FT-IR spectra of the untreated PU film show a wide absorption band from 1681 to 1722 cm ' 1 , which is designated as the group -C = O bound (centered around 1698 cm' 1 ) and group -C = The free (centered around 1716 cm ' 1 ) with comparable intensities. The untreated PU film also exhibits absorptions at 1450 and 1523 cm ' 1 , attributed to the linked -CH 2 and -NH groups, respectively. On the other hand, the unreacted polyisocyanate shows characteristic absorption peaks centered around 2270 cm-1 due to -NCO groups and 1683 cm ' 1 due to -C = O groups. In addition, the polyacrylate component shows an absorption peak around 1722 cm ' 1 due to -C = O groups in the ester type environment.
    When polyisocyanate reacts with the hydroxyl groups in the polyacrylate, new polyurethane bonds are created, producing new absorption peaks around 1698 cm ' 1 and 1716 cm' 1 , again with comparable intensities. Therefore, the peak around 1720 cm ' 1 represents the contribution of the group -C = O bound in polyurethane and -C = O in polyacrylate, while the peak around 1680 cm' 1 represents contributions from the group -C = O free in polyurethane and -C = O in polyisocyanate.
    The IR spectra were obtained in different incremental steps and normalized against the absorption peak at 1720 cm 1 (Figure 17).
    The characteristic absorption peak of the PU film, for example, 1523 cm ' 1 ,
    74/85 increases continuously with increases in probing depth up to about step 10. Based on color changes from FT-IR imaging, an estimated penetration depth of about 11 pm and 7 μηΊ was obtained for treatment with treatment materials at 3 gsm and 7 gsm, respectively (Table 16). As mentioned above, the diffusion of treatment materials for the PU film contributes to the retention of the forming / stretching capacity of the PU films.
    Table 16 - Diffusion depth
    Substrates Coating weight and drying conditions Coating thickness applied * [m] Thickness ofcoating layer above the PU film [m] Depth ofdiffusion [m] PET 3gsm-215-300-300 2.6 2.8 0 PU 3gsm-215-240-250 2.6 0.5-0.6 Not available PU 3gsm-215-300-300 2.6 0.9 11 PU 7gsm-250-250-250 6.0 2.3 Not available PU 7gsm-250-300-300 6.0 2.7 7
    * Calculated using a coating density of 1.17g / cm 3 .
    Cross-sectional measurements by optical microscopy were performed for PU films treated with the treatment materials at a coating weight of 3 gsm and 7 gsm and dried at different temperatures to measure the actual thickness of these materials arranged above the surface of both PET and PU substrates. The density of the dry coating material from this treatment composition was measured to be about 1.17 g / cm 3 , which is the same as the Coronate HXLV compound. The results are also summarized in Table 16. Material 3 gsm-215-240-250 applied to the PET substrate has a marked interface with a layer thickness of about 2.8 pm, which is comparable with the theoretical thickness of 2.6 pm. In comparison, the same amount of material applied to the PU substrate shows a layer thickness of about 0.5 pm to 0.9 pm, which is about 1/3 of the theoretical thickness (2.6 pm). Similar results were also found for
    75/85 materials 7 gsm-250-300-300, which show a thickness of 2.4 to
    2.7 pm or less than 1/2 of the theoretical thickness (6.0 pm) on the PU film.
    These results suggest that more than 50% of the coating materials have diffused to the PU film substrate.
    Additional evidence of diffusion, though indirect, was found when the treatment solution above was applied to PET and aluminum foil and cured / dried under the same conditions. The coating remains hand-adherent on both substrates. The adherent surface is caused by the presence of an excessive amount of polyisocyanate component that could not penetrate or diffuse on these substrates. Molecular weight measurements by a GPC instrument indicate that the Mw of the polyacrylate material is about 17,800 and that of the polyisocyanate Coronate HXLV is only 631. The smaller size of the polyisocyanate molecule is consistent with the enhanced diffusion in the film of PU.
    In typical 2K polyurethane coatings based on isocyanate reactions and compounds bringing hydroxyl groups, the NCO / -OH ratio of slightly above 1.0 is typically used to compensate for slight losses due to reaction with residual moisture and to completely convert the hydroxyl groups to urethane bonds. In the preferred embodiments of the present invention, part of the isocyanate crosslinking agent diffuses into the PU substrate, therefore, even more excessive amounts of polyisocyanate crosslinking agent are needed to compensate for the extra loss incurred by the poly crosslinking agent. - widespread isocyanate. The polyisocyanate crosslinking agent that has diffused into the PU film can also react with moisture or other compounds having reactive hydrogen atoms within the PU film, leading to complex reactions and new functionality. For example, if the plastic film contains reactive groups, such as carboxyl or hydroxyl groups, the isocyanate crosslinking agent can also react with these groups to form amide and urethane bonds, respectively. Under suitable conditions, such as the presence of a reaction catalyst, the polyisocyanate crosslinking agent can also react with the urethane group in the film
    76/85 PU to form allophanate structures. Thus, a three-dimensional reaction network can be activated by the crosslinking agent, which reacts with both reactive components of 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 8-7 exemplificative treatment composition was further tested for stability under different environments, including high temperatures, high humidity and external sunlight. In Figure 18, the% elongation variation is plotted after exposure to 70 ° C for 4 days and 8 days. The% elongation decreased by about 20-30% after 4 days and became stable afterwards. On the other hand, when the treated PU films are exposed to a high humidity environment, such as a humidity of 90%, no change in the% elongation occurs, as shown in Figure 19. It is assumed that the decrease in the% elongation after exposure to elevated temperatures is due to continuous cross-linking reactions between unreacted polyisocyanate and polyacrylate. In comparison, when treated PU films are exposed to a high humidity environment, reactions occur mainly between unreacted polyisocyanate and moisture to form urea, which is not crosslinked. This is consistent with the fact that moisture is more reactive with isocyanate groups than with hydroxyl groups in a polyol compound. Alternatively, FT-IR measurements indicate that, after exposure to high temperature or high humidity environments, all residual polyisocyanates in the treated PU film reacted in less than 100 hours. In addition, Sharpie's performance has been significantly improved and has become perfect, that is, the writing ink can be cleaned completely and it is difficult to say where the ink was applied (rating of 10).
    The stability of PU films against exposure to sunlight from the outside environment was imitated by accelerated testing on a CÍ5000
    Atlas Weather-Ometer following the SAE J-1960 test protocol. Changes in b * values (Ab *) and total color (ΔΕ) were measured before and after exposure to the test conditions and the results are shown in Figure
    77/85
    20. Very little color change (ΔΕ <0.6) was observed for all samples after testing for 850 hours. In fact, any color variation that is below 2.0 is almost imperceptible, if at all, by the naked human eye. Excellent yellowing resistance is well known for aliphatic polyisocyanate and polyacrylate materials.
    Elongation changes% of treated PU films were measured after exposure to UV wear conditions for 385 hours (Figure 21). The elongation% to deformation remains basically unchanged, similar to that observed in the exposure to high humidity. This result suggests that the majority of post-reactions occurred between polyisocyanate and humidity during the UV weather test. FT-IR measurements indicate that all residual polyisocyanate reacted after testing the weather for about 100 hours. Sharpie's performance was significantly improved and became perfect (grade 10) for all samples, also similar to the results obtained after exposure to high humidity environments.
    Example 9
    Thermally curable formulations were prepared by adding a FASCAT® 2003 reaction catalyst (Arkema Inc.) to the thermally curable treatment composition 8-7. The use of a reaction catalyst is intended to reduce curing temperatures. FASCAT® 2003 is a light yellow liquid consisting of 97% by weight of tin octoate and 3% by weight of 2-ethylhexanoic acid. The FASCAT® 2003 catalyst is used extensively for the production of urethanes from the reaction of isocyanates and polyols. Two new compositions were prepared with different% solids, as shown in Table 17. The composition with the lowest% solids is intended for treatment with less coating weight without changing the liquid distribution system and / or process conditions. PU / PSA / PET films were treated with the two treatment solutions at a dry coating weight of 2.6 gsm and 1.3 gsm on a pilot coating apparatus, respectively, and dried at various drying temperatures. The properties of treated PU films
    78/85 with both treatment compositions are summarized in Table 18.
    Table 17 - Treatment Compositions
    Composition[% by weight] MEK BYK SIL-CLEAN 3700 % of CoronateHXLV FASTCAT®2300 % solids 9-1 55.5 27.7 16.6 0.17 23.9 9-2 76.4 14.7 8.8 0.09 12.5
    Table 18 - Properties of Treated Polyurethane Films
    Composition Process Conditions Stretching[%] Resistance toMo-tor [Ab] Oil ResistanceEngine [ΔΕ1 ClassificationSharpie 9-1 2.6 gsm-200-250-250 125.4 0.16 0.34 5 9-1 2.6 gsm-250-250-250 121.4 0.16 0.33 5 9-2 1.3 gsm-250-250-250 135.0 1.00 1.00 6
    As shown in Table 18, PU films treated at a coating weight of 1.3 gsm show much higher% elongation than those treated with a coating weight of 2.6 gsm. This effect can be attributed both to the intensified diffusion of treatment composition 9-2, which contains more solvents, and to the smaller amount of treatment materials applied due to a lower% solids.
    Variations in b value and total color density after testing with engine oil indicate that a coating weight of 1.3 gsm is more than enough to protect the PU film against yellowing by the used engine oil.
    Sharpie's performance (Table 18) of the PU films treated15 is slightly worse than those treated with the same composition, but without catalyst (Table 13). This result suggests that, in the present catalyst loading, the effect of the catalyst is not strong enough to compensate for the adverse effect of lower drying temperatures 79/85. Sharpie's performance is comparable at a coating weight of 1.3 gsm and 2.6 gsm, again suggesting that the coating weight of
    1.3 gsm is enough to prevent the ink from leaking into the PU film.
    Although not shown, all treated films have a turbidity of less than 3.0% and a brightness at 60 ° above 90.
    Example 10
    Thermally curable treatment compositions have been made including a component (f) in an exemplary treatment composition 8-7. Component (f) was a silicon-containing compound having hydroxyl groups, i.e., a POSS® material of phenyltrisilanol (SO1458) available from Hybrid Plastics (Hattiesburg, MS) as a white powder. SO1458 is typically used as a surface modification (dispersant) additive, moisture resistance enhancing agent and processability enhancing agent for plastic materials. SO1458 contains hydroxyl groups which are capable of reaction with the polyisocyanate crosslinking agent and chemically bonded to the coating matrix. The chemical composition of the freshly prepared treatment compositions is shown in Table 19. The treatment compositions were applied to the 150 pm thick Argotec PU film (PU / PSA / PET) using an Automatic Film Applicator at a coating weight of 10 pm and dried in a thermal oven at 260 ° F for 3 minutes. The properties of PU films thus treated and their performance are shown in Table 20.
    80/85
    % by weight of POSS® based on total solids incomposition 19.05 32.00 41.38 % solids 27.63 31.25 34.52 Liquid treatment composition [% by weight] _______________________________ POSS®%SO1458 5.26 00’0L 14.29 % of CORONATE HXLV 15.79 15.00 14.29 % Polyacrylate 6.58 6.25 5.95 % of total solvents 72.37 68.75 65.48 % MEK 52.63 50.00 47.62The 105(Λ theAnd the ox— oh x ~ 10-2 10-3
    Table 20 - Properties of Treated Polyurethane Films Classification ofSharpie CONon-uniform coating Oil ResistanceEngine [ΔΕ] 0.98 1.33 Engine Oil Resistance [Abl 0.97 1.26 Module 32.2 26.4 Stretching [%] 124.9 the o VN Samples τ-ΟX— 10-2 _______ 10-3
    81/85
    Treatment composition 10-3, which comprises 14.29% SO1458 in the liquid composition, exhibits a milky surface covered with solid materials SO1458 after drying. The 10-2 treatment composition, which contains 10.0% SO1458, forms an optically transparent coating, but becomes milky after stretching for a 40% elongation. The appearance of the milky surface for both treatment compositions 10-2 and 10-3 suggests that some of the POSS® SO1458 materials did not react with the polyisocyanate crosslinking agent and, as a result, they are not chemically bonded to the matrix of the treatment materials and separate from the latter when drawn. In order to maintain an elongation of> 40%, the POSS® SO1458 in the treatment composition needs to be less than about 32% based on total solids.
    Sharpie's performance of treatment compositions comprising SO1458 is worse compared to treatment compositions without POSS® SO1458 (Table 13), which can be attributed to the reduced contribution of the polyacrylate component, which provides silicone groups with low surface energy on the surface and a reduced reaction of the hydroxyl groups in the polyacrylate with the polyisocyanate crosslinking agent. Example 11
    Thermally curable treatment compositions were prepared by including colloidal silica nanoparticles in the treatment composition of Example 8-7. Colloidal silica was obtained from Nissan Chemical Industries, Ltda. (Huston, TX) under the trademark MIBK-ST. It is a light yellow liquid with 31% amorphous silica dispersed in the MIBK solvent. Thus, the new treatment compositions include three solvents: MEK, MPA, and MIBC. Amorphous silica also contains hydroxyl functional groups on the surface of the particle. The composition of the new treatment compositions comprising colloidal silica is shown in Table 21. Again, the treatment compositions were applied at a thickness of 150 pm to PU film substrates (PU / PSA / PET) using an Automatic Film Applicator at a thickness wet at 10 pm and dried in a thermal oven at 260 ° F for 3 minutes. The properties of PU films thus treated and their performance are shown in Table 22.
    82/85
    % by weight of silica based on total solidsi 6.80 12.73 17.95 22.59 % solids 24.00 24.35 24.67 24.95 Net Composition [% by weight] ________________________ Silica 1.63 3.10 co 5.64 CORONATEHXLV 15.79 15.00 14.29 13.64 Polyacrylate 6.58 6.25 5.95 5.68 Solventstotals 76.00 75.65 75.33 75.05 LU 52.63 50.00 47.62 45.45Compositions 11-1 CXI X - X - CO1x—x— 11-4
    Table 22 - Properties of Treated Polyurethane Films Classification ofSharpiein in m Engine Oil Resistance [ΔΕ] 0.98 1.30 1.09 1.06 Engine Oil Resistance [Ab] 0.95 ____________ 1.22 00 oT— 0.97 Module [MPa] 40.0 43.9 53.1 56.6 Stretching [%] 97.0 to 65.8 59.6 Samples 11-1 CXIX— x ~ coV " 11-4
    83/85
    Although not shown, all PU films treated with the above compositions are optically transparent, with a turbidity% less than 3.0 and a 60 ° gloss of more than 90. Additionally, 6.8% by weight of silica in the dry coating, the treated PU film obtained 97% elongation without deformation. However, larger amounts of silica tend to degrade the elongation performance below about 60% with 22.6% by weight of silica, based on the total solids in the treatment composition.
    Inorganic particles, such as amorphous silica, are widely used to increase the hardness of the coating, which leads to improved sea / scratch resistance. As shown in Table 22, even with a loading of 6.80% by weight of silica, the module of the treated PU film (40.0 MPa) is considerably larger than that of the untreated PU film (29.0 MPa) ; it is also much larger compared to PU film treated with POSS® SO1458 nanomaterial treatment compositions (32.2 MPa, Table 20). As expected, the module maintains itself with the increased amount of silica loading.
    Where tested, all samples achieved excellent performance in response to the engine oil test described here. Sharpie's performance was equal to or slightly worse than those treated with the same solution, but without silica.
    Example 12
    A 150 pm Argotec PU film over a PET (PU / PET) vehicle was treated with a dry thickness of 6.5 gsm of the first exemplary Sila-Max ™ U-1006 treatment composition. The PU film thus treated was successfully recorded on a continuous embossing device. The embossing conditions and the depth of the embossed patterns are shown in Table 23.
    Table 23 - Embossing and Depth Conditions
    Test No. Line Speed (inch / min) Temperature (° F) Pressure (psi) DepthRecorded (pm) 1 12 305 90 3.9 2 36 260 90 4.0 3 12 260 90 3.8
    84/85
    Example 13
    A 150 μηι thick PU film laminated to a PSA (PU / PSA / PET) was treated with the exemplary treatment composition 8-10. The surface thus treated was embossed using a stationary thermal press. The upper plate of the press was heated using an IR source. The treated surface was placed on a Master pad with a retro-reflective cube pattern and embossed at a pressure of 90 psi and an IR warm-up time of about 4 seconds.
    Example 14
    An Argotec PU film 150 μΓΠ thick laminated to a PSA (PU / PSA / PET) was treated with the exemplary treatment composition 8-10. A 1.7 mm thick PET / MR Trans-Kote ® Lamination Film was obtained from Transilwrap Company Inc. (Franklin Park, IL). The film was thermally laminated to the surface of the PU film treated on a laboratory scale thermal laminator (Cheminstruments, Fairfield, OH) at a temperature of 250 ° F, a lamination speed of 2 cm / sec and a pressure of 40 psi. The PET lamination layer adheres firmly to the treated surface and can be easily and cleanly delaminated.
    Example 15
    A 150 pm thick black (poly) vinyl chloride (PVC) film was 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 pm in thickness applied to wet and cured in a thermal oven at 220 ° F for 3 minutes. The properties of the PVC film thus treated are shown in Table 25. The untreated PVC film has an elongation of about 500% and a 60 ° gloss of 30.1. When writing with a Sharpie pen, the writing ink does not contract and only traces of the ink can be erased (classification 1). After treatment with an exemplary treatment composition, the brightness at 60 ° of the PVC surface was increased to 91.6, while
    85/85 flexibility / stretching ability was substantially maintained, as shown by a 151.5% strain elongation. When writing using a Sharpie pen, the writing ink contracts instantly and a significant amount of writing ink can be erased (Rating of 7). 3M 810® adhesive tape did not show any delamination of the treatment materials from the PVC film.
    Table 24 - Treatment Composition
    Compositions Net Composition [% by weight] % Solid MEK Solventstotals Polyacrylate Desmodur®3300A 15-1 26.3 75.7 16.4 7.9 24.3
    Table 25 - Properties of Treated Films
    Samples Elongation% to deformation Module[MPa] Brightness at 60 ° Classification ofSharpie Untreated PVC 498.1 218.9 30.1 1 Treated PVC 150.1 143.6 91.6 7
    All patents, published orders and articles mentioned herein are incorporated by reference in their entirety.
    In any case, it will be appreciated that the different exemplary modality aspects can be selectively employed as appropriate to obtain other alternative modalities suitable for desired applications, the other alternative modalities, thereby realizing the respective advantages of the incorporated aspects. In summary, the present specification was presented with reference to the preferred modalities. Obviously, changes and alterations will occur for others when reading and understanding this specification. The invention is intended to be interpreted as including all these modifications and alterations, as long as they are within the scope of the appended claims or their equivalents.
    权利要求:
    Claims (87)
    [1]
    1. Protective film comprising:
    a solid plastic film with an upper and lower surface and a surface treatment region including one or more ingredients applied as a coating composition to the upper surface of said film, wherein said one or more coating ingredients diffuse at least partially in the film, causing significant changes in at least one of the mechanical properties, optical properties, chemical resistance and surface properties of the film and the coating composition is thermally curable.
    [2]
    Protective film according to claim 1, wherein the plastic film is a polyurethane (PU) film or polyvinyl chloride.
    [3]
    Protective film according to claim 1, wherein the plastic film consists of a film with multiple layers.
    [4]
    Protective film according to claim 1, wherein the coating composition comprises:
    at least one compound with functional hydroxyl groups and at least one cross-linking agent capable of reacting with the hydroxyl groups.
    [5]
    Protective film according to claim 4, wherein the at least one compound carrying hydroxyl functional groups further includes hydrophobic groups.
    [6]
    Protective film according to claim 5, wherein the hydrophobic groups comprise at least one of hydrocarbon groups, silicone groups and fluorinated groups.
    [7]
    Protective film according to claim 4, wherein the coating composition further comprises at least one carrier fluid.
    [8]
    Protective film according to claim 4, wherein the coating composition further comprises nano-sized particles including at least one of nano-sized organic particles, nano-sized inorganic particles and organic-inorganic particles
    2/8 unique nano-sized hybrids.
    [9]
    Protective film according to claim 4, wherein the coating composition further comprises at least one of an organic or inorganic matting agent.
    [10]
    Protective film according to claim 8, wherein the nanosized particle is a material derived from a silsesquinoxane compound.
    [11]
    Protective film according to claim 8, wherein the nanosized particle is a silica particle.
    [12]
    Protective film according to claim 8, wherein the nano-sized particle includes reactive functional groups capable of reacting with the cross-linking agent.
    [13]
    Protective film according to claim 4, wherein the coating composition further comprises at least one reaction catalyst.
    [14]
    Protective film according to claim 13, wherein the at least one reaction catalyst consists of an organometallic compound.
    [15]
    Protective film according to claim 4, wherein the at least one crosslinking agent is an isocyanate or polyisocyanate based crosslinking agent.
    [16]
    Protective film according to claim 4, wherein the coating composition further comprises a colorant.
    [17]
    17. Protective film according to claim 4, in which the compound with hydroxyl group adds up to 10% to 85% by weight and the cross-linking agent adds up to 90 to 15% by weight, based on the total solids in the composition.
    [18]
    Protective film according to claim 1, wherein the film is free from a defined limit which divides the coating and the film into separate separate layers.
    [19]
    19. Protective film according to claim 1, wherein the coating composition is diffused into the plastic film, thereby
    3/8 mixing one or more coating ingredients with it.
    [20]
    Protective film according to claim 1, wherein the coating composition exhibits bidirectional diffusion with a low surface energy component that preferably migrates to the upper surface and one or more components that diffuse in the plastic film.
    [21]
    21. Protective film according to claim 1, wherein at least 10% of the coating ingredients diffuse into the plastic film.
    [22]
    22. Protective film according to claim 1, wherein at least 20% of the coating ingredients diffuse into the plastic film.
    [23]
    23. Protective film according to claim 1, wherein at least 30% of the coating ingredients diffuse in the plastic film.
    [24]
    24. Protective film according to claim 1, wherein at least 40% of the coating ingredients diffuse into the plastic film.
    [25]
    25. Protective film according to claim 1, wherein at least 50% of the coating ingredients diffuse in the plastic film.
    [26]
    26. Protective film according to claim 1, wherein the concentration of coating ingredients diffused in the plastic film gradually decreases with depth in the plastic film.
    [27]
    27. Protective film according to claim 1, wherein the diffusion of the coating ingredients in the plastic film creates a new composition for the region for surface treatment arranged above the plastic film, which is different from the initial coating composition.
    [28]
    28. Protective film according to claim 1, wherein the coating composition is diffused more than 3 pm in the plastic film.
    [29]
    29. Protective film according to claim 1, wherein the coating composition is diffused more than 5 pm in the plastic film.
    [30]
    30. Protective film according to claim 1, wherein the
    4/8 coating composition is diffused over 10 pm on the plastic film.
    [31]
    31. Protective film according to claim 1, wherein the coating composition is diffused over 25 µm in the plastic film.
    [32]
    32. Protective film according to claim 1, wherein the thickness of the coating which remains on the upper surface of the plastic film is less than 50 µm.
    [33]
    33. Protective film according to claim 1, wherein the thickness of the coating which remains on the upper surface of the plastic film is less than 25 µm.
    [34]
    34. Protective film according to claim 1, wherein the thickness of the coating which remains on the upper surface of the plastic film is less than 10 pm.
    [35]
    35. Protective film according to claim 1, wherein the thickness of the coating which remains on the upper surface of the plastic film is less than 5 pm.
    [36]
    36. Protective film according to claim 1, wherein the thickness of the coating which remains on the upper surface of the plastic film is less than 3 pm.
    [37]
    37. Protective film according to claim 1, wherein the weight of the applied liquid coating of the coating composition is between about 0.1 pm and about 100 pm.
    [38]
    38. Protective film according to claim 1, wherein the plastic film is treated discontinuously.
    [39]
    39. Protective film according to claim 1, wherein the treated plastic film contains textures on the surface.
    [40]
    40. Protective film according to claim 1, wherein the film is affixed to an article.
    [41]
    41. Protective film according to claim 1, wherein the film is affixed to the body of an automobile.
    [42]
    42. Protective film according to claim 1, wherein the film is affixed to the body, screen or on the body or screen of an electronic device for the consumer.
    5/8
    [43]
    43. Protective film according to claim 1, wherein the film is affixed to an electrical appliance.
    [44]
    44. Protective film according to claim 1, wherein the film is affixed to the body of a ship.
    [45]
    45. Protective film according to claim 1, wherein the film is affixed to the blade of a wind power generator.
    [46]
    46. Protective film according to claim 1, wherein the film is affixed to the body of an airplane.
    [47]
    47. Protective film according to claim 1, wherein the film can withstand at least 40% elongation without failure.
    [48]
    48. Protective film according to claim 1, wherein the film can withstand at least 70% elongation without failure.
    [49]
    49. Protective film according to claim 1, wherein the film can withstand at least 100% elongation without failure.
    [50]
    50. Protective film according to claim 1, wherein the film can withstand at least 150% elongation without failure.
    [51]
    51. Protective film according to claim 39, wherein the film is affixed to an article.
    [52]
    52. Protective film according to claim 39, wherein the film is affixed to the body of an automobile.
    [53]
    53. Protective film according to claim 39, wherein the film is affixed to the body, screen or over the body or screen of an electronic device for the consumer.
    [54]
    54. Protective film according to claim 39, wherein the film is affixed to an electrical appliance.
    [55]
    55. Protective film according to claim 39, wherein the film is affixed to the body of a ship.
    [56]
    56. Protective film according to claim 39, wherein the film is affixed to the blade of a wind energy generator.
    [57]
    57. Protective film according to claim 39, wherein the film is affixed to the body of an airplane.
    [58]
    58. Protective film comprising:
    6/8 a solid plastic film with an upper and lower surface and a surface treatment region including one or more ingredients applied as a coating composition to the upper surface of said film, wherein said one or more coating ingredients are they diffuse at least partially in the film, causing significant changes in at least one of the mechanical properties, optical properties, chemical resistance and surface properties of the film, where the coating composition is curable by irradiation and the treated surface contains textures.
    [59]
    59. Protective film according to claim 58, wherein the surface texture is created by means of printing.
    [60]
    60. Protective film according to claim 58, wherein the surface texture is created by embossing.
    [61]
    61. Protective film according to claim 58, wherein the surface texture is random.
    [62]
    62. Protective film according to claim 58, wherein the film is thermoformed.
    [63]
    63. Protective film according to claim 58, wherein the film is affixed to an article.
    [64]
    64. Protective film according to claim 58, wherein the film is affixed to the body of an automobile.
    [65]
    65. Protective film according to claim 58, wherein the film is affixed to the body, screen or over the body or screen of an electronic device for the consumer.
    [66]
    66. Protective film according to claim 58, wherein the film is affixed to an electrical appliance.
    [67]
    67. Protective film according to claim 58, wherein the film is affixed to the body of a ship.
    [68]
    68. Protective film according to claim 58, wherein the film is affixed to the blade of a wind energy generator.
    [69]
    69. Protective film according to claim 58, wherein
    7/8 the film is affixed to the body of an airplane.
    [70]
    70. Protective laminate including the protective film as defined in claim 1.
    [71]
    71. Protective laminate according to claim 70, wherein the protective film is laminated in a release-prone coating coated with a pressure sensitive adhesive (Pressure Sensitive Adhesive PSA).
    12. Protective laminate according to claim 70, wherein the protective film is self-rolled and has no release lining.
    [72]
    73. Protective laminate according to claim 70, wherein the protective film is laminated in a functional layer substantially free of adhesive for fixing the laminate to an object surface.
    [73]
    74. Protective laminate according to claim 70, further comprising a protective layer over the region for surface treatment.
    [74]
    75. Protective laminate according to claim 73, wherein the substantially adhesive-free functional layer acquires adhesive property after activation by heat or radiation.
    [75]
    76. Protective laminate including the protective film as defined in claim 39.
    [76]
    77. Protective laminate according to claim 76, wherein the protective film is laminated in a release-able coating coated with a pressure sensitive adhesive (Pressure Sensitive Adhesive - PSA).
    [77]
    78. Protective laminate according to claim 76, wherein the protective film is self-rolled and has no release lining.
    [78]
    79. Protective laminate according to claim 76, wherein the protective film is laminated in a functional layer substantially free of adhesive for fixing the laminate to an object surface.
    [79]
    80. Protective laminate according to claim 76, further comprising a protective layer over the region for treatment of
    8/8 surface.
    [80]
    81. Protective laminate according to claim 79, wherein the substantially adhesive-free functional layer acquires adhesive property after activation by heat or radiation.
    [81]
    82. Protective laminate including the protective film as defined in claim 58.
    [82]
    83. Protective laminate according to claim 82, wherein the protective film is laminated to a release-able coating coated with a pressure sensitive adhesive (Pressure Sensitive Adhesive - PSA).
    [83]
    84. Protective laminate according to claim 82, wherein the protective film is self-rolled and has no release lining.
    [84]
    85. Protective laminate according to claim 82, wherein the protective film is laminated in a functional layer substantially free of adhesive for fixing the laminate to an object surface.
    [85]
    86. Protective laminate according to claim 82, further comprising a protective layer over the region for surface treatment.
    [86]
    87. Protective laminate according to claim 85, wherein the substantially adhesive-free functional layer acquires adhesive property after activation by heat or radiation.
    [87]
    88. Method of using a protective film, the method comprising the steps of:
    providing a film with an upper and lower surface;
    providing a treatment composition;
    application of the treatment composition on the upper surface of the film; and applying heat to the treatment composition to cure the composition with at least part of the composition diffusing to the upper surface of the film.
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    同族专利:
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    US20130059120A1|2013-03-07|
    US20100297376A1|2010-11-25|
    MX2012013466A|2013-04-29|
    US8568849B2|2013-10-29|
    EP2571682A1|2013-03-27|
    JP2013533131A|2013-08-22|
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    法律状态:
    2019-08-13| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|
    2019-10-29| B11Y| Definitive dismissal - extension of time limit for request of examination expired [chapter 11.1.1 patent gazette]|
    2020-01-28| B25B| Requested transfer of rights rejected|Owner name: AVERY DENNISON CORPORATION (US) Free format text: INDEFERIDO(S) O(S) PEDIDO(S) DE TRANSFERENCIA(S) CONTIDO(S) NA PETICAO 870160055482 DE 28/09/2016 EM VIRTUDE DO DESPACHO PUBLICADO NA RPI NO 2547 DE 29/10/2019. |
    2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US12/784,160|US8568849B2|2009-05-20|2010-05-20|Surface treated film and/or laminate|
    PCT/US2011/032658|WO2011146188A1|2010-05-20|2011-04-15|Surface treated film and/or laminate|
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