Adhesive-stabilized overlaminate film articles

Abstract

Decorative constructions include a printed surface and an overlaminate article disposed on the printed surface. The overlaminate article includes an optically clear non- fluorinated film and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated film. The pressure sensitive adhesive includes a (meth)acrylate-based pressure sensitive adhesive matrix and 5-13 weight % of at least one UV absorber material. The pressure sensitive adhesive has a peel adhesion to printed film of at least 90 N / dm. Upon exposure to weathering of 2513 MJ / m2 of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same pressure sensitive adhesive layer that does not contain the UV absorber material.

Description

[0001] PA102785W002

[0002] ADHESIVE-STABILIZED OVERLAMINATE FILM ARTICLES

[0003] Summary

[0004] Disclosed herein are decorative construction comprising overlaminate articles, overlaminate articles, and methods of preparing decorative constructions. In some embodiments, the decorative constructions comprise a printed surface and an overlaminate article disposed on the printed surface. The overlaminate article comprises an optically clear non-fluorinated fdm and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated fdm and in contact with the printed surface, where the optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material. The at least one UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive. The optically transparent pressure sensitive adhesive has a peel adhesion to printed fdm of at least 90 N / dm, and upon exposure to weathering of 2513 MJ / m2of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material.

[0005] Also disclosed are overlaminate articles. In some embodiments, the overlaminate article comprises an optically clear non-fluorinated fdm and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated fdm, where the optically transparent pressure sensitive adhesive comprises a (methacrylate- based pressure sensitive adhesive matrix and at least one UV absorber material. The at least one UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive. The optically transparent pressure sensitive adhesive has a peel adhesion to printed fdm of at least 90 N / dm, and upon application to a printed surface and exposure to weathering of 2513 MJ / m2of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material. Also disclosed are methods of preparing decorative constructions. In some embodiments. The method comprises providing a printed surface, providing an overlaminate article, where the overlaminate article is described above.

[0006] Brief Description of the Drawings

[0007] The present application may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings.

[0008] Figure 1 is a cross-sectional view of an overlaminate fdm article of this disclosure.

[0009] Figure 2 is a cross-sectional view of a printed fdm article of this disclosure.

[0010] Figure 3 is a cross-sectional view of an overlaminate construction of this disclosure.

[0011] Detailed Description

[0012] A wide range of graphic fdms are used for decorative and information purposes. Among the uses are transportation vehicles such as trains, trucks, buses and the like. It is desired that these decorative fdms be durable for long periods of time. In many cases it is desirable for the decorative fdms to be stable for years, often up to 10 years. This is particularly difficult as the decorative films are exposed to the environment, including wind, rain, dirt, and UV radiation.

[0013] Often the graphic fdms are protected by overlaminate fdms. The overlaminate fdms are optically clear so as to not obscure the decorative fdm, and typically are adhered to the decorative fdm with an optically clear or optically transparent adhesive. While the overlaminate fdm protects the decorative fdm from damage and aging, the overlaminate fdm is subject to the environmental conditions. One solution to this is to prepare stabilized overlaminate fdms that have enhanced durability, however this process is expensive as specialized fdms need to be made, and the high level of stabilization materials required to protect some print chemistries may exceed the solubility limits of some fdm materials. Another consideration is the desire to get away from the use of fluorinated materials such as fluorinated fdms that are sometimes used in overlaminate fdm articles. This replacement can be difficult as the fluorinated fdms have desirable properties and generally good durability. Thus, a desirable fdm category is not a suitable candidate for use in UV-durable overlaminate fdm articles, thereby making the development of such articles even more difficult. Therefore, methods for increasing the durability, especially UV durability, of overlaminate film articles that use conventional films without fluorinated materials or special stabilization treatments is needed.

[0014] In this disclosure, decorative articles are described that include a printed surface and an overlaminate article disposed on the printed surface, where the overlaminate article comprises an optically clear non-fluorinated film and an optically transparent pressure sensitive adhesive layer that is a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, where the UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive. Surprisingly, it was discovered that the UV absorber material, even though present in a relatively high level does not destroy the adhesive strength of the pressure sensitive adhesive layer. Additionally, and even more surprisingly, the relatively high level of UV absorber material not only provides UV stability to the pressure sensitive adhesive layer, but also enhances the UV stability of the printed surface to which the adhesive layer is applied and also enhances the UV stability of the optically clear non-fluorinated film of the overlaminate article. Also disclosed are methods for preparing decorative articles.

[0015] The term “adhesive” as used herein refers to polymeric compositions useful to adhere together two adherends. Examples of adhesives are pressure sensitive adhesives.

[0016] Pressure sensitive adhesive compositions are well known to those of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be cleanly removable from the adherend. Materials that have been found to function well as pressure sensitive adhesives are polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power. Obtaining the proper balance of properties is not a simple process.

[0017] The term “(meth)acrylate” refers to monomeric acrylic or methacrylic esters of alcohols. Acrylate and methacrylate monomers or polymers are referred to collectively herein as "(meth)acrylates”. Materials referred to as “(meth)acrylate functional” are materials that contain one or more (meth)acrylate groups. The terms "room temperature" and "ambient temperature" are used interchangeably to mean temperatures in the range of 20°C to 25°C.

[0018] The term “adjacent” as used herein when referring to two layers means that the two layers are in proximity with one another with no intervening open space between them. They may be in direct contact with one another (e.g. laminated together) or there may be intervening layers.

[0019] The terms “polymer” and “macromolecule” are used herein consistent with their common usage in chemistry. Polymers and macromolecules are composed of many repeated subunits. As used herein, the term “macromolecule” is used to describe a group attached to a monomer that has multiple repeating units. The term “polymer” is used to describe the resultant material formed from a polymerization reaction.

[0020] The term “non-fluorinated” is used herein in accordance with its common usage in the polymer arts, and refers to materials, fdms or articles that do not contain fluorine or fluorinated materials.

[0021] The term “alkyl” refers to a monovalent group that is a radical of an alkane, which is a saturated hydrocarbon. The alkyl can be linear, branched, cyclic, or combinations thereof and typically has 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

[0022] The term “aryl” refers to a monovalent group that is aromatic and carbocyclic. The aryl can have one to five rings that are connected to or fused to the aromatic ring. The other ring structures can be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, peryl enyl, and fluorenyl.

[0023] The terms “free radically polymerizable” and “ethylenically unsaturated” are used interchangeably and refer to a reactive group which contains a carbon-carbon double bond which is able to be polymerized via a free radical polymerization mechanism.

[0024] Unless otherwise indicated, the terms “optically transparent”, and “visible light transmissive” are used interchangeably, and refer to an article, film or adhesive that has a high light transmittance over at least a portion of the visible light spectrum (about 400 to about 700 nm). Typically, optically transparent articles have a visible light transmittance of at least 90% and a haze of less than 10%.

[0025] Unless otherwise indicated, "optically clear" refers to an adhesive or article that has a high light transmittance over at least a portion of the visible light spectrum (about 400 to about 700 nm), and that exhibits low haze, typically less than about 5%, or even less than about 2%. In some embodiments, optically clear articles exhibit a haze of less than 1% at a thickness of 50 micrometers or even 0.5% at a thickness of 50 micrometers. Typically, optically clear articles have a visible light transmittance of at least 95%, often higher such as 97%, 98% or even 99% or higher.

[0026] Disclosed herein are decorative constructions. In some embodiments, the decorative construction comprises a printed surface and an overlaminate article disposed on the printed surface. The overlaminate article comprises an optically clear nonfluorinated film and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated film and in contact with the printed surface. The optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, where the at least one UV absorber material is present in an amount of X weight % based on the total weight of the optically transparent pressure sensitive adhesive. The relatively high loading of the UV absorber material does not adversely affect the adhesion of the optically transparent pressure sensitive adhesive, as evidenced by the peel adhesion to printed film of an adhesive / film article having at least 90 N / dm. Additionally, upon exposure to weathering of 2513 MJ / m2of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material. Weathering is typically modeled using machine weathering to expose samples to UV light as is described in the Examples section. In some cases, this enhanced stability indicates that the optically transparent pressure sensitive adhesive layer not only is protecting the printed surface from UV degradation but also protecting the nonfluorinated film of the overlaminate article from UV degradation.

[0027] A wide variety of printed surfaces are suitable for use in the decorative constructions. The printing can be in the form of indicia, logos, information, or decorative designs. While in some embodiments the printed surface may have printing directly on a surface such as the side or top of a vehicle, typically the printed surface comprises a fdm substrate with a printed surface. Typically, the film substrate is adhered to a surface, such as the surface of a vehicle, with an adhesive layer. In this way, the printed surface can be removed and replaced with a different film substrate with a printed surface.

[0028] A wide variety of film substrates are suitable. Examples of films suitable for use as the film substrates include PVC films (polyvinyl chloride), polyester films, polyolefin films, polyurethane films, ionomeric films, poly(meth)acrylate films, polycarbonate films, polyvinyl butyral films, cellulose acetate propionate films, films that are blends of these materials, and the like.

[0029] The adhesive layer used to adhere the film substrate to a surface can be a pressure sensitive adhesive, a heat activated adhesive (where the adhesive is non-tacky at room temperature but becomes tacky upon heating), or hot melt adhesives (where the adhesive flows and is tacky in the molten state and then hardens to a non-tacky state).

[0030] The printing on the surface of the film substrate can be any printing suitable for the decorative articles. Examples include inkjet printing, screen printing, gravure printing, and the like. Printing of graphic articles for use as decorative films is well- understood in the art.

[0031] The decorative constructions of this disclosure also comprise an overlaminate article disposed on the printed surface. These overlaminate articles comprise an optically clear non-fluorinated film and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated film. The adhesive layer is also in contact with the printed surface.

[0032] A wide range of optically clear non-fluorinated films are suitable for use in the overlaminate article. Examples include a PVC (polyvinyl chloride) film, an ionomeric film, a polyester film, cellulose acetate propionate film, an acetate film, an aliphatic polyurethane film, a (meth)acrylate film, or blends thereof. As was mentioned above it is desirable that the film be able to be used as supplied by the film manufacturer and does not require stabilizing treatments or components and that the film be non-fluorinated. The ability to use standard, readily available films make the overlaminate articles easier to prepare as well as more economical. The optically clear non-fluorinated films of the overlaminate articles can have a wide range of thicknesses. Typically, the thickness ranges from 25 micrometers to 750 micrometers, more typically 25-500 micrometers, 25-250 micrometers or even 25-100 micrometers.

[0033] In some embodiments, it may be desirable to surface treat the surface of the optically clear non-fluorinated film to which the pressure sensitive adhesive is to adhere to increase the adhesion of adhesive to the film surface. The surface treatment may involve a physical treatment of the surface such as corona or flame treatment, or it may involve applying a primer layer to the surface. A wide range of suitable primers are known to one of skill in the adhesive arts. Typically, primers are not necessary in the currently disclosed overlaminate articles.

[0034] The overlaminate articles also comprise an optically transparent pressure sensitive adhesive layer. The optically transparent pressure sensitive adhesive layer is a (meth)acrylate-based polymeric matrix. Typically the (meth)acrylate-based polymeric matrix is crosslinked.

[0035] While a wide range of (meth)acrylate-based pressure sensitive adhesive are suitable, one particularly suitable class of adhesives are the adiabatically polymerized pressure sensitive adhesives prepaerd by a method similar to that described in US Patent No. 5,986,011.

[0036] In some embodiments, the polymerization method comprises providing a first reaction mixture, deoxygenating the first reaction mixture, heating the first reaction mixture to a temperature above the activation temperature of the thermal initiator of the first reaction mixture; allowing the first reaction mixture to polymerize under essentially adiabatic conditions to yield an at least partially polymerized mixture, cooling the at least partially polymerized mixture, adding an additional thermal initiator, and a chain transfer agent to the partially polymerized mixture to form a second reaction mixture, deoxygenating the second reaction mixture, heating the second reaction mixture to a temperature above the activation temperature of the additional thermal initiator, and allowing the second reaction mixture to polymerize under essentially adiabatic conditions to form a polymer. The first reaction mixture comprises at least one alkyl(meth)acrylate monomer with alkyl groups comprising 1-14 carbon atoms, at least one reinforcing monomer, at least one photocrosslinkable monomer, and at least one thermal initiator.

[0037] A wide range of alkyl(meth)acrylate monomers are suitable. The alkyl(meth)acrylate monomers are described by Formula I:

[0038] CH2=CR1-(CO)-O-R2

[0039] Formula I where R1is an H atom or a methyl group;

[0040] -(CO)- is a carbonyl group C=O; and

[0041] R2is an alkyl group with 1-14 carbon atoms.

[0042] Examples of suitable alkyl (meth)acrylate comprises methyl (meth)acrylate, ethyl (meth)acrylate, iso-propyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, 2-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 4- methyl-2-pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-octyl (meth)acrylate, n- nonyl (meth)acrylate, isononyl (meth)acrylate, isobomyl (meth)acrylate), adamantyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isotridecyl (meth)acrylate, and combinations thereof.

[0043] In some embodiments, the reaction mixture contains a mixture of alkyl (meth)acrylate monomers. In some embodiments the reaction mixture contains a first alkyl (meth)acrylate monomer with 1-4 carbon atoms and a second alkyl (meth)acrylate monomer with 6-14 carbon atoms. Examples of the first alkyl (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, iso-propyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate. Examples of the second alkyl (meth)acrylate monomer include 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isobomyl (meth)acrylate), n-decyl (meth)acrylate, and isodecyl (meth)acrylate. The first and second alkyl (meth)acrylate monomers may also be mixtures.

[0044] The first reaction mixture also comprises at least one reinforcing monomer. A wide variety of reinforcing monomers are suitable, typically acid-functional monomers, base-functional monomers, or macromonomers. Examples of acid-functional monomers include ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, and ethylenically unsaturated phosphoric acids, and mixtures thereof. Examples of such compounds include, but are not limited to, those selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, B-carboxyethyl acrylate, sulfoethyl methacrylate, and the like, and mixtures thereof.

[0045] Examples of base-functional monomers include acrylamides, N,N -dialkyl substituted acrylamides, N-vinyl lactams, and N,N-dialkylaminoalkyl acrylates, and mixtures thereof. Illustrative examples include, but are not limited to, those selected from the group consisting of N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N- diethyl acrylamide, N,N-diethyl methacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, N,N -dimethylaminoethyl acrylate, N,N- dimethylaminopropyl acrylate, NVP (N-vinyl pyrrolidone), and the like, and mixtures thereof.

[0046] Macromers are macromolecular monomers. Examples of macromonomers are macromeric (meth)acrylates. Examples of macromeric (meth)acrylates such as (meth)acrylate-terminated styrene oligomers and (meth)acrylate-terminated polyethers, such as are described in PCT Patent Application WO 84 / 03837 and European Patent Application EP 140941. Methacrylate -terminated polydimethylsiloxane macromer are described in US Patent No. 4,693,935 (Mazurek).

[0047] Particularly suitable reinforcing monomers include acrylic acid, NVP (N-vinyl pyrrolidone), a siloxane-containing macromer, or a styrene-containing macromer.

[0048] The first reaction mixture further comprises at least one photocrosslinker. Photocrosslinkers have a free radically polymerizable group to co-polymerize with the monomers described above, and also contain a photosensitive group. Upon exposure to the right wavelength of light, typically high intensity ultra-violet (UV) radiation, the photosensitive group forms free radicals which can form crosslinks in the polymer.

[0049] Suitable photocrosslinkers in the mono-ethylenically unsaturated aromatic ketone co-monomers that are free of ortho-aromatic hydroxyl groups such as those described in US Patent No. 4,737,559 (Kellen et al.). Specific examples include para- acryloxybenzophenone (ABP), para-acrylyoxyethoxybenzophenone, para-N- (methylacryloxyethyl)-carbamoylethoxybenzophenone, para-acryloxyacetophenone, ortho-acrylamidoacetophenone, acrylated anthraquinones, and the like. Particularly suitable are ABP para-acryloxybenzophenone and AEBP Acryloxy Ethyl Benzophenone.

[0050] The first reaction mixture also includes at least one thermal initiator. Suitable thermal initiators include various azo compound such as those commercially available under the trade designation VAZO from E. I. DuPont de Nemours Co. (Wilmington, DE, USA) including VAZO 67, which is 2,2’-azobis(2-methylbutane nitrile), VAZO 64, which is 2,2’-azobis(isobutyronitrile), VAZO 52, which is (2,2’-azobis(2,4- dimethylpentanenitrile), and VAZO 88, which is l,l’-azobis(cyclohexanecarbonitrile); various peroxides such as benzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, di- tert-amyl peroxide, tert-butyl peroxy benzoate, di-cumyl peroxide, and peroxides commercially available from Atofina Chemical, Inc. (Philadelphia, PA) under the trade designation LUPEROX (e.g., LUPEROX 101, which is 2,5-bis(tert-butylperoxy)-2,5- dimethylhexane, and LUPEROX 130, which is 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3- hexyne); various hydroperoxides such as tert-amyl hydroperoxide and tert-butyl hydroperoxide; and mixtures thereof.

[0051] Particularly suitable (meth)acrylate-based polymers suitable for use as the pressure sensitive adhesives of the current disclosure include ones based upon methyl acrylate (MA), iso-octyl acrylate (IOA), acrylic acid (AA), and AEBP. In some embodiments the (meth)acrylate-based polymers contain 60-75 wt% IOA, 18-30 wt% MA, 5-12 wt% AA, and 0.1-0.5 wt % AEBP.

[0052] The optically transparent pressure sensitive adhesive layer of the overlaminate articles also comprise at least one UV absorber material. A wide range of UV absorber materials are suitable. In some embodiments, the UV absorber material comprises a benzotriazole, a benzophenone, a triazine, a benzoxazine, an octocrylene, nano-sized titanium dioxide, or combinations thereof.

[0053] In many embodiments, the UV absorber material comprises a hydroxyphenyl benzotriazole. Particularly suitable is the UV absorber TINUVIN 928 from BASF, Charlotte, NC.

[0054] The amount of added UV absorber material to the optically transparent pressure sensitive adhesive layer is relatively high, being at least 5% by weight of the total optically transparent pressure sensitive adhesive layer. In some embodiments, the UV absorber material is present in a range of 5-13 % by weight, or even 6-13% by weight, or even 7-13% by weight.

[0055] Besides the UV absorber material, the optically transparent pressure sensitive adhesive layer may also comprise at least one additional additive. These additives can comprise a HALS (hindered amine light stabilizer) or an antioxidant. Such additives are not necessary but can be added if desired as long as they do not interfere with the optical or stability properties of the optically transparent pressure sensitive adhesive layer.

[0056] As mentioned above, the relatively high loading of the UV absorber material does not adversely affect the desirable properties of the adhesive. The adhesion of the optically transparent pressure sensitive adhesive, as evidenced by the peel adhesion to printed film of an adhesive / film article having at least 90 N / dm. Peel adhesion is measured as described in the Examples section. Additionally, the optical properties of the pressure sensitive adhesive layer are equally essential. While the pressure sensitive adhesive is described as being optically transparent, the pressure sensitive adhesive may be optically clear having a transmission of at least 95% and haze of less than 5%.

[0057] The optically transparent pressure sensitive adhesive layer can have a wide range of thicknesses. The optically transparent pressure sensitive adhesive layer thickness can range from 10 micrometers to 100 micrometers. More typically the optically transparent pressure sensitive adhesive layer thickness is from 15-100 micrometers, or even 25-75 micrometers.

[0058] As mentioned above, the decorative constructions of this disclosure have a variety of desirable stability properties. These properties can be tested in a variety of ways. One way is to apply the decorative constructions to a vehicle and observe changes in the decorative article over time. However, as this is a laborious and time-consuming process, a variety of modeling tests have been developed. Samples to be tested can be placed in weathering chambers and exposed to a variety of conditions including exposure to UVA radiation. For most useful data, the testing was carried out using the complete decorative construction and the color retention of the printed layer is monitored. Since the feature to be tested is the ability of the optically transparent pressure sensitive adhesive layer to provide durability to the decorative construction, if the same testing is carried out with an identical decorative construction with an overlaminate adhesive layer that is a conventional optically transparent pressure sensitive adhesive, the effect of the adhesive layer can be determined. In some embodiments of the articles of this disclosure, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material. This enhanced stability indicates that the optically transparent pressure sensitive adhesive layer not only is protecting the printed surface from UV degradation but also protecting the non-fluorinated fdm of the overlaminate article from UV degradation. Typically, the testing is carried out to an exposure of 1000 MJ / m2up to 2500 MJ / m2.

[0059] Additionally, long term environmental again can be carried out. In some embodiments, the optically clear non-fluorinated fdm of the overlaminate article retains optical clarity for greater than 5 years.

[0060] Also disclosed herein are overlaminate articles. These overlaminate articles are described in detail above and have a variety of uses besides their use in the decorative constructions described above. In some embodiments, the overlaminate article comprises an optically clear non-fluorinated fdm and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated fdm where the optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive. The optically transparent pressure sensitive adhesive has a peel adhesion to printed fdm of at least 90 N / dm, and upon application to a printed surface and -exposure in a xenon arc weathering device with daylight fdters operated at high-irradiance in accordance with ASTM Practice G155, (radiation from the xenon arc source was fdtered so as to provide an excellent match to the ultraviolet portion of the solar spectrum) the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material. The components of the overlaminate articles are described in detail above.

[0061] Also described herein are methods for preparing decorative constructions. In some embodiments, the method comprises providing a printed surface, providing an overlaminate article comprising an optically clear non-fluorinated fdm and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non- fluorinated film, and disposing the optically transparent pressure sensitive adhesive layer on the printed surface.

[0062] Suitable printed surfaces, overlaminate articles, and their compositions and properties are described in detail above. Additionally, the properties of the formed decorative constructions are also described in detail above.

[0063] The articles of this disclosure may be more fully understood by referring to the figures. Figure 1 shows article 100, an overlaminate film article comprising overlaminate film 110 and pressure sensitive adhesive layer 120.

[0064] Figure 2 shows printed film article 200 comprising a printable film substrate 230 and printed layer 240. In some embodiments, the printable layer is a discontinuous layer in the form of a design or indicia. In other embodiments, printable film substrate 230 is unprinted.

[0065] Figure 3 shows an overlaminate construction 300. The construction comprises overlaminate film 310, pressure sensitive adhesive layer 320, printable film substrate 330 and printed layer 340. Construction 300 is prepared by laminating together articles 100 and 200.

[0066] Examples

[0067] These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise. The following abbreviations are used: cm = centimeters; dm = decimeters; m = meters; in = inch; lb = pounds; N = Newtons min = minutes; mJ = milliJoules; MJ = MegaJoules. The terms “weight %”, “% by weight”, and “wt%” are used interchangeably.

[0068] Table of Abbreviations

[0069] Test Methods

[0070] Film Weathering

[0071] Film samples to be tested were adhered to a metal plate and were exposed in a xenon arc weathering device with daylight filters operated at high-irradiance in accordance with ASTM Practice G155. Radiation from the xenon arc source was filtered so as to provide an excellent match to the ultraviolet portion of the solar spectrum. Samples were checked at exposures of 359, 718, 1077, 1436, and 1795 MJ / m2.

[0072] 180° Peel Adhesion

[0073] This peel adhesion test is similar to the test method described in ASTM D 3330- 90.

[0074] Three-layer laminates were prepared of printed film / adhesive / overlaminate film, where the overlaminate film was Film-1 or Film-4 and the printed film was either Film -2 or Film-3. The laminates were cut into 1.27 centimeter by 15 centimeter strips. Each strip was then adhered to a 17.8 centimeter by 33 centimeter desmutted aluminum panel using the pressure sensitive adhesive on the back side of the printed film using a 2.3 kg rubber roller. The bonded assembly dwelled at room temperature for about 24 hours and was tested for 180° peel adhesion using an Instron Tensile Tester commercially available from Instron (Norwood, MA) operated at a crosshead speed of 30 centimeters / minute (12 inches / minute) or 2.3 meters / minute (90 inches / minute) over a five second data collection time. The samples were measured in Ibf (pound-force) per inch and converted to Newtons / decimeter and are reported in both units.

[0075] Color Change (DE*) Testing

[0076] Color change (DE*) was quantified using an X-Rite (Grand Rapids MI) Ci6X handheld colorimeter calibrated with a Ci62- 162-02 calibration tile, comparing color to identical samples stored under cool, dark conditions.

[0077] Examples

[0078] Examples Exl-Ex20 and Comparative Examples CE1-CE4

[0079] Preparation and testing of Laminate Constructions:

[0080] A series of laminate construction examples were prepared that contain up to 4 layers. The layers in sequence were printable film / printed layer / PSA layer / overlaminate film. The constructions are formed by preparing pressure sensitive adhesive samples with or without UV ABSORBER and laminating these adhesives to an overlaminate film to form an overlaminate article. The overlaminate articles are laminated to a film article comprising either a printable film or a printable film with a printed layer on it. The constructions are described in Table 1.

[0081] Table 1

[0082] Weathering Testing of Laminate Constructions

[0083] The Examples described above were weathered according to the test methods described above. The data are shown in Table 2 show the Color Change (D*) values upon exposure to radiation described in the Weathering Test Method.

[0084] Table 2

[0085] Preparation and Testing of Peel Adhesion

[0086] To test the effect of the added UV absorber on the adhesive strength, a series of samples were prepared and tested according to the test method described above. The results are shown in Table 3. The samples reflect different PSA compositions, different backing fdms, and different peeling speeds. For the Examples, the failure mode was at the bond between the test fdm and the adhesive except for the Comparative Examples where the failure mode was the bond between the adhesive and the aluminum substrate. Table 3

Claims

What is claimed is:

1. A decorative construction comprising: a printed surface; and an overlaminate article disposed on the printed surface, wherein the overlaminate article comprises: an optically clear non-fluorinated fdm; and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated film and in contact with the printed surface, wherein the optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, wherein the at least one UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive, and wherein the optically transparent pressure sensitive adhesive has a peel adhesion to printed film of at least 90 N / dm, and wherein upon exposure to weathering of 2513 MJ / m2ofUV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material.

2. The decorative construction of claim 1, wherein the printed surface comprises a film substrate with a printed surface.

3. The decorative construction of claim 1, wherein the optically clear non-fluorinated film of the overlaminate article comprises a PVC (polyvinyl chloride) film, an ionomeric film, a polyester film, cellulose acetate propionate film, an acetate film, an aliphatic polyurethane film, a (meth)acrylate film, or blends thereof.

4. The decorative construction of claim 1, wherein the optically transparent pressure sensitive adhesive layer comprises a (meth)acrylate polymer or co-polymer prepared from a reaction mixture comprising at least one alkyl(meth)acrylate monomer with alkyl groups comprising 1-14 carbon atoms, at least one reinforcing monomer, at least one photocrosslinkable monomer, and at least one thermal initiator.

5. The decorative construction of claim 1, wherein the optically transparent pressure sensitive adhesive layer comprises a (meth)acrylate co-polymer prepared from a reaction mixture comprising an alkyl (meth)acrylate monomer with alkyl groups comprising 1-4 carbon atoms, an alkyl (meth)acrylate monomer with alkyl groups comprising 6-14 carbon atoms, acrylic acid, AEBP (Acryloxy Ethyl Benzophenone), and at least one thermal initiator.

6. The decorative construction of claim 1, wherein the optically transparent pressure sensitive adhesive layer is a crosslinked pressure sensitive adhesive layer.

7. The decorative construction of claim 1, wherein the UV absorber material comprises a benzotriazole, a benzophenone, a triazine, a benzoxazine, an octocrylene, nano-sized titanium dioxide, or combinations thereof.

8. The decorative construction of claim 1, wherein the UV absorber material comprises a hydroxyphenyl benzotriazole.

9. The decorative construction of claim 1, wherein the optically transparent pressure sensitive adhesive layer comprises at least one additional additive10. The decorative construction of claim 1, wherein the optically clear non-fluorinated fdm of the overlaminate article retains optical transparency for greater than 5 years.

11. An overlaminate article comprising: an optically clear non-fluorinated fdm; andan optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated fdm, wherein the optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, wherein the at least one UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive, and wherein the optically transparent pressure sensitive adhesive has a peel adhesion to printed fdm of at least 90 N / dm, and wherein upon application to a printed surface and exposure to weathering of 2513 MJ / m2of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same optically transparent pressure sensitive adhesive layer that does not contain the UV absorber material.

12. The overlaminate article of claim 11, wherein the optically clear non-fluorinated fdm of the overlaminate article comprises a PVC (polyvinyl chloride) fdm, an ionomeric fdm, a polyester fdm, cellulose acetate propionate fdm, an acetate fdm, an aliphatic polyurethane fdm, a (meth)acrylate fdm, or blends thereof.

13. The overlaminate article of claim 11, wherein the optically transparent pressure sensitive adhesive layer comprises a (meth)acrylate polymer or co-polymer prepared from a reaction mixture comprising at least one alkyl(meth)acrylate monomer with alkyl groups comprising 1-14 carbon atoms, at least one reinforcing monomer, at least one photocrosslinkable monomer, and at least one thermal initiator.

14. The overlaminate article of claim 11, wherein the optically transparent pressure sensitive adhesive layer comprises a (meth)acrylate co-polymer prepared from a reaction mixture comprising an alkyl (meth)acrylate monomer with alkyl groups comprising 1-4 carbon atoms, an alkyl (meth)acrylate monomer with alkyl groups comprising 6-14 carbon atoms, acrylic acid, AEBP (Acryloxy Ethyl Benzophenone), and at least one thermal initiator.

15. The overlaminate article of claim 11, wherein the optically transparent pressure sensitive adhesive layer is a crosslinked pressure sensitive adhesive layer.

16. The overlaminate article of claim 11, wherein the UV absorber material comprises a benzotriazole, a benzophenone, a triazine, a benzoxazine, an octocrylene, nano-sized titanium dioxide, or combinations thereof.

17. The overlaminate article of claim 11, wherein the UV absorber material comprises a hydroxyphenyl benzotriazole.

18. The overlaminate article of claim 1, wherein the optically clear non-fluorinated film of the overlaminate article retains optical transparency for greater than 5 years.

19. A method of preparing a decorative construction comprising: providing a printed surface; providing an overlaminate article, wherein the overlaminate article comprises: an optically clear non-fluorinated film; and an optically transparent pressure sensitive adhesive layer disposed on the optically clear non-fluorinated film, wherein the optically transparent pressure sensitive adhesive comprises a (meth)acrylate-based pressure sensitive adhesive matrix and at least one UV absorber material, wherein the at least one UV absorber material is present in an amount of 5-13 weight % based on the total weight of the optically transparent pressure sensitive adhesive, and wherein the optically transparent pressure sensitive adhesive has a peel adhesion to printed film of at least 90 N / dm; and disposing the optically transparent pressure sensitive layer of the overlaminate article on the printed surface to form the decorative construction, such that upon exposure to weathering of 2513 MJ / m2of UV light, the printed surface retains more color than the same decorative article with an overlaminate article that has the same opticallytransparent pressure sensitive adhesive layer that does not contain the UV absorber material.

20. The method of claim 19, wherein the printed surface comprises a printed fdm.

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