TWI576237B - Primer compositions for optical films - Google Patents

Description

Primer composition for optical film

The present invention relates generally to optical films and laminates, and more particularly to primer compositions suitable for improving adhesion to optical films.

One problem often encountered in polymer film technology is that it is difficult to provide a strong adhesion between the substrate and the functional coating applied thereto. This is especially true for polyester based substrates. To solve this problem, a primer layer or coating is often applied to the polyester substrate to improve the adhesion between the substrate and the functional coating.

A primer technique that has been used to improve the adhesion between a polyester-based substrate and a functional coating applied thereto is the use of an amine decane coating as described in U.S. Patent No. 5,064,722 (Swofford et al.). Improving the adhesion at temperatures below freezing; as described in U.S. Patent No. 7,189,457 (Anderson), the use of PET (polyethylene terephthalate) film coated with a polyallylamine primer Adhesion to a PET film of a polyvinyl butyral or ionoplast resin layer; a glass laminate for reducing sound transmission as described in U.S. Patent No. 7,297,407 (Anderson), which may include a polyester film in two a three-layer laminate between different polymer layers; and a primer layer for a multilayer optical film, as described in PCT Publication No. WO 2009/123921, wherein the primer layer may comprise a sulfonic acid group Ester and crosslinker.

Articles are disclosed herein, including articles as optical films, and laminates. In some real In an embodiment, the article comprises a substrate having a first polyester surface and a second polyester surface, a crosslinked polyurethane-based primer applied to the surface of the first polyester, and adjacent to The crosslinked polyurethane-based primer is an optically clear heat activated adhesive. In some embodiments, the crosslinked polyurethane-based primer comprises a reaction product of a polyurethane-based dispersion and a crosslinking agent.

In some embodiments, the article comprises a substrate having a first polyester surface and a second polyester surface, a crosslinked polyurethane based coating applied to the first polyester surface and the second polyester surface. An ester primer and a pressure-sensitive adhesive layer of the crosslinked polyurethane-based primer adjacent to the surface of the first polyester.

Also disclosed is a laminate construction comprising a first inlaid glass substrate comprising a first major surface and a second major surface; a film article adhered to the first major surface of the first inlaid glass substrate, the film article comprising a substrate having a first polyester surface and a second polyester surface, a first crosslinked polyurethane-based primer coated on the surface of the first polyester, and coated on the second poly a second crosslinked polyurethane-based primer on the surface of the ester, and a first optically clear heat-activated adhesive adjacent to the first cross-linked polyurethane-based primer and A layer adjacent to the second crosslinked polyurethane-based primer.

Also disclosed is a method of making an article, the method comprising providing a substrate having a first polyester surface and a second polyester surface; applying a curable primer composition to the first polyester surface of the substrate or the second At least one of the polyester surfaces, wherein the curable primer composition comprises a polyurethane-based dispersion and a crosslinking agent; a dry curable primer composition; heating while stretching the substrate and curing A primer composition to form a crosslinked primer layer on the stretched polyester surface; and an optically clear heat activated adhesive applied to the crosslinked primer layer to form an optically clear heat activated adhesive layer.

Optical applications are increasingly using membranes. A wide variety of optical films contain a polyester surface. An optical film comprising a polyester surface comprises a polyester film, a multilayer film having an outer polyester film layer, and a film having a polyester coating or a polyester layer on the outer surface. In many cases it is desirable to surface treat the polyester surface of the film to aid in the ability of a functional coating, such as an adhesive layer, to adhere to the polyester surface of the film. This surface treatment may include physical surface treatment methods such as corona treatment, flame treatment, and the like, or it may involve chemical treatment, such as applying a primer coating. Because membranes are often used in optical applications, this surface treatment is required to not substantially alter the optical properties of the film. Not all of the above techniques have been successfully applied to polyester surfaces, and thus there is still a need for novel surface treatments for polyester surfaces of films such as optical films.

Heat activated adhesives are widely used in optical films. Some types of heat activated adhesives are particularly difficult to adhere to the polyester surface. This is especially true for heat activated adhesives such as polyvinyl butyral (PVB), a heat activated adhesive widely used in optical films. The use of conventional adhesion enhancement techniques (such as the use of surface treatments (such as corona or flame treatment)) and the use of conventional primers can sometimes improve adhesion, but it is not always useful. In particular, the non-suitability of various conventional primers will be discussed in detail below and in the Examples section. Therefore, there is still a need for a primer that enhances the adhesion of the heat activated adhesive to the surface of the polyester. In the present invention, a class of polyurethane based primers are described which are suitable for use in various polyester surfaces and heat activated adhesives. In addition, because the polyurethane-based primers described herein can be applied to the surface of the polyester so conveniently, they can also be applied to the surface of the polyester that is not coated with a heat activated adhesive to enhance Adhesion or other properties of other types of coatings. The primer coating is advantageous even without the application of other coatings because it provides enhanced roll gliding and easier roll-up and unwinding of the film roll.

All numbers expressing feature sizes, quantities, and physical properties used in the specification and claims are to be understood as being modified by the term "about" in all instances unless otherwise indicated. Therefore, unless indicated to the contrary, the numerical parameters set forth in the above description and the accompanying claims are intended to be The teachings shown seek to obtain an approximation of the desired nature. The recitation of numerical ranges by endpoints includes all numbers that are included in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within the scope.

The singular forms "a", "an" and "the" are intended to encompass the embodiment of the invention. For example, reference to "a layer" encompasses an embodiment having one, two or more layers. The term "or" is generally used in its meaning including "and/or" as used in the specification and the appended claims.

As used herein, the term "adhesive" refers to a polymeric composition suitable for bonding two adhesives together. Examples of the adhesive are heat activated adhesives and pressure sensitive adhesives.

The heat-activated adhesive is non-tacky at room temperature, but becomes viscous at high temperatures and can adhere to the substrate. Such adhesives generally have a temperature above the T _g (glass transition temperature) or melting point (T _m). When the temperature rises above T _g or T _m, the storage modulus usually decreases and the adhesive become sticky.

It is well known to those skilled in the art that pressure sensitive adhesive compositions have properties including (1) aggressive and permanent tack, (2) no more than a finger pressure, and (3) an ability to remain on the adhesive. And (4) a bonding strength sufficient to be cleanly removed from the adhesive. Materials which have been found to function well as pressure sensitive adhesives are polymers which have been designed and formulated to exhibit the requisite viscoelastic properties to provide the desired balance of tack, peel adhesion and shear retention. Getting the right balance of properties is not a simple process.

The term "(meth)acrylate" refers to a monomeric acrylic or methacrylic ester of an alcohol. Acrylate and methacrylate monomers or oligomers are collectively referred to herein as "(meth)acrylates." Polymers or copolymers described as "(meth)acrylate-based" polymers are predominantly (more than 50% by weight) prepared from (meth) acrylate monomers and may include other olefinic systems Unsaturated monomer.

Unless otherwise indicated, "optical transmission" refers to an article, film or adhesive composition having a high light transmission in at least a portion of the visible spectrum (about 400 to about 700 nm). The term "transmissive film" refers to a film having a thickness and visible through the thickness of the transparent film (on or adjacent to the substrate) when the film is placed on the substrate. In many embodiments, the transmissive film allows visible images to pass through the thickness of the film without substantially losing image clarity. In some embodiments, the transmissive film has a matt or shiny surface.

Unless otherwise indicated, "optically transparent" refers to an adhesive or article that exhibits high light transmission and exhibits low haze in at least a portion of the visible spectrum (about 400 to about 700 nm).

As used herein, the term "urethane-based" refers to a macromolecule that is a copolymer or block copolymer containing at least one urethane linkage. The urethane group has a general structure (-O-(CO)-NR-) wherein (CO) defines a carbonyl group C=O and R is hydrogen or an alkyl group. The term "block copolymer" refers to a copolymer of bonded segments, each segment primarily constituting a single structural unit or a single type of repeating unit.

As used herein, the term "adjacent" when referring to two layers means that the two layers are in close proximity to one another without voids therebetween. They may be in direct contact with each other (eg, laminated together) or there may be an intervening layer.

Disclosed herein is an article comprising a substrate having a first polyester surface and a second polyester surface, a crosslinked polyurethane-based primer applied to the surface of the first polyester, and adjacent thereto A cross-linked, polyurethane-based, optically clear heat-activated adhesive.

A wide variety of substrates having first and second polyester surfaces are suitable. In some embodiments, the substrate comprises a single polyester film. In other embodiments, the substrate comprises a film having an outer polyester coating or layer. In other embodiments, the film comprises a multilayer film having a film layer other than the polyester layer.

Examples of suitable polyester films include various films which contain a polymer containing a polyester. Suitable polyester polymers include, for example, terephthalate, isophthalate and/or naphthalene Polymers of formate comonomer units, such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and copolymers and blends thereof. Other examples of suitable polyester copolymers are provided in PCT Patent Publication Nos. WO 99/36262 and WO 99/36248. Various suitable polyester materials (including amorphous polyester resins) are available from Bostik, Middleton, MA, such as VITEL 1070B, 1750B and 3300B under the trade name VITEL; and from Evonik Degussa Corp., Parsippany, NJ under the trade name DYNAPOL. Such as DYNAPOL S1313, S1421, S1420, S1606 and S1611. Other suitable polyester materials include polycarbonates, polyarylates and other polymers containing naphthalates and terephthalates, such as polybutylene naphthalate (PBN), polynaphthalene dicarboxylic acid Propyl ester (PPN), polybutylene terephthalate (PBT), poly(trimethylene terephthalate) (PPT), and any of the above, in combination with other polyesters or non-polyester polymers Compounds and copolymers. The polymeric film may contain multiple layers of the same or different polyester materials, or may comprise one or more non-polyester layers (as described below).

An example of a suitable film having an outer polyester coating or layer includes a multilayer optical film having an outer polyester film layer. A variety of multilayer optical films having an outer film layer (which is a polyester material) are suitable. These multilayer optical films can comprise any of a variety of materials, including polyester and non-polyester layers, as long as the outer surface comprises a polyester film layer. Examples of suitable materials include polyesters such as polyethylene terephthalate, polyethylene naphthalate, copolymers based on naphthalene dicarboxylic acid or polyester blends; polycarbonate; polystyrene; benzene Ethylene-acrylonitrile; cellulose acetate; polyether oxime; poly(meth) acrylate, such as polymethyl methacrylate; polyurethane; polyvinyl chloride; polycycloolefin; polyimine; ; paper; or a combination or blend thereof. Specific examples include polyethylene terephthalate, polymethyl methacrylate, polyvinyl chloride, and cellulose triacetate. In some embodiments, the multilayer optical film comprises polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, polypropylene, polyester, polycarbonate, polymethyl methacrylate, poly Yttrium, polyamine or a blend thereof. In general, multilayer optical films are sufficient to withstand temperature and aging so that the performance of the article does not suffer over time. The thickness of the multilayer optical film is typically less than about 2.5 mm. The multilayer optical film can also be an orientable film, such as in a tenter The previously cast cast mesh substrate is oriented in operation.

Multilayer optical films are suitable for use in optical applications. Suitable multilayer optical films are designed to control the flow of light. It can have a transmittance of greater than about 90%, and a turbidity value of less than about 5% (eg, less than 2% or less than 1%). Properties considered when selecting a suitable multilayer optical film include mechanical properties such as flexibility, dimensional stability, self-sustaining force, and impact resistance. For example, a multilayer optical film may need to be structurally strong enough to allow an article to be assembled into a portion of a display device.

Multilayer optical films are used in a wide variety of applications, such as graphic arts and optical applications. Suitable multilayer optical films can be described as reflective films, polarizer films, reflective polarizer films, diffuse blended reflective polarizer films, diffuser films, brightness enhancing films, turning films, mirror films, or combinations thereof. A multilayer optical film can have ten or fewer layers, hundreds or even thousands of layers, all of which are made up of all birefringent optical layers, some birefringent optical layers, or all isotropic optical layers. Combined composition. In one embodiment, the multilayer optical film has alternating layers of first and second optical layers, wherein the refractive indices of the first and second optical layers along at least one axis differ by at least 0.04. Multilayer optical films having refractive index mismatch are described in the references cited below. In another embodiment, the multilayer optical film may comprise one or more of the above multilayer optical films such that the primer layer is embedded in either of them, thereby making the article itself a reflective film, polarizer A film, a reflective polarizer film, a diffuse blended reflective polarizer film, a diffuser film, a brightness enhancing film, a turning film, a mirror film, or a combination thereof. The optical film can contain a microstructured surface. In some embodiments, the optical film can contain a microstructured surface to redirect visible light.

Suitable multilayer optical films include VIKUITI Dual Brightness Enhancement Film (DBEF), VIKUITI Brightness Enhancement Film (BEF), VIKUITI Diffuse Reflectance Polarizer Film (DRPF), VIKUITI Enhanced Specular Reflector (ESR) and VIKUITI Advanced Polarizing Film (APF) Commercially available optical films sold, all available from 3M Company, St. Paul, MN. Suitable optical films are also described in the following patents: U.S. 5,825,543; 5,828,488 (Ouderkirk et al.); 5,867,316; 5,882,774; 6,179,948 B1 (Merrill et al.); 6,352,761 B1; 6,368,699 B1; 6,927,900 B2; 6,827,886 (Neavin et al); 6,972,813 B1 (Toyooka); 6,991,695; 2006/0084780 A1 (Hebrink et al); 2006/0216524 A1; /0226561 A1 (Merrill et al.); 2007/0047080 A1 (Stover et al.); WO 95/17303; WO 95/17691; WO 95/17692; WO 95/17699; WO 96/19347; WO 97/01440; 99/36248; and WO 99/36262. Such multilayer optical films are merely illustrative and are not intended to be an exhaustive list of suitable multilayer optical films that can be used.

The articles of the present invention also include a crosslinked polyurethane-based primer applied to the surface of the first polyester. In some embodiments, the crosslinked polyurethane-based primer is applied to two polyester surfaces. In other embodiments, the second polyester surface contains a surface treatment of a non-primer coating. The non-primer surface treatment includes, for example, flame treatment, plasma treatment, and corona treatment.

There is a primer on the surface of the first polyester to aid adhesion between the polyester film layer and the optically clear heat activated adhesive layer. It has been observed that heat activated adhesive layers are often difficult to adhere well to polyester films. In some cases, surface treatments such as corona, flame or plasma treatment may be sufficient to modify the surface of the polyester film to which the heat activated adhesive can adhere. However, it is not uncommon for such surface treatments to be insufficient to provide proper adhesion or to be ineffective in improving adhesion. Therefore, the polyurethane-based primer of the present invention was developed. The polyurethane based primer comprises a reaction product of a polyurethane based dispersion and a polyisocyanate crosslinking agent.

The polyurethane-based dispersion consists of, consists essentially of, or at least comprises a solvent-based or water-based polyurethane. In some embodiments, the polyurethane is a polyester based polyurethane, a polycarbonate based polyurethane, or a combination or blend of the two. The water-based polyurethane can be made from a water-based polyurethane dispersion (ie, PUD), and the solvent-based polyurethane can be Made from a solvent based polyurethane solution (ie PUS). PUDs may be required due to the elimination of volatile solvents typically associated with the use of PUS. Particularly desirable PUDs are polycarbonate based polyurethanes and polyester based polyurethanes. Examples of particularly suitable PUDs are described in PCT Publication WO 2006/118883 (Ho et al.).

The polyurethane may be the reaction product of one or more polyol segments with one or more diisocyanate segments. One or more triisocyanate segments may need to be used with a diisocyanate. It may be desirable to use up to about 10% of the triisocyanate segments with the diisocyanate based on the total weight of the reaction components. In some embodiments, the polyol is a polyester polyol, a polycarbonate polyol, or a combination of the two. It has also been found desirable to use diisocyanates such as isophorone diisocyanate, bis(4-isocyanate-cyclohexyl)methane or a combination of the two.

It is generally desirable to use aliphatic materials in the primer compositions of the present invention, especially when the primer composition is used in applications such as window inlaid glass applications. Examples of suitable materials include water-based aliphatic polyurethanes, polycaprolactone-based aliphatic thermoplastic polyurethanes, or both. Thus, in the preparation of polyurethanes, it may be desirable to use one or a combination of an aliphatic polyol, an aliphatic diisocyanate, and an aliphatic triisocyanate.

The polyurethane based primer also contains a crosslinking agent. The crosslinker can be a polyfunctional isocyanate functional material or a melamine formaldehyde crosslinker such as CYMEL 327 available from Cytec Industries, Inc., Woodland Park, NJ. In many embodiments, the crosslinking agent is a polyfunctional isocyanate functional compound. The polyfunctional isocyanate functional compound comprises at least two isocyanate groups (diisocyanates) and may contain more than two isocyanate groups (triisocyanates, tetraisocyanates, etc.). Examples of suitable diisocyanates include, but are not limited to, aromatic diisocyanates such as 2,6-cresyl diisocyanate, 2,5-cresyl diisocyanate, 2,4-cresyl diisocyanate, Diphenyl isocyanate, phenyl diisocyanate, methylene bis(o-chlorophenyl diisocyanate), methylene diphenyl phenyl 4,4'-diisocyanate, Methylene diphenyl phenyl diisocyanate modified with polycarbodiimide, (4,4'-diisocyanate Base-3,3',5,5'-tetraethyl)biphenylmethane, 4,4'-diisocyanate-3,3'-dimethoxybiphenyl, diisocyanate 5-chloro-2 , 4-methyl ester, 1-chloromethyl-2,4-diisocyanate benzene; aromatic-aliphatic diisocyanate, such as m-xylylene diisocyanate, tetramethyl-m-xylene diisocyanate Ester; aliphatic diisocyanate, such as 1,4-diisocyanate butane, 1,6-diisocyanate hexane, 1,12-diisocyanate decane, 2-methyl-1,5-diisocyanate a pentane; and a cycloaliphatic diisocyanate such as methylene-bicyclohexyl 4,4'-diisocyanate and 3-isocyanate methyl-3,5,5-trimethyl isocyanate - cyclohexyl ester (isophorone diisocyanate).

Suitable triisocyanates include aliphatic and aromatic triisocyanates and examples of such compounds include aliphatic triisocyanate 1,3,6-cyclohexyl triisocyanate, and aromatic triisocyanate polymethylene polyphenyl isocyanate (PAPI). .

Also suitable are isocyanates containing internal isocyanate-derived moieties such as triisocyanates containing biurets (eg DESMODUR N-100, available from Bayer), triisocyanates containing isocyanurate (eg IPDI-1890, available from Huls AG, Germany) and diisocyanates containing azetidinary diones (e.g., DESMODUR TT, available from Bayer). Other diisocyanates or triisocyanates are also suitable, such as DESMODUR L and DESMODUR W (both from Bayer) and tris-(4-isocyanatephenyl)-methane (purchased from Bayer as DESMODUR R).

Typically, the polyisocyanate crosslinker comprises an aliphatic diisocyanate, a blocked isocyanate or a combination thereof. Particularly suitable polyisocyanate crosslinkers are aliphatic isocyanate crosslinkers available from Bayer Material Science under the trade designation "BAYHYDOR", such as BAYHYDOR 303, BAYHYDOR 305, BAYHYDOR 401-70, BAYHYDOR XP2487/1 and BAYHYDOR XP7165; The trade name "ESAQUA" is available from Perstorp Polyols, Inc. Toledo, OH, an aliphatic isocyanate crosslinker such as ESAQUA XD 401 and ESAQUA XM 501.

Examples of suitable blocked isocyanates include the trade name BAYHYDOR VPLS 2310 and BAYHYDOR BL 5335 are available from blocked isocyanates of Bayer Material Science, and blocked isocyanates available from Baxenden Chemicals Limited under the tradenames TRIXENE B1 7986 and TRIXENE B1 7987.

A wide variety of optically clear heat activated adhesives can be used in conjunction with the above polyurethane based primers. Examples of suitable optically clear heat-activated adhesives include polyacrylate hot melt adhesives, polyvinyl butyral, ethylene vinyl acetate, ionomers, polyolefins, or combinations thereof.

The optically clear heat-activated adhesive may be a (meth) acrylate-based hot melt adhesive. Hot melt adhesives are typically prepared from (meth)acrylate polymers having a glass transition temperature ( _Tg ) above room temperature, more typically above about 40 °C, and prepared from alkyl (meth)acrylate monomers. . Suitable alkyl (meth)acrylates (ie, alkyl acrylate monomers) include linear or branched monofunctional unsaturated acrylates or methacrylates of non-tertiary alkyl alcohols, wherein the alkyl group has 4 to 14, especially 4 to 12 carbon atoms. The poly(meth)acrylic hot melt adhesive may also contain comonomer components as appropriate, such as (meth)acrylic acid, vinyl acetate, N-vinylpyrrolidone, (meth)acrylamide , vinyl esters, fumarates, styrene macromonomers, alkyl maleates and alkyl fumarates (based on maleic acid and fumaric acid, respectively) Or a combination thereof.

In some embodiments, the adhesive layer is at least partially formed from polyvinyl butyral. The polyvinyl butyral layer can be formed by a known aqueous or solvent based acetalization process in which polyvinyl alcohol is reacted with butyraldehyde in the presence of an acidic catalyst. In some cases, the polyvinyl butyral layer may comprise or be formed from polyvinyl butyral available from Solutia Incorporated (St. Louis, MO) under the trade designation "BUTVAR" resin.

In some cases, the polyvinyl butyral layer can be produced by mixing a resin with (as appropriate) a plasticizer and extruding the blend formulation through a sheet mold. If a plasticizer is included, the polyvinyl butyral may comprise from about 20 to 80 parts per hundred resin or from about 25 to 60 parts plasticizer. Examples of suitable plasticizers include polybasic acids or esters of polyhydric alcohols. Suitable for plasticizing The agent is bis(2-ethylbutyric acid) triethylene glycol ester, bis-(2-ethylhexanoic acid) triethylene glycol ester, diheptanoic acid triethylene glycol ester, diheptanoic acid tetrastrand Ethylene glycol ester, dihexyl adipate, dioctyl adipate, cyclohexyl adipate, cyclohexyl adipate, a mixture of heptyl adipate and decyl adipate, diisononyl adipate, Heptyl adipate, dibutyl sebacate, polymeric plasticizers (such as oil-modified sebacic alkyd resins), and phosphates and adipates (such as disclosed in U.S. Patent No. 3,841,890) And mixtures of adipates such as disclosed in U.S. Patent No. 4,144,217.

Examples of suitable ethylene vinyl acetate (EVA) adhesives include a wide variety of commercially available EVA hot melt adhesives. Typically, such EVA hot melt adhesives have a vinyl acetate content of from about 18% to about 29% by weight of the polymer. Adhesives typically have high levels of tackifiers and waxes. An exemplary composition is a composition having 30-40% by weight EVA polymer, 30-40% by weight tackifier, 20-30% by weight wax, and 0.5-1% by weight stabilizer. An example of a suitable EVA hot melt adhesive is the BYNEL series 3800 resin (including BYNEL 3810, BYIEL 3859, BYIEL 3860 and BYNEL 3861) available from DuPont, Wilmington, DE. A particularly suitable EVA hot melt adhesive is a material available from Bridgestone Corp. Tokyo, JP under the trade designation "EVASAFE".

An example of a suitable dispersing adhesive is "ionoplast resin". The ionoplast resin is a copolymer of ethylene and an unsaturated carboxylic acid in which at least a portion of the acidic groups in the copolymer have been neutralized in the form of an acid salt. Extruded sheets of ionoplast resin suitable for use in the present invention are commercially available from DuPont Chemicals, Wilmington, DE under the trade designation "SENTRYGLASS PLUS".

Examples of suitable polyolefin adhesives include ethylene/α-olefin copolymers. As used herein, the term "ethylene/α-olefin copolymer" refers to a polymer comprising a class of hydrocarbons produced by catalytic oligomerization (ie, polymerization to a low molecular weight product) of ethylene and a linear alpha-olefin monomer. . The ethylene/α-olefin copolymer can be catalyzed, for example, using a single site catalyst (such as a metallocene catalyst) or a multi-site catalyst (such as Ziegler-Natta and Phillips). Made). The linear alpha-olefin monomer is typically 1-butene or 1-octene, but may be in the range of C3 to C20 straight chain, branched chain or cyclic alpha-olefin. The α-olefin may be a branched olefin only when the branched chain is at least the alpha position of the double bond, such as 3-methyl-1-pentene. Examples of the C3-C20 α-olefin include propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. The α-olefin may also contain a cyclic structure such as cyclohexane or cyclopentane to produce an α-olefin such as 3-cyclohexyl-1 propylene (allyl cyclohexane) and vinylcyclohexane. Although not an alpha-olefin in the typical sense of the term, certain cyclic olefins, such as norbornene and related olefins, are alpha-olefins and may be used for the purposes of the present invention. Similarly, for the purposes of the present invention, styrene and its related olefins (e.g., alpha-methyl styrene) are alpha olefins. However, for the purposes of the present invention, acrylic acid and methacrylic acid and their individual ionomers, as well as acrylates and methacrylates, are not alpha-olefins. Illustrative ethylene/α-olefin copolymers include ethylene/1-butene, ethylene/1-octene, ethylene/1-butene/1-octene, ethylene/styrene. The polymers can be block or random polymers. Exemplary commercially available low crystalline ethylene/alpha-olefin copolymers are sold under the trade designation "ENGAGE" ethylene/1-butene and ethylene/1-octene copolymers and "FLEXOMER" ethylene/1-hexene copolymers. Resins from Dow Chemical Co.; and homogeneous branched chains, substantially linear ethylene/α-olefin copolymers such as "TAFMER" from Mitsui Petrochemicals Company Limited and "EXACT" from ExxonMobil Corp. As used herein, the term "copolymer" refers to a polymer made from at least two monomers.

In some such embodiments, the alpha-olefin portion of the ethylene/[alpha]-olefin copolymer comprises four or more carbons. In some embodiments, the ethylene/[alpha]-olefin copolymer is a low crystalline ethylene/[alpha]-olefin copolymer. As used herein, the term "low crystallization" means that the degree of crystallinity (as disclosed in ASTM F2625-07) is less than 50% by weight. In some embodiments, the low crystalline ethylene/[alpha]-olefin copolymer is a butene alpha-olefin. In some embodiments, the alpha-olefin of the low crystalline ethylene/[alpha]-olefin copolymer has 4 or more carbons.

In some embodiments, the low crystalline ethylene/α-olefin copolymer has a small DSC melting point At or equal to 50 ° C. As used herein, the term "DSC peak melting point" means the melting point determined by DSC (10 ° C/min) as the peak having the largest area under the DSC curve under nitrogen purge.

As noted above, the articles of the present invention may also comprise a crosslinked polyurethane-based primer applied to the surface of the second polyester of the substrate. The crosslinked polyurethane-based primer can be the same as or different from the cross-linked polyurethane-based primer applied to the first polyester surface of the substrate. Typically, the crosslinked polyurethane based primers are the same for ease of coating and handling. Suitable crosslinked polyurethane based primers are described in detail above.

Like the first polyester surface of the substrate, the crosslinked polyurethane-based primer coating on the second polyester surface of the substrate may also be adjacent to the crosslinked polyurethane based A layer of primer coating. This layer may comprise an optically clear heat activated adhesive layer, a cured hard coat layer, an optical layer or a pressure sensitive adhesive layer.

Optically clear heat activated adhesives are described in detail above. If the layer of the crosslinked polyurethane-based primer coating on the surface of the second polyester adjacent to the substrate is an optically transparent heat-activated adhesive, it may be adjacent to the first layer adjacent to the substrate The cross-linked, polyurethane-based primer-coated optically clear heat-activated adhesive on the surface of the ester is the same or different.

In some embodiments, it may be desirable for the second polyester surface to contain a layer that is not an optically clear heat activated adhesive, such as a cured hard cover layer, an optical layer, or a pressure sensitive adhesive layer.

A hard mask is a coating that is typically placed on a surface to provide protection, such as abrasion resistance and paint resistance. Typically, the hard cover surface is optically transmissive. The hard cover layer can be made of any suitably curable polymeric material. As used herein, "polymeric material" is understood to include polymers, copolymers (eg, polymers formed using two or more different monomers), oligomers, and combinations thereof, as well as miscible blends. A polymer, copolymer or oligomer formed in the form of a compound. Examples of materials suitable for the hard cover layer are polyfunctional or crosslinkable monomers. Examples of suitable hard cover layers include U.S. Patent Publication No. 2009/0000727 (Kumar et al.). Said.

Examples of crosslinkable monomers include polyfunctional acrylates, urethanes, urethane acrylates, decanes, and epoxides. In some embodiments, the crosslinkable monomer comprises a mixture of a polyfunctional acrylate, an urethane acrylate, or an epoxide.

Suitable acrylates include, for example, poly(meth)acrylonitrile monomers, such as compounds containing bis(methyl) propylene fluorenyl, compounds containing tris(meth) propylene thiol, containing higher functionality (methyl a compound of an acrylonitrile group and an oligo(meth)acrylonitrile compound.

Suitable compounds containing a bis(meth)acrylonitrile group include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 - hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexane dihydric alcohol diacrylate, alkoxylated hexane Alcohol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, caprolactone modified neopentyl glycol hydroxypivalic acid Ester diacrylate, cyclohexane dimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol A diacrylate, ethoxylated (3 Bisphenol A diacrylate, ethoxylated (30) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, hydroxypivalaldehyde modified trimethylolpropane diacrylate Ester, neopentyl glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxy Neopentyl glycol diacrylate, tetraethylene glycol diacrylate extending, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate and extend three projecting glycol diacrylate.

Suitable compounds containing tris(meth)acrylinyl groups include glyceryl triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylate (eg ethoxylated (3) trimethylolpropane III Acrylate, ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate ), pentaerythritol triacrylate, propoxylated triacrylate (eg propoxylated (3) Triacrylate, propoxylated (5.5) glyceryl triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane triacrylate), Trimethylolpropane triacrylate, pentaerythritol triacrylate and bis(2-hydroxyethyl)isomeric cyanide triacrylate.

Suitable compounds containing higher functional (meth) acrylonitrile include di-trimethylolpropane tetraacrylate, diisopentyltetraol pentoxide, ethoxylated (4) isovaerythritol tetraacrylate Ester, pentaerythritol tetraacrylate and caprolactone modified diisoamyltetraol hexaacrylate.

Suitable oligo(meth) propylene fluorenyl compounds include urethane acrylates, polyester acrylates, epoxy acrylates; polypropylene phthalamide analogs of the above, such as N,N-dimethyl propylene Indoleamine; and combinations thereof.

Many poly(meth)acrylonitrile monomers are widely available from, for example, the following suppliers: Sartomer Company, Exton, Pa.; UCB Chemicals Corporation, Smyrna, Ga.; and Aldrich Chemical Company, Milwaukee, Wis. Other suitable (meth) acrylate materials include poly(meth) acrylates containing a carbamide moiety, as described, for example, in U.S. Patent No. 4,262,072 (Wendling et al.).

In an illustrative embodiment, the hard cap layer comprises a monomer having at least two or three (meth) acrylate functional groups. Commercially available crosslinkable acrylate monomers include monomers available from Sartomer Company, Exton, Pa., such as trimethylolpropane triacrylate available under the trade designation SR351, and isoamyl 4 available under the trade designation SR444. Alcohol triacrylate, diisoamyl alcohol triacrylate available under the trade name SR399LV, ethoxylated (3) trimethylolpropane triacrylate available under the trade name SR454, available under the trade name SR494 Ethoxylated (4) isovaerythritol triacrylate, ginseng (2-hydroxyethyl) isomeric cyanurate triacrylate available under the trade designation SR368 and available in the product name SR508 Propylene glycol diacrylate.

Suitable urethane acrylate monomers include, for example, from EBECRYL 8301 Radcure UCB Chemicals (Smyrna, Ga.), hexafunctional urethane urethane available from Sartomer Company (Exton, Pa.) with CN981 and CN981B88, and bifunctional acrylate amine available from Radcure UCB Chemicals as EBECRYL 8402 Carbamate. In some embodiments, the hard cap layer resin comprises a poly(meth)acrylate and polyurethane material, which may be referred to as "acrylic acid urethane."

In some embodiments, the hard cap layer can include a plurality of inorganic nanoparticles. The inorganic nanoparticles may include, for example, ceria, alumina or zirconia (the term "zirconia" includes zirconia metal oxide) nanoparticles. In some embodiments, the nanoparticles have an average diameter in the range of 1 to 200 nm or 5 to 150 nm or 5 to 125 nm. The content of the nanoparticles may be from 10 to 200 parts per 100 parts of the hard coat monomer.

Suitable cerium oxide nanoparticles are available from Nalco Chemical Co. (Naperville, Ill.) under the product designation NALCO COLLOIDAL SILICAS. For example, cerium oxide includes NALCO products 1040, 1042, 1050, 1060, 2327, and 2329. Suitable zirconia nanoparticles are available from Nalco Chemical Co. (Naperville, Ill.) under the product designation NALCO OOSSOO8.

The surface treatment or surface modification of the nanoparticles can provide a stable dispersion in the hard coat resin. The surface treatment stabilizes the nanoparticles so that the particles will disperse well in the polymerizable resin and produce a substantially homogeneous composition. Further, the nanoparticles may be modified with a surface treating agent on at least a portion of their surface such that the stabilized particles may be copolymerized or reacted with the polymerizable hard cover resin during curing.

A photoinitiator can be included in the hard cap layer. Examples of the initiator include organic peroxides, azo compounds, quinine, nitro compounds, mercapto halides, hydrazines, mercapto compounds, hydroquinone compounds, imidazoles, chlorotriazines, benzoin, benzoin alkyl ethers, diketones. Phenyl ketone and its analogues. Commercially available photoinitiators include under the tradenames DAROCUR 1173, DAROCUR 4265, IRGACURE 651, IRGACURE 184, IRGACURE 1800, IRGACURE 369, IRGACURE 1700, IRGACURE 907, IRGACURE 819 was purchased from Ciba Geigy and a photoinitiator available from Aceto Corp. (Lake Success, N.Y.) under the trade designations UV1-6976 and UV1-6992. Phenyl hexafluoroantimonate [p-(2-hydroxytetradecyloxy)phenyl]anthracene is a photoinitiator available from Gelest (Tullytown, Pa.). Phosphine oxide derivatives include LUCIRIN TPO available from BASF (Charlotte, N. C.) which is 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. In addition, other suitable photoinitiators are described in U.S. Patent Nos. 4,250,311, 3,708,296, 4,069,055, 4,216,288, 5,084,586, 5,124,417, 5,554,664, and 5,672,637. The photoinitiator can be used in a concentration of from about 0.1 to 10% by weight or from about 0.1 to 5% by weight, based on the organic portion (phr) of the formulation.

Examples of optical layers include almost any layer for controlling light. These include various optical films and coatings. As used herein, the term "optical film" refers to a film that can be used to create an optical effect. The optical film is usually a film containing a polymer, which may be a single layer or multiple layers. The optical film is flexible and can have any suitable thickness. The optical film is often at least partially transmissive, reflective, anti-reflective, polarized, optically transparent or diffuse for some wavelengths of the electromagnetic spectrum, such as the visible, ultraviolet or infrared wavelengths of the electromagnetic spectrum. Exemplary optical films include, but are not limited to, visible mirror films, colored mirror films, solar reflective films, infrared reflective films, ultraviolet reflective films, reflective polarizer films (such as brightness enhancing films and dual brightness enhancing films), and absorbing polarizer films. , optical transparent film, dye film and anti-reflection film. The optical film can contain a microstructured surface. In some embodiments, the optical film can contain a microstructured surface to redirect visible light.

In some embodiments, the optical layer can be a coating or can include an optical film having a coating. In general, coatings are used to enhance the function of the film or to provide other functionality to the film. Examples of coatings include, for example, a hard cover (as described above), an anti-fog coating, a scratch resistant coating, a security coating, or a combination thereof. Coatings such as hard covers, anti-fog coatings and scratch-resistant coatings provide enhanced durability. Examples of security coatings include, for example, opaque or enamel coatings that provide opaque viewing or louvered films that limit viewing angles.

Suitable pressure sensitive adhesives include natural rubber, synthetic rubber, and styrene based A pressure sensitive adhesive of a segment copolymer, a polyvinyl ether, an acrylic acid, a poly-α-olefin, a polyfluorene oxide, a urethane or a urea.

Suitable natural rubber pressure sensitive adhesives generally comprise artificial natural rubber, from 25 parts to 300 parts of one or more tackifying resins per 100 parts of natural rubber and usually from 0.5 to 2.0 parts of one or more antioxidants. Natural rubber grades can range from light-colored ruin rubber grade to dark crepe tobacco rubber and include examples such as CV-60 (Control Viscose Rubber Grade) and SMR-5 (Wrinkle Smoke Sheet Rubber Grade).

The tackifying resins used with natural rubber generally include, but are not limited to, wood rosin and its hydrogenated derivatives; various softening point bismuth resins, and petroleum based resins such as the "ESCOREZ 1300" series C5 aliphatic olefins from Exxon. Derivatized resins and "PICCOLYTE S" series from Hercules, Inc. The use of antioxidants delays the oxidative attack on natural rubber, which results in a loss of bond strength of the natural rubber adhesive. Suitable antioxidants include, but are not limited to, amines such as N-N' bis-β-naphthyl-1,4-phenylenediamine available as "AGERITE D"; phenolic systems such as "SANTOVAR A" 2,5-di-(tripentyl)hydroquinone from Monsanto Chemical Co., 购[3-(3',5'-di-t-butyl) available from Ciba-Geigy Corp. as "IRGANOX 1010" -4'-hydroxyphenyl)methylene propionate]methane and 2-2'-methylenebis(4-methyl-6-tert-butylphenol) commercially available as antioxidant 2246; and disulfide A urethane such as zinc dithiodibutylcarbamate. Other materials may be added to the natural rubber adhesive for special purposes, wherein the addition may include a plasticizer, a pigment, and a curing agent for the partially vulcanized pressure-sensitive adhesive.

Another type of pressure sensitive adhesive is a pressure sensitive adhesive comprising synthetic rubber. These adhesives are generally rubbery elastomers which are self-adhesive or non-tacky and require a tackifier.

Self-adhesive synthetic rubber pressure sensitive adhesives include, for example, butyl rubber, isobutylene copolymers containing less than 3% isoprene, polyisobutylene, isoprene homopolymer, polybutadiene (such as "TAKTENE 220 BAYER"") or styrene / butadiene rubber. Butyl rubber pressure sensitive adhesives often contain an antioxidant such as zinc dibutyl dithiocarbamate. Polyisobutylene pressure sensitive adhesives typically do not contain an antioxidant. Synthetic rubber pressure sensitive adhesives generally require tackifiers and are generally easier to melt process. It comprises polybutadiene or styrene/butadiene rubber, from 10 parts to 200 parts of tackifier and generally from 0.5 to 2.0 parts of antioxidant per 100 parts of rubber (such as "IRGANOX 1010"). An example of a synthetic rubber is "AMERIPOL 1011A", a styrene/butadiene rubber available from BF Goodrich. Suitable tackifiers include rosin derivatives such as "FORAL 85" (a stable rosin ester from Hercules, Inc.), "SNOWTACK" series rosin gum from Tenneco and "AQUATAC" series high oil rosin from Sylvachem; Synthetic hydrocarbon resins such as "PICCOLYTE A" series (from Hercules, Inc.), "ESCOREZ 1300" series C ₅ aliphatic olefin derived resins, "ESCOREZ 2000" series C ₉ aromatic/aliphatic olefin derived resins and poly C ₉ aromatic resins, such as those from Hercules, Inc of the "PICCO 5000" series of aromatic hydrocarbon resins. Other materials may be added for special purposes, including hydrogenated butyl rubber, pigments, plasticizers, liquid rubbers (such as "VISTANEX LMMH" polyisobutylene liquid rubber available from Exxon) and curing agents for partially vulcanized adhesives.

The styrene block copolymer pressure sensitive adhesive generally comprises an AB or ABA type elastomer, wherein A represents a thermoplastic polystyrene block and B represents polyisoprene, polybutadiene or poly(ethylene/butene). And rubbery block of resin. Examples of various block copolymers suitable for use in the block copolymer pressure sensitive adhesive include linear, radial, star and wedge styrene-isoprene block copolymers such as those available from Shell Chemical Co. "KRATON D1107P" and "EUROPRENE SOL TE 9110" from EniChem Elastomers Americas, Inc.; linear styrene-(ethylene-butylene) block copolymer such as "KRATON G1657" from Shell Chemical Co.; linear Styrene-(ethylene-propylene) block copolymers such as "KRATON G1750X" available from Shell Chemical Co.; and linear, radial and star styrene-butadiene block copolymers such as those available from Shell Chemical Co. KRATON D1118X and purchased from EniChem Elastomers Americas, Inc "EUROPRENE SOL TE 6205". The polystyrene block tends to form a domain of a spherical body, a cylinder or a plate-like shape, so that the block copolymer pressure-sensitive adhesive has a two-phase structure. Resins combined with rubber generally produce stickiness in pressure sensitive adhesives. Examples of the rubber phase-binding resin include aliphatic olefin-derived resins such as "ESCOREZ 1300" series and "WINGTACK" series available from Goodyear; rosin esters such as "FORAL" series and "STAYBELITE" ester 10, both of which are purchased from Hercules. , Inc.; hydrogenated hydrocarbons such as the "ESCOREZ 5000" series available from Exxon; polyterpenes such as the "PICCOLYTE A" series; and phenolic resins derived from petroleum or turpentine sources, such as "PICCOFYN" from Hercules, Inc. A100". Resins combined with thermoplastics tend to stiffen the pressure sensitive adhesive. Thermoplastic phase-binding resins include polyaromatics such as the "PICCO 6000" series of aromatic hydrocarbon resins available from Hercules, Inc.; coumarone-indene resins such as the "CUMAR" series available from Neville; and derived from coal tar or Other high solubility parameter resins with petroleum and softening points above about 85 ° C, such as the "AMOCO 18" series alpha methyl styrene resin available from Amoco, "PICCOVAR 130" alkyl aromatic polyfluorene available from Hercules, Inc. Resin and "PICCOTEX" series of alpha methyl styrene / vinyl toluene resin available from Hercules. Other materials may be added for special purposes, including rubber phase plasticized hydrocarbon oils such as "TUFFLO 6056" from Lydondell Petrochemical Co., polybutene-8 from Chevron, "KAYDOL" from Witco and purchased from Shell. "SHELLFLEX 371" of Chemical Co.; pigments; antioxidants such as "IRGANOX 1010" and "IRGANOX 1076" (both from Ciba-Geigy Corp.), "BUTAZATE" from Uniroyal Chemical Co., purchased from American Cyanamid's "CYANOX LDTP" and "BUTASAN" from Monsanto Co.; anti-ozonants such as "NBC" (a nickel dibutyl dithiocarbamate) from DuPont; liquid rubber such as "VISTANEX LMMH" Polyisobutylene rubber; and ultraviolet light inhibitors such as "IRGANOX 1010" and "TINUVIN P" available from Ciba-Geigy Corp.

Polyvinyl ether pressure sensitive adhesives are generally blends of homopolymers of vinyl methyl ether, vinyl ethyl ether or vinyl isobutyl ether, or homopolymers of vinyl ethers and vinyl ethers. A blend of acrylate copolymers that are used to achieve the desired pressure sensitive properties. Depending on the degree of polymerization, the homopolymer may be a viscous oil, a viscous soft resin or a rubbery substance. The polyvinyl ether used as a raw material in the polyvinyl ether adhesive includes a polymer based on vinyl methyl ether such as "LUTANOL M 40" available from BASF, and "GANTREZ M" from ISP Technologies, Inc. 574" and "GANTREZ 555"; vinyl ethyl ethers such as "LUTANOL A 25", "LUTANOL A 50" and "LUTANOL A 100"; vinyl isobutyl ether such as "LUTANOL I30", "LUTANOL I60" "LUTANOL IC", "LUTANOL I60D" and "LUTANOL I 65D"; methacrylate/vinyl isobutyl ether/acrylic acid, such as "ACRONAL 550 D" available from BASF. Antioxidants suitable for stabilizing the polyvinyl ether pressure-sensitive adhesive include, for example, "IONOX 30" available from Shell, "IRGANOX 1010" from Ciba-Geigy, and "ZKF" from Bayer Leverkusen. Other materials may be added for special purposes, including tackifiers, plasticizers, and pigments, as described in the BASF literature.

The acrylic pressure-sensitive adhesive generally has a glass transition temperature of about -20 ° C or lower and may contain 100 to 80% by weight of a C ₃ -C ₁₂ alkyl ester component, such as isooctyl acrylate or 2-ethyl acrylate. -hexyl ester and n-butyl acrylate; and 0 to 20% by weight of a polar component such as acrylic acid, methacrylic acid, ethylene vinyl acetate, N-vinylpyrrolidone and styrene macromonomer. Generally, the acrylic pressure-sensitive adhesive contains 0 to 20% by weight of acrylic acid and 100 to 80% by weight of isooctyl acrylate. Acrylic pressure-sensitive adhesives may be self-adhesive or tackified. Suitable tackifiers for acrylics are rosin esters such as "FORAL 85" available from Hercules, Inc.; aromatic resins such as "PICCOTEX LC-55WK"; aliphatic resins such as those available from Hercules, Inc. "PICCOTAC 95"; and anthracene resins such as α-pinene and β-pinene available from "PICCOLYTE A-115" and "ZONAREZ B-100" from Arizona Chemical Co. Other materials may be added for special purposes, including hydrogenated butyl rubber, pigments and curing agents for partially vulcanized adhesives.

Poly-α-olefin pressure-sensitive adhesives, also known as poly(1-olefin) pressure-sensitive adhesives, generally comprising, for example, U.S. Patent No. 5,209,971 (Babu et al.) incorporated herein by reference. The substantially uncrosslinked polymer or uncrosslinked polymer to which the radioactive functional group is grafted may be grafted thereon. The poly-[alpha]-olefin polymer can be self-adhesive and/or include one or more tackifying materials. If not crosslinked, the intrinsic viscosity of the polymer is generally between about 0.7 dL/g and 5.0 dL/g as measured by ASTM D 2857-93 "Standard Specification for Viscosity of Diluent Solutions of Polymers". Additionally, the polymer is generally predominantly amorphous. Suitable poly-α-olefin polymers include, for example, C ₃ -C ₁₈ poly(1-olefin) polymers, typically C ₅ -C ₁₂ alpha-olefins and their alpha-olefins with C ₃ or C ₆ -C ₈ the α- olefin copolymers and their copolymers with C ₃ of. The tackifying material is usually a resin which is miscible in the poly-α-olefin polymer. The total amount of the tackifying resin in the poly-α-olefin polymer is in the range of from 0 to 150 parts by weight per 100 parts of the poly-α-olefin polymer, depending on the particular application. The resin comprises a viscosity increasing applied by polymerizing a C ₅ to C ₉ unsaturated hydrocarbon monomers, polyterpenes, synthetic polyterpene resin and the like and derivatives of. Examples of such commercially available resins based on a C ₅ olefin fraction of this type available from the Goodyear Tire and Rubber Co's "WINGTACK 95" and "WINGTACK 15" by sticky resin. Other hydrocarbon resins include "REGALREZ 1078" and "REGALREZ 1126" available from Hercules Chemical Co., and "ARKON P115" from Arakawa Chemical Co. Other materials may be added for special purposes including antioxidants, fillers, pigments, and radioactive crosslinkers.

Polyoxygen pressure sensitive adhesives contain two main components, polymers or gums and tackifying resins. The polymer is typically a high molecular weight polydimethyl methoxyoxane or polydimethyldiphenyl decane having a residual stanol functional group (SiOH) at the end of the polymer chain or comprising a polydiorganotoxime A block copolymer of a soft segment and a urea-terminated hard segment. The tackifying resin is typically a three dimensional phthalate structure that is capped with trimethyl decyloxy (OSiMe ₃ ) and also contains some residual stanol functional groups. Examples of tackifying resins include SR 545 from General Electric Co., Silicone Resins Division, Waterford, NY, and MQD-32-2 from Shin-Etsu Silicones of America, Inc., Torrance, Calif. The manufacture of a typical polyoxyxene pressure sensitive adhesive is described in U.S. Patent No. 2,736,721 (Dexter). The manufacture of polyoxyxazone block copolymer pressure sensitive adhesives is described in U.S. Patent No. 5,214,119 (Leir et al.). Other materials may be added for special purposes including pigments, plasticizers and fillers. The filler is usually used in an amount of from 0 to 10 parts per 100 parts of the polyoxygen pressure-sensitive adhesive. Examples of the filler which can be used include zinc oxide, cerium oxide, carbon black, pigments, metal powders, and calcium carbonate.

Suitable polyurethanes and suitable polyurea pressure sensitive adhesives include, for example, WO 00/75210 (Kinning et al.) and U.S. Patent Nos. 3,718,712 (Tushaus), 3,437,622 (Dahl) and 5,591,820 ( Revealed in Kydonieus et al.).

Also disclosed is an article comprising a substrate having a first polyester surface and a second polyester surface, a crosslinked polyurethane-based primer applied to the surface of the first polyester, and adjacent thereto A cross-linked polyurethane-based pressure sensitive adhesive layer is substituted for the heat activated adhesive. Examples of suitable pressure sensitive adhesives include those described above.

As with the above items, the second polyester surface of the substrate may also comprise a crosslinked polyurethane-based primer coating. The crosslinked polyurethane-based primer can be the same as or different from the cross-linked polyurethane-based primer applied to the first polyester surface of the substrate. Typically, such crosslinked polyurethane based primers are also easy to apply and handle. Suitable crosslinked polyurethane based primers are described in detail above.

The film article may be used to prepare a laminate article comprising a substrate having a first polyester surface and a second polyester surface and a coating applied to the first polyester surface and the second polyester surface A polyurethane based primer. In such laminate articles, the film article is adhered to the inlaid glass substrate.

A wide variety of mosaic glass substrates are suitable for use in the laminate articles of the present invention. In some embodiments, there is a single damascene glass substrate, and in other embodiments, there are multiple damascene glass substrate. In some embodiments, the above primed film article is attached to the outer surface of the inlaid glass substrate, and in other embodiments, the above primed film article is positioned between the two inlaid glass substrates.

Suitable inlaid glass substrates are at least optically transmissive and can be optically transparent. Examples of suitable substrates include, for example, windows. The window can be made from a variety of different types of inlaid glass substrates (such as a variety of glasses) or from polymeric materials such as polycarbonate or polymethyl methacrylate. In some embodiments, the window may also include other layers or processes. Examples of other layers include, for example, other layers designed to provide films of dyeing, chipping resistance, and the like. Examples of other processing that the window may be present include, for example, coatings or various types (such as hard masks), and etching (such as decorative etching).

In some embodiments, the first and second crosslinked polyurethane-based primer coatings have an optically clear heat-activated adhesive layer adjacent to the primer coating. In other embodiments, one of the polyurethane-based primer coatings has an optically clear heat-activated adhesive layer adjacent to the primer coating and the other is based on a polyurethane-based primer layer. The lacquer coating has a layer adjacent to the primer layer. As noted above, the layer can be a cured hard mask, an optical layer, or a pressure sensitive adhesive. An article having two optically clear heat-activated adhesive layers or an optically clear heat-activated adhesive layer and a pressure-sensitive adhesive layer can be used to prepare a sandwich laminate, that is, wherein the film article is interposed between two embedded glass substrates between.

Typically, the laminates have desirable optical properties such as high luminescent transmittance and low turbidity. Typically, the laminates of the present invention have an illuminating transmittance of at least about 90% and a haze of less than about 3% in the 400 to 700 nm wavelength range. Both the luminescent transmittance and the turbidity can be determined using, for example, the method of ASTM-D 1003-95.

Methods for preparing articles are also disclosed. The method includes providing a substrate having a first polyester surface and a second polyester surface, the curable primer composition being applied to at least one of the first polyester surface or the second polyester surface of the substrate Drying the curable primer composition, heating and simultaneously stretching the substrate and the curable primer composition to the stretched polyester sheet A crosslinked primer layer is formed on the face, and an optically clear heat activated adhesive is applied to the crosslinked primer layer to form an optically clear heat activated adhesive layer. Because the curable primer composition is applied to the substrate prior to heating while stretching (a process known as "stretching"), the curable primer coating is sometimes referred to as a "staggered front coating." The curable tenter primer coating comprises a polyurethane based dispersion and a crosslinking agent such as those described in detail above.

In some embodiments, a primer composition is applied to the first polyester surface of the substrate and the second polyester surface to form first and second cured primer layers. Coating the two surfaces not only provides an article having two surfaces suitable for receiving other coatings, but also provides two identical items. Having the same film on both sides eliminates the need to remember which side has a primer coating during processing. Additionally, it has been discovered that the primer coatings of the present invention provide increased film handling capabilities in addition to providing a modified surface suitable for receiving other coatings. This increased film handling capability includes, for example, enhanced roll gliding and easier roll-up and unwinding of the film roll. In some embodiments, this enhanced slip can be achieved or enhanced by including various polymeric or inorganic additives in the primer composition. Such additives include, for example, slip additives such as water-based dispersions of aerosolized cerium oxide available from Degussa Corporation (Parsippany, NJ) under "AERODISP W 1226."

The curable primer coating can be applied to one or both of the polyester surfaces of the substrate using any suitable coating or coating method or combination of methods suitable for coating a water-based or solvent-based mixture. Examples of suitable coating equipment include a knife coater, a roll coater, a reverse roll coater, a notch bar coater, a curtain coater, a rotary gravure coater, a rotary press, and the like. . The viscosity of the aqueous or solvent mixture can be adjusted to suit the type of coater used. After application of the coating, it can be dried by any suitable drying process. Examples of suitable drying processes include air drying and application of heat for drying, such as the use of IR lamps or ovens (such as forced air ovens).

After drying the primer layer on the substrate, the coated substrate can then be drawn or stretched in one or two dimensions to orient the film. Process for orienting a film (especially a polyester film) is described in the polymerization The Encyclopedia of Polymer Science and Engineering, Vol. 12, vol. 12, pp. 193-216. A typical process for making a biaxially oriented polyester film comprises four main steps: (1) melt extruding the polyester resin and quenching it to form a web; (2) stretching the web in the machine direction or machine direction (3) subsequently or simultaneously stretching the web in a lateral direction to form a film; and (4) heat setting the film. If biaxial orientation is desired, the primer composition can be applied to the multilayer optical film after the multilayer optical film has been stretched in the machine direction, but before it is subsequently stretched in the cross direction. Further discussion regarding the orientation of polymeric membranes can be found, for example, in PCT Publication WO 2006/130142. Multilayer optical films are typically produced in a process utilizing a draw ratio in the range of 6: 1 or greater, significantly above 3.5: 1-4: 1 for the preparation of monolithic PET films. Unlike many of the primers used in the art, it has been found that the primers of the present invention produce coatings having good clarity, decorative and adhesive properties (even after stretching at 6:1).

After the primed film article is stretched and oriented, a plurality of different layers can be contacted with the primer surface. These layers are an optically transparent hard mask layer, a hard mask layer, an optical layer, and a pressure sensitive adhesive layer. All of these layers are described in detail above and can be applied using conventional coating or lamination techniques.

Instance

The advantages and embodiments of the present invention are further illustrated by the following examples, but the particular materials and amounts thereof, as well as other conditions and details, are not to be construed as limiting the invention. In these examples, all percentages, ratios, and ratios are by weight unless otherwise indicated.

These abbreviations are used in the following examples: g = gram; min = minute; mol = mole; hr = hour; mL = milliliter; nm = nanometer; wt = weight; fpm = 呎 / minute; psi = pound / square 吋; kPa = kilopascals; PSA = pressure sensitive adhesive. Chemicals were purchased from Sigma-Aldrich, St. Louis, MO, unless otherwise indicated.

material list

Synthetic polyurethane dispersion 3

The isocyanate-terminated prepolymer was prepared as follows in pounds per 100 pounds of feed. Polyol-1 (0.003 equivalents), polyol-1 (0.020 equivalents) and dimethylpropionic acid (0.024 equivalents from GEO Specialty Chemicals) in 2-butanone were gradually treated with 80% H12MDI solution (0.069 eq.). 70% solids) and a mixture of dibutyltin dilaurate catalyst (0.1 wt%, available from Air Products Chemicals Inc). The mixture was stirred at 102 ° C (215 ° F) for 3-4 hours. The resulting prepolymer solution was cooled to 79 ° C (175 ° F), then gradually added to triethylamine (0.009 equivalents, available from Air Products and Chemicals Inc.) and ethylenediamine (0.017 equivalents, available from Dow Chemical Company). ) in a dilute aqueous solution. The mixture was stirred under high agitation for 1 hour, followed by stripping under reduced pressure to give a 25% solid aqueous polyurethane dispersion.

General procedure for preparation of coating solutions

All laboratory scale coating solutions were prepared in 100 g quantities unless otherwise stated. Stir the container containing the main polyurethane binder, then gradually add the specific pure Crosslinker solution. For larger scale experiments using more than about 1 gallon of coating solution, a premixed solution of crosslinker was prepared at 20% solids. The amount of isocyanate crosslinker solid used in each case was 20% by weight of the total binder solids (i.e., a 4:1 mixture of polyurethane and crosslinker). After stirring the binder and crosslinker for 15 minutes, the material was diluted with deionized water to a final concentration of 15% solids, followed by the addition of a surfactant (0.08% by weight of the total solution) and a slip aid (if used). The solution was stirred for another 15 minutes, followed by a coating operation. The order of sequential addition, such as loading the binder and crosslinker into the stirred deionized water and surfactant solution, is determined to be carried out equally.

Coating and tentering procedure

Laboratory membrane samples were coated using a No. 6 Mayer coating rod from RD Specialties, Inc. (Webster, NY). The coated film was dried in a 165 °F (74 °C) oven for 3-5 minutes, followed by similarly coating and drying the other side of the film. The film was subsequently stretched in "KARO IV LABORATORY STRETCHING MACHINE" from Brückner, Siegsdorf, Germany using the following procedure: (i) preheating at 97 ° C for 25 seconds; (ii) simultaneously at 14% / sec in the machine direction (MD) stretched 3.33 times and stretched 3.46 times in the cross-web (TD) direction; (iii) heated film at 193 ° C for 60 seconds; (iv) stretched the film at MD at 50% / sec to 3.43 times and stretched to 3.56 times in TD. For testing on manufacturing scale equipment, a reverse gravure roll coating process was used to coat the coating. The gravure roll speed was set to 125% stretch and a final speed of 45.75 fpm. The blade pressure is set to 40 psi. After coating, the film was processed through a drying oven (130 °F), a preheating and drawing zone (200-202 °F), a heat setting zone (422 °F), and a final cooling zone (100 °F). The tensile parameters are nominally the same as described for the laboratory samples. The thickness of the dried coating is nominally 80-150 nm.

Multilayer optical film with PET surface layer

A cast multilayer optical film (MOF) is applied, followed by stretching, and then used in the articles and laminates described herein. After the stretching and heat setting steps, the film resembles CM 875, a 2 mil (51 micron) nominal quarter-wave IR reflective film containing 224 polyterephthalic acid extensions. Alternate layers of ethyl ester (PET) and coPMMA (polymethyl methacrylate), as well as the same PET skin layer outside the multilayer stack. This film is described in U.S. Patent No. 6,797,396 (Example 5).

Preparation and testing of glass laminates

The glass laminate was 12 Å x 12 Å. The laminate was constructed as follows: 2.1 mm glass / 15 mil PVB / experimental film / 15 mil PVB / 2.1 mm glass. The laminates were passed through a roll to remove residual air, then passed through an autoclave, ramped to 285 °F / 175 psi over 30 minutes, held for 30 minutes, and gradually cooled over 30-60 minutes.

Compression shear testing was performed using a 1.00 吋 +/- 0.02 吋 square sample cut from a 12" x 12" glass laminate prepared as described above. The square samples were loaded into a test fixture of a MTS Alliance RT/50 machine equipped with a 11,000 lb-f (50,000 N) dynamometer to apply a 45 degree compression shear. The dynamometer was moved at a rate of 0.1"/min. The force that caused the glass laminate to break was recorded and the average reported as measured from 6-10 replicate measurements.

Turbidity and percent transmission were measured using a BYK Gardner Plus AT-4725 instrument. The material of the film sample and the glass laminate was tabulated.

Comparison example C1:

A film was prepared as described in "Multilayer Optical Film with PET Skin Layer". The film is applied without a primer, but is drawn as described in the "Coating and Stretching Procedure" above and made into a glass/PVB/film/PVB/glass construction and such as "Preparation and Testing of Glass Laminates" Tested as described in . The results are presented in Table 1.

Compare example C2:

A PAA coating solution was prepared as in U.S. Patent No. 5,411,845, which was coated onto a CM875 film as described above, tentered as described above, and made into a glass/PVB/film/PVB/glass construction and as " The test was carried out as described in Preparation and Testing of Glass Laminates. The results are presented in Table 1.

Comparison example C3:

A 1% AEAPTMS coating solution was prepared as in U.S. Patent No. 5,064,722. And ratio The glass/PVB/film/PVB/glass construction was prepared in the same manner as in Example C1, but the film was first coated on both sides of a multilayer optical film having AAEPTMS as described in "Preparation and Testing of Glass Laminates". The results are presented in Table 1.

Compare example C4:

A glass/PVB/PVB/glass construction was prepared and tested as in Comparative Example C1, but without a multilayer optical film having a PET skin. The results are presented in Table 1.

Example 1:

A coating solution was prepared using PUD-1 as a main binder and AIC-2 as a crosslinking agent as described in "General Procedure for Solution Preparation". Films were prepared and processed as described in "Multilayer Optical Films with PET Surface Layer" and "Coating and Stretching Procedures". The resulting processed film was made into a glass/PVB/film/PVB/glass construction and tested as described in "Preparation and Testing of Glass Laminates." The results are presented in Table 1.

Example 2:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that a slip agent was added to provide a sliding particle content of 2.5% by weight of the dried coating. The results are presented in Table 1.

Example 3:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PUD-3 was used as the primary binder. The results are presented in Table 1.

Example 4:

The coating solutions, films and laminates were prepared and tested as described above for Example 3 except that a slip agent was added to provide a sliding particle content of 2.5% by weight of the dried coating. The results are presented in Table 1.

Example 5:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PUD-2 was used as the primary binder. The results are presented in Table 1.

Example 6:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PU-1 and ARC-1 were used as the primary binder and crosslinker, respectively. The results are presented in Table 1.

Example 7:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PU-1 and AIC-2 were used as the primary binder and crosslinker, respectively. The results are presented in Table 1.

Example 8:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PUD-3 and ARC-1 were used as the primary binder and crosslinker, respectively. The results are presented in Table 1.

Example 9:

The coating solutions, films and laminates were prepared and tested as described above for Example 1, except that PUD-3 and AIC-2 were used as the primary binder and crosslinker, respectively. The results are presented in Table 1.

*NM=not measured

Example 10-16:

The coating solution, the coated and processed film and laminate construction were prepared and tested as described above for Example 1, using PUD-1 as the primary binder and a plurality of different crosslinking agents. For Example 10, the crosslinker was AIC-6; for Example 11, the crosslinker was AIC-7; for Example 12, the crosslinker was AIC-1; for Example 13, the crosslinker was AIC-2; 14. The crosslinker is AIC-3; for Example 15, the crosslinker is AIC-4; for Example 16, the crosslinker is AIC-5. The results are presented in Table 2.

Example 17-23:

The coating solution, the coated and processed film and laminate construction were prepared and tested as described above for Example 1, using PUD-3 as the primary binder and a plurality of different crosslinking agents. For Example 17, the crosslinker was AIC-6; for Example 18, the crosslinker was AIC-7; for Example 19, the crosslinker was AIC-1; for Example 20, the crosslinker was AIC-2; 21, the crosslinker is AIC-3; for Example 22, the crosslinker is AIC-4; for Example 23, the crosslinker is AIC-5. The results are presented in Table 3.

Example 24-27:

The coating solution, the coated and processed film and laminate construction were prepared and tested as described above for Example 1, using PUD-1 as the primary binder and a plurality of different crosslinking agents. For Example 24, the crosslinker was BI-1; for Example 25, the crosslinker was BI-2; for Example 26, the crosslinker was BI-3; for Example 27, the crosslinker was BI-4. The results are presented in Table 4.

Example 28-30:

The coating solution, the coated and processed film and laminate construction were prepared and tested as described above for Example 1, using PUD-3 as the primary binder and a plurality of different crosslinking agents. For Example 28, the crosslinker was BI-2; for Example 29, the crosslinker BI-3; for Example 30, the crosslinker was BI-4. The results are presented in Table 4.

Examples 31-33 and Comparative Examples C5 and C6:

A glass laminate was prepared using an optically clear heat activated adhesive in combination with a double-sided polyurethane-based primer film and an unprimed bare film. A primer and primerless film was prepared as described in "Multilayer Optical Film with PET Skin Layer". Two primer films were as described in Examples 2 and 4. The unprimed film was as described in Comparative Example 1. The glass laminate was prepared with two optically clear heat activated adhesives HAA-1 and HAA-2. The final laminate was constructed as a 2.1 mm glass/optical transparent heat activated adhesive/film/optical transparent heat activated adhesive/2.1 mm glass.

The glass laminate was prepared by the following method. The laminate was first degassed in a vacuum bag. The vacuum bag treated laminate was then placed in an autoclave and ramped to 135 ° C (275 ° F) / 1207 kPa (175 psi) for 60 minutes, then allowed to gradually cool and then removed from the autoclave. Examples 31 and 32 were carried out using the films of Examples 1 and 2, respectively, but PVB was replaced with HAA-1. Example 33 was carried out using the film of Example 2, but PVB was replaced with HAA-2. Comparative Examples C5 and C6 were carried out using the film of Comparative Example C1, but PVB was replaced with HAA-1 and HAA-2, respectively. The test was carried out as described in "Preparation and Testing of Glass Laminates". The results are presented in Table 5.

Examples 34-41 and Comparative Examples C7-C10:

A solvent based acrylic polymer PSA adhesive coating solution was directly coated onto the primed PET substrate and dried in a convection oven with a dry coating thickness of 6.35 microns (0.25 mils +/- 0.1 mils). Solution A and coating solution B were applied using two coating solutions. The primed substrate is a primed substrate C which is a substrate as described in Example 1; an primed substrate D which is a substrate as described in Example 2; and a primed substrate E, It is a sulphonated polyester-primed PET (as described in U.S. Patent No. 5,439,785). The PSA-coated and primed PET substrate was applied to the pre-wash/pre-cleaned borosilicate glass by dry and wet coating techniques. Immediately after coating and after heat aging in a convection oven at 66 ° C (150 ° F) for 24 hours, 72 hours and 1 week, the samples were peeled from the glass at an angle of approximately 90°. The peel rate exceeded 90 吋/min (229 cm/min). After the peel test, the amount of the adhesive transferred to the glass substrate was evaluated. The results are presented in Table 6.

Claims (21)

An article comprising: a substrate having a first polyester surface and a second polyester surface; a crosslinked polyurethane-based primer applied to the surface of the first polyester; and adjacent to The crosslinked polyurethane-based primer is an optically clear heat activated adhesive. The article of claim 1 wherein the crosslinked polyurethane-based primer comprises a reaction product of a polyurethane-based dispersion and a crosslinking agent. The article of claim 1 wherein the crosslinked polyurethane-based primer comprises a polyurethane-based, polyester-based polyurethane, polycarbonate-based polyamine Formate primer or a combination thereof. The article of claim 1, wherein the crosslinked polyurethane-based primer comprises a polyurethane-based aliphatic primer or a polyester-based aliphatic polyurethane primer . The article of claim 2, wherein the crosslinking agent comprises an aliphatic diisocyanate, a blocked isocyanate, a melamine formaldehyde crosslinking agent, or a combination thereof. The article of claim 1, wherein the substrate comprises a multilayer substrate. The article of claim 1 wherein the substrate comprises an oriented film. The article of claim 1 wherein the optically clear heat activated adhesive comprises a polyacrylate hot melt adhesive, polyvinyl butyral, ethylene vinyl acetate, an ionomer, a polyolefin, or a combination thereof. The article of claim 1 further comprising a crosslinked polyurethane-based primer applied to the surface of the second polyester. The article of claim 1 further comprising the adjacent to the second polyester surface A layer of a cross-linked polyurethane-based primer comprising an optically clear heat-activated adhesive layer, a cured acrylate layer or a pressure-sensitive adhesive layer. An article comprising: a substrate having a first polyester surface and a second polyester surface; a cross-linked polyurethane-based coating applied to the first polyester surface and the second polyester surface a primer; and a pressure-sensitive adhesive layer of the crosslinked polyurethane-based primer adjacent to the surface of the first polyester. A laminate construction comprising: a first inlaid glass substrate comprising a first major surface and a second major surface; a film article adhered to the first major surface of the first inlaid glass substrate, the film article comprising a substrate of a polyester surface and a second polyester surface; a first crosslinked polyurethane-based primer applied to the surface of the first polyester, and coated on the second polyester surface a second cross-linked polyurethane-based primer; and a first optically transparent heat-activated adhesive adjacent to the first cross-linked polyurethane-based primer and adjacent A layer of the second crosslinked polyurethane-based primer. The laminate construction of claim 12, wherein the layer adjacent to the second crosslinked polyurethane-based primer comprises a second optically clear heat-activated adhesive, and further comprising a second mosaic glass a second inlaid glass substrate comprising a first major surface and a second major surface, wherein the first major surface of the second inlaid glass substrate is adhered to the second optically transparent heat activated adhesive such that the film article comprises Interlayer article and the first mosaic glass substrate, the interlayer article and the second inlay The glass-embedded substrate forms a sandwich structure. A method of preparing an article, comprising: providing a substrate having a first polyester surface and a second polyester surface; applying a curable primer composition to the first polyester surface of the substrate or the second polyester In at least one of the surfaces, wherein the curable primer composition comprises a polyurethane-based dispersion and a crosslinking agent; drying the curable primer composition; heating while stretching the substrate and the Curing the primer composition to form a crosslinked primer layer on the surface of the stretched substrate; and applying an optically clear heat-activated adhesive to the cross-linked primer layer to form an optically transparent heat-activated adhesive layer . The method of claim 14, wherein the curable primer composition is applied to the first polyester surface of the substrate and the second polyester surface to form first and second cured primer layers. The method of claim 14, wherein the heating while stretching comprises stretching in at least one direction. The method of claim 16, wherein the stretching comprises biaxial stretching. The method of claim 15, further comprising applying a second optically clear heat activated adhesive to the second cured primer layer to form a second optically clear heat activated adhesive layer. The method of claim 15, further comprising applying a curable material to the second cured primer layer and curing to form a cured layer adjacent to the second cured primer layer. The method of claim 19, wherein the cured layer comprises a hard cover layer and/or an optical layer. The method of claim 15, further comprising applying a pressure sensitive adhesive material to the second cured primer layer to form a pressure sensitive adhesive layer adjacent to the second cured primer layer.