2K PU dual-cure adhesive for lamination molding

Abstract

Disclosed herein are two-part polyurethane adhesives and dual-cure polyurethane-based adhesives for use in laminate films. The adhesives are particularly useful for producing photochromic and clear-polarizing laminates for ophthalmic lens applications.

Description

[Technical Field]

[0001] The present invention relates to adhesive systems for functional laminates that can be used in ophthalmic lens applications. [Background technology]

[0002] The optical properties of ophthalmic lenses can be modified by incorporating films into the lenses. These films, often referred to as functional films, impart various optical functionalities to the base ophthalmic lens. For example, a clear film containing a photochromic dye can automatically darken when exposed to sunlight. This process is reversible, and the photochromic film returns to its clear state when placed indoors. Photochromic films find use in prescription lenses, temporarily darkening the lens into a sunglass-like lens. This variable darkness functionality is consumer-friendly, as it eliminates the need for prescription eyeglass wearers to purchase a separate pair of prescription sunglasses.

[0003] A relatively new advancement in functional films involves non-polarizing films that reversibly convert to polarizing films when exposed to ultraviolet (UV) radiation, such as that found in sunlight. These transparent-polarizing functional films return to their non-polarized state when UV radiation is absent, such as when placed indoors and away from sunlight. Until recently, polarization existed only as a static film incorporated into or on the lens. Transparent-to-polarizing (C2P) functional films can be provided in combination with photochromic films to provide prescription lenses that offer the reduced transparency effect of sunglasses as well as the glare-reducing benefits of polarized lenses.

[0004] Photochromic (PhCh) semi-finished lenses can be produced by a casting process or injection molding of a thermoplastic resin such as polycarbonate (PC) on the back of a thermoplastic photochromic laminate. Polarized semi-finished lenses can also be produced by injection molding of a thermoplastic resin such as PC on the back of a thermoplastic polarizing laminate. Clear-polarized semi-finished lenses can be produced by a casting process or a post-injection molding process in which a thermoplastic resin such as polycarbonate (PC) is first injected to produce the lens, and then a C2P laminate is attached to the front of the PC lens using heat from the remaining injection mold. The photochromic, polarized, and clear-polarized laminates are attached to the front of the lens using a pressure-sensitive adhesive (PSA).

[0005] Photochromic and clear-polarizing compositions are typically provided in highly flexible thermoplastic polyurethane (TPU) or thermoplastic elastomer (TPE) films. These films lack mechanical rigidity and cannot be formed to maintain any kind of physical shape. To solve these problems, functional films must be laminated so that they can be isolated from the casting environment and formed into spherical or non-spherical shapes. Good adhesives are needed to hold the multilayer laminate together during manufacturing, handling, shipping, and casting or injection molding. Summary of the Invention [Means for solving the problem]

[0006] The inventors have discovered that the adhesives disclosed herein can be used to produce laminates with photochromic and / or transparent-polarizing films. The adhesives exhibit sufficient preliminary adhesive strength (green strength) so that they maintain their integrity during the lamination process. The adhesives disclosed herein include two-component polyurethane adhesives and dual-cure polyurethane-based adhesives. These adhesives can be used in batch or roll-to-roll processes to produce photochromic and / or transparent-polarizing functional films.

[0007] Some aspects of the present disclosure are directed to a functionalized optical article comprising an optical lens comprising at least one polymerized monomer or thermoplastic material, a functional multilayer laminate comprising a functional film, a first thermoplastic film positioned on one side of the functional film, and a second thermoplastic film on an opposite side of the functional film, and a lamination adhesive disposed between the functional film and the first thermoplastic film and between the functional film and the second thermoplastic film. In some embodiments, the functionalized optical article is as described in the claims.

[0008] In some embodiments, the functional film comprises a photochromic material, a dichroic material, a photochromic-dichroic material, or a combination thereof. In some aspects, the functional film is selected from the group consisting of a stretched thermoplastic elastomer film, a non-stretched thermoplastic elastomer film, a stretched thermoplastic urethane film, and a non-stretched thermoplastic urethane film. The first and second thermoplastic films each independently comprise a material selected from the group consisting of cellulose triacetate (TAC), polycarbonate (PC), polyacrylate, polymethacrylate (PMMA), polystyrene methyl methacrylate (PSMMA), polymethyl methacrylate-acrylonitrile-butadiene styrene (PMABS), cyclic olefin copolymer (COC), polyester, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polyamide nylon, and polystyrene (PS).

[0009] In some embodiments, prior to curing, the adhesive comprises at least one polyisocyanate, at least one polyol, and optionally a catalyst. This adhesive is referred to herein as a two-part polyurethane adhesive. In some embodiments, the at least one polyol has a functionality of at least 2. The at least one polyol is selected from the group consisting of polyester polyols, polyether polyols, polyols containing amide groups, polyacrylate polyols, epoxy polyols, polyvinyl polyols, urethane polyols, and mixtures thereof.

[0010] In other embodiments, the adhesive, prior to curing, comprises at least one polyisocyanate compound, at least one polyol, at least one polymerization initiator, at least one aliphatic urethane acrylate, at least one acrylate monomer, and optionally a catalyst. This adhesive, referred to herein as a polyurethane-based adhesive, is obtained by reacting the above-listed components. In some embodiments, the polyurethane-based adhesive is used to attach a functional film to one or more thermoplastic films. In some embodiments, the aliphatic urethane acrylate has a functionality of at least 2. In some aspects, the aliphatic urethane acrylate is a hydroxy-functionalized acrylate. In some aspects, the at least one polyol is a polyester polyol, a polyether polyol, a polyol containing amide groups, a polyacrylate polyol, an epoxy polyol, a polyvinyl polyol, a urethane polyol, or a mixture of two or more of these polyols. In some embodiments, the at least one acrylate monomer is selected from the group consisting of 2-phenoxyethyl acrylate, benzyl methacrylate, isobornyl acrylate, neopentyl glycol diacrylate, and 1,3-butylene glycol dimethacrylate.

[0011] Some embodiments of the present disclosure are directed to polyurethane adhesives that, prior to curing, comprise at least one polyisocyanate compound, at least one polyol, at least one polymerization initiator, at least one aliphatic urethane acrylate, at least one acrylate monomer, and optionally a catalyst. Some aspects of the present disclosure are directed to roll-to-roll lamination processes, in which a polyurethane adhesive obtained by reacting at least one polyisocyanate compound, at least one polyol, at least one polymerization initiator, at least one aliphatic urethane acrylate, at least one acrylate monomer, and optionally a catalyst is used to adhere two or more films in a roll-to-roll lamination process. The two-component polyurethane adhesives or polyurethane adhesives disclosed herein can be used in batch or roll-to-roll processes to produce photochromic and / or transparent-polarizing functional films.

[0012] An "ophthalmic lens" according to the present disclosure is defined as a lens for mounting in eyeglasses, which is fitted, i.e., whose function is to protect the eye and / or correct vision. The lens may be an afocal, unifocal, bifocal, trifocal, or progressive lens. The ophthalmic lens may be corrective or non-corrective. The eyeglasses in which the ophthalmic lens is mounted may be either a conventional frame with two distinct ophthalmic lenses, one for the right eye and one for the left eye, or a similar mask, sun visor, helmet sight, or goggles, in which one ophthalmic lens faces both eyes simultaneously. The ophthalmic lens may be produced in a conventional geometric shape such as a circle, or may be produced to fit the intended frame. The ophthalmic lens may be manufactured from a thermosetting or thermoplastic material.

[0013] Any embodiment of any of the disclosed compositions and / or methods can consist of or consist essentially of any of the described elements and / or features and / or steps, rather than comprising / including / containing / having any of the described elements and / or features and / or steps. Thus, in any of the claims, the terms "consisting of" or "consisting essentially of" can be substituted with any of the open-ended linking verbs listed above in order to modify the scope of a given claim from that which would result from the use of an open-ended linking verb.

[0014] The term "substantially" and variations thereof are defined as generally, but not necessarily entirely, as specified, as would be understood by one of ordinary skill in the art; in one non-limiting embodiment, "substantially" refers to a range of within 10%, within 5%, within 1%, or within 0.5%. The terms "about" or "approximately" or "substantially unchanged" are defined as close to what would be understood by one of ordinary skill in the art; in one non-limiting embodiment, these terms are defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0015] In the claims and / or specification, when used in conjunction with the term "comprising," the use of the terms "a" or "an" may mean "one," but is also consistent with the meanings of "one or more," "at least one," and "one or more than one."

[0016] The phrase "and / or" means "and" or "or." For example, A, B, and / or C includes A only, B only, C only, A and B in combination, A and C in combination, B and C in combination, or A, B and C in combination. In other words, "and / or" operates as an inclusive disjunction.

[0017] As used in this specification and claims, the words "comprising" (and all forms of compris- ing , such as "comprise" and "comprises"), "having" (and all forms of having, such as "have" and "has"), "including" (and all forms of including, such as "includes" and "include"), or "containing" (and all forms of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0018] The present compositions and methods for their use can "comprise," "consist essentially of," or "consist of" any of the ingredients or steps disclosed throughout this specification. Regarding the transitional phase "consisting essentially of," in one non-limiting aspect, a basic and novel feature of the compositions and methods disclosed herein includes using the urethane-based adhesives disclosed herein in a laminate manufacturing process.

[0019] Other objects, features, and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and examples, while indicating specific embodiments of the present invention, are given by way of illustration only. Moreover, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0020] Various features and advantageous details will be described in more detail with reference to non-limiting embodiments illustrated in the accompanying drawings and detailed in the following description. It should be understood, however, that the detailed description and specific examples, while illustrating embodiments, are given by way of illustration only and not by way of limitation. Various substitutions, modifications, additions, and / or rearrangements will become apparent to those skilled in the art from this disclosure.

[0021] In the following description, numerous specific details are provided to provide a thorough understanding of embodiments of the present disclosure. However, it will be understood by those skilled in the art that the present invention can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the present invention.

[0022] Functionality (fn) is the average number of a particular type of functional group present on a molecule. For example, a polyol with a functionality of 2 refers to a molecule that contains an average of two hydroxyl groups per molecule. Aliphatic urethane acrylates can be characterized by the number of unsaturated acrylate groups per molecule. Monoacrylate molecules contain only one unsaturated acrylate group. Diacrylates contain two unsaturated acrylate groups. All materials with functional groups can be defined by their equivalent weight (Ew).

[0023] A polyol is a compound containing at least two hydroxy (OH) functional groups per molecule. Polyols can be characterized by the amount of hydroxyl (OH) groups in the material in percentage (%) (%OH). Polyols can be characterized by their hydroxyl number (OH#), which is the number of milligrams of potassium hydroxide (KOH) required to neutralize the acetic acid incorporated in the acetylation of one gram of a chemical containing a free hydroxyl group. A molecule can be referred to as its equivalent weight (Ew), which is the molecular weight (Mw) of a polyol containing only one OH functional (fn) group. The equation is Ew=Mw / fn. Exemplary polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, butanediol, hexanediol, neopentyl glycol, trimethylolpropane, poly(propylene oxide)diol, poly(propylene oxide)triol, copoly(ethylene oxide-propylene oxide)diol, poly(tetramethylene oxide)diol, bisphenol A ethoxide, bisphenol S ethoxide, spiroglycol, caprolactone-modified diols, carbonate diols, trimethylolpropane, pentaerythritol, polyester polyols, polyether polyols, polyacrylic polyols, polybutadiene polyols, polycarbonate polyols, homopolymers or copolymers of polyethylene and polypropylene glycol.

[0024] Polyisocyanates are compounds containing at least two isocyanate (NCO) functional groups per molecule. Polyisocyanates can be characterized by the amount of isocyanate groups (NCO) in the material in percentage (%) (%NCO) and by Ew. Examples of suitable polyisocyanates include 1,5-naphthylene diisocyanate, 2,2-, 2,4-, and 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (HMDI), allophanates of MDI, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkylenediphenylmethane diisocyanates, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of toluene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatocyclohexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatocyclohexane, 1,6-diisocyanato-2,4,4-trimethyl ... These include, but are not limited to, diisocyanates containing reactive halogen atoms such as anatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), chlorinated and brominated diisocyanate phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, phthalic acid-bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, or 3,3-bis-chloromethylether-4,4'-diphenyl diisocyanate. Other suitable diisocyanates are, for example, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, dimeric fatty acid diisocyanates.Additional exemplary diisocyanates include tetramethylene, hexamethylene, undecane, dodecamethylene, 2,2,4-trimethylhexane, 2,3,3-trimethylhexamethylene, 1,3-cyclohexane, 1,4-cyclohexane, 1,3- and 1,4-tetramethylxylene, isophorone, 4,4-dicyclohexanemethane, and lysine ester diisocyanates.

[0025] Polyurethanes are formed by reacting one or more polyisocyanates, such as diisocyanates, with one or more polyols. The polyurethane adhesives disclosed herein are formed by reacting one or more polyisocyanates, one or more polyols, a polymerization initiator, at least one aliphatic urethane acrylate, and at least one acrylate monomer. The formation of polyurethanes or polyurethane adhesives may further involve the inclusion of a catalyst during the formation reaction. The relative amounts of polyisocyanate and polyol are referred to as the isocyanate:hydroxyl (NCO:OH) ratio. The NCO:OH ratio is defined as the number of moles of isocyanate groups to the number of moles of hydroxyl groups in the polyurethane-forming or polyurethane adhesive-forming reaction.

[0026] Non-limiting examples of acrylate monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, neopentyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylonitrile, glycidyl methacrylate, ethoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, pentaerythritol methacrylate, benzyl methacrylate, p-tolyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, naphthyl methacrylate, methyl acrylate, ethyl acrylate, propanediol, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl meth ... butyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, neopentyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylonitrile, glycidyl acrylate, ethoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, isobornyl acrylate, pentaerythritol acrylate, benzyl acrylate, p-tolyl acrylate, phenyl acrylate, phenoxyethyl acrylate, naphthyl acrylate, neopentyl diglycol diacrylate, di-acrylates, tri-acrylates, tetra-acrylates, penta-acrylates, polyacrylates, and mixtures thereof.

[0027] The polymerization initiator generates or liberates free radicals upon the addition of energy to the composition, such as thermal energy, actinic radiation, or electron beam radiation. The addition of energy to the polymerization initiator results in the generation or liberation of free radicals, which then react with reactive monomers to start the polymerization process.

[0028] Thermally activated free radical polymerization initiators include organic peroxides, organic hydroperoxides, azo initiators and other known initiators, such as peroxide polymerization initiators, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1,4-bis[(tert-butylperoxy)isopropyl]benzene, 1,3-bis[(tert-butylperoxy)isopropyl]benzene, 2,5-dimethyl-2,5-bis(tert- butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxyoctoate, tert-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxybenzoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(2-ethylhexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis(3-methoxybutyl) peroxydicarbonate, bis(2-ethoxyethyl) peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, O-tert-butyl-O-isopropyl peroxycarbonate, and succinic acid peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diiso ...3-ethoxyethyl) peroxydicarbonate, bis(3-tert-butylcyclohexyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis(3-tert-butyl) peroxydicarbonate, bis isopropylbenzene hydroperoxide, p-methane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide; azo polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 4,4'-azobis(4-cyanovaleric acid); inorganic peroxides such as potassium persulfate and sodium persulfate; and the like.

[0029] The free radical polymerization initiator suitable for use herein is a photoinitiator that liberates free radicals when the composition of the present invention is irradiated with suitable electromagnetic radiation (ultraviolet light).Useful photoinitiators include but are not limited to 1-hydroxy-cyclohexyl-phenyl-ketone, 3-hydroxyphenylmethylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-1-(4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl)-2-methylpropan-1-one, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide. These polymerization initiators may be used alone, in combination with one or more other polymerization initiators, or in combination with one or more thermal initiators. It may also be possible to use a polymerization initiation system that uses ultraviolet irradiation, electron beam irradiation, X-ray irradiation, or radioactive irradiation. Regarding the polymerization initiation method, the method described in Moad and Solomon's "The Chemistry of Free Radical Polymerization," Pergamon, London, 1995, pp. 53-95, may be used.

[0030] The amount of the polymerization initiator used is not particularly limited. In addition to controlling the amount of the polymerization initiator, in order to control the amount of radical species generated during polymerization, it is preferable to control the temperature in the case of a thermal polymerization initiator that causes thermal dissociation, or the amount of energy in the case of a polymerization initiation system that generates radicals by light, ultraviolet light, electron beam, or the like.

[0031] The reaction to form the two-component polyurethane adhesive or polyurethane-based adhesive can be catalyzed by conventional catalysts known for this purpose. Exemplary, non-limiting catalysts include dibutyltin dilaurate, dibutyltin maleate, dibutyltin dilauryl mercaptide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, stannous naphthenate, stannous oxalate, stannous stearate, cadmium octoate, bismuth stearate, zinc octoate, cobalt naphthenate, bismuth nitrate, bismuth carboxylate, zirconium octoate, triphenylantimony dichloride, and the like.

[0032] Polyurethane adhesives contain ultraviolet radiation-curable and heat-curable components and are therefore cured using a dual-cure method. The term "dual-cure" means that the adhesive undergoes a first cure followed by a second cure. Additionally, when monomer species are cured independently and heterogeneously, an intertwined interpenetrating network (IPN) results. A sequential IPN is one in which a first monomer, crosslinker, and curing agent are polymerized, followed by a second, identical or different, monomer, crosslinker, and curing agent. For example, a first mixture of monomer, crosslinker, and curing agent is first polymerized, e.g., by ultraviolet radiation, and the resulting network swollen with a second, identical or different, monomer, crosslinker, and curing agent is then polymerized, e.g., thermally, to form an IPN. Each polymerization creates a separate crosslinked polymer network in which the two networks are intertwined. A simultaneous IPN is one in which two different monomers, crosslinkers, and curing agents are polymerized by two different, non-interfering curing mechanisms. A curing mechanism in which the first polymerization is different from that of the second polymerization allows for the formation of two independent entangled polymer networks. For example, a formulation comprising a first group of acrylic monomers, a crosslinker, and an organic peroxide curing agent and a second group of condensation monomers, a crosslinker, and a curing agent can be simultaneously polymerized by a thermal mechanism to form two independent, unconnected, entangled crosslinked polymers. However, if the first group of ingredients has functionality that allows them to react with the second group, some connectivity between the first and second crosslinked polymer networks can occur. Without being bound by theory, it is believed that the first cure provides a first level of cure, generating several polymer species and pre-solidifying the adhesive, while the second cure solidifies the adhesive to provide a strong final bond. The first cure can be achieved by exposing the uncured adhesive to heat, ultraviolet radiation, and / or electron beam radiation. The first cure allows for the nearly instantaneous development of sufficient bond strength to secure one substrate to another. The pre-adhesion established by the first cure is referred to as green strength and can be quantified using a peel strength test, such as the ASTM D1876 adhesive peel strength test.The second cure can be achieved by exposure to a different radiation energy than that used for the first cure. If ultraviolet radiation and / or electron beam radiation is used for the first cure, heat may be used for the second cure, or vice versa. In a preferred embodiment, ultraviolet radiation is used for the first cure and heat is used for the second cure. The second cure solidifies the adhesive to provide a strong final bond. If ultraviolet radiation and / or electrons are used for the first cure, allowing the adhesive to rest at room temperature for an extended period (e.g., at least one day) may be used as a condition to affect the second cure. In some embodiments, the polyurethane-based adhesive is exposed to first and second cure conditions, followed by an extended rest period to reach a fully cured state. The dual-cure adhesive has a sufficiently long pot life that it is easily adaptable for use with conventional film lamination processes and equipment. Furthermore, the adhesive can be formulated to be solvent-free (thereby avoiding emission issues) yet maintain a low enough viscosity to allow for easy handling and application.

[0033] In some embodiments, the functional films disclosed herein comprise a photochromic material, a dichroic material, a photochromic-dichroic material, or a combination thereof. The inclusion of a photochromic material in the film allows the film to reversibly change from a first clear (colorless) transmissive state to a second, darker or colored transmissive state upon exposure to light of a given frequency. This light of a given frequency reversibly activates a chemical species to convert between two forms with different absorption spectra. Removing or reducing the intensity of the light of a given frequency below a threshold value causes the film to change color or fade, returning to its original, inactivated, clear (colorless) state. The inclusion of a photochromic-dichroic material in the film allows the film to reversibly change the degree to which it filters plane-polarized light, such as glare. Films with photochromic-dichroic materials become colored and polarized upon exposure to actinic radiation. The orientation of the molecules allows the film to transmit light whose oscillation plane is not parallel to the molecular orientation. In effect, the horizontal molecular orientation reduces the amount of horizontal glare that penetrates the film and reaches the eye. Examples of photochromic-dichroic materials are included in U.S. Patent No. 7,256,921, which is incorporated by reference in its entirety. [Example]

[0034] A. Polyurethane adhesive (two-component adhesive) Example 1 Polyol 1 (OH value: 540 mg KOH / g, average molecular weight: 240 g / mol, mixed functionality: 2.4, viscosity: 300 cP at 20°C) and Polyisocyanate 1 (NCO content: 19.0-21.0%, viscosity: 2,400-3,600 cP at 23°C) were weighed out to yield an NCO:OH molar ratio of 1.5:1 NCO to OH. The polyisocyanate and polyol were added to a clear glass vial, mixed thoroughly, and then vacuum degassed for approximately 1 hour until foaming subsided.

[0035] A sheet of cellulose triacetate was treated in 10% caustic at 60° C. for 4 minutes, rinsed in deionized water, and then dried for 15 minutes at 50° C. A thermoplastic polyamide-polyether block elastomer (TPE) was stretched by stretching approximately 4:1, washed, and dried.

[0036] Multilayer composites comprising two TAC support layers and stretched TPE sheets were hand-laminated using the polyol / polyisocyanate (polyurethane) adhesive described above between rubber rollers at approximately 20 psig and cured at 60-80°C for approximately 24 hours. The resulting TAC / TPE / TAC laminate had acceptable cured adhesion, with a peel force of 11.5 N / inch. Primer was applied to the laminate, and disks were punched and cast in allyl diglycol carbonate (CR39). Lens adhesion was excellent, with no delamination of the laminate observed within the lens, even after surfacing and edging. The remaining adhesive in the glass vial was cured overnight at 60°C. The resulting bulk-cured adhesive was clear and hard.

[0037] Example 2 Same ingredients and conditions as in Example 1, except that the NCO:OH molar ratio was 2:1. The resulting laminate had a peel force of 12-14 N / inch and acceptable cured adhesion. The bulk cured adhesive was permeable and rubber-hard.

[0038] Example 3 The ingredients and conditions were the same as in Example 1, except that the NCO:OH molar ratio was 3:1. The resulting TAC / TPE / TAC laminate had a peel force of <10 N / inch and was manually peelable. The bulk-cured adhesive was transparent and soft. NCO:OH ratios of 1:1 or less are expected to limit or eliminate the free NCO functional groups necessary for bonding with the TAC and TPE. NCO:OH ratios >3:1 result in a soft bulk material upon cure, and excess unreacted NCO may discolor over time. Peel strength was not measured because the samples had poor cured adhesion and were easily peelable by hand, i.e., generally considered to be <10 N / inch.

[0039] [Table 1]

[0040] Example 4 Same ingredients and conditions as Example 1, except a different polyisocyanate (Polyisocyanate 2 with an NCO content of 23.0% and a viscosity of 2,500 cP at 23°C) was used in the formulation. The bulk cure of the adhesive is transparent. A primer was applied to the laminate, and disks were die-cut and cast in CR39. The cured laminate showed excellent hand-peel adhesion with no delamination. Lens polarization performance was rated good with an average degree of polarization (DP) of 85.

[0041] Example 5 Same ingredients and conditions as in Example 1, except that Polyisocyanate 3 (NCO content: 21.8, viscosity: 2,500 cP at 25°C) was used in the formulation. The cured laminate had poor adhesion and was easily peeled apart by hand. The bulk cured adhesive was opaque.

[0042] Example 6 Same ingredients and conditions as in Example 1, except that Polyisocyanate 4 (an aliphatic polyisocyanate with an NCO content of 11.9% and a viscosity of 600 cP at 23°C) was used in the formulation. The adhesion of the cured laminate was poor, and the laminate was easily peeled apart by hand. The bulk cured adhesive was hazy.

[0043] Example 7 Same ingredients and conditions as in Example 1, except for the use of Polyisocyanate 5 (a blend of cycloaliphatic polyisocyanate A with an NCO content of 17-17.6% and aliphatic polyisocyanate B with an NCO content of 21.8% and a viscosity of 3,000 cP at 23°C; total NCO content: 21.0%). The adhesion of the cured laminate was poor, and the laminate was easily peeled apart by hand. The bulk cured adhesive was hazy.

[0044] Example 8 Same ingredients and conditions as in Example 1, except that Polyisocyanate 6 (NCO content: 21.8%, viscosity: 3,000 cP at 23°C) was used. The peel force was 7.5 N / inch, and the adhesion of the cured laminate was poor. The bulk cured adhesive was hazy.

[0045] Example 9 Same ingredients and conditions as in Example 4, except the lamination was scaled up and run on a roll-to-roll laminator. A larger adhesive batch was prepared by mixing Polyol 1 (79 g) and Polyisocyanate 2 (236 g) in a glass jar. All ingredients were degassed under vacuum for approximately 30 minutes until foaming subsided. A TAC membrane (80 μm) was treated in an 18% caustic at 45°C for 4 minutes, rinsed three times with deionized water, and dried by passing it through an 80°C oven at 0.8 m / min (approximately 4 minutes). The TPE membrane was stretched approximately 4:1 to a thickness of approximately 40 μm.

[0046] The TAC / TPE / TAC and adhesive were laminated in a wet bonding nip on a roll-to-roll laminator with a line speed of approximately 0.4-0.5 m / min, then passed through a 130°C oven (approximately 6-7.5 minutes). Upon exiting the horizontal oven, the adhesive was uncured and wet, and the laminate was easily separated. The laminate then passed through several rollers. The first idler roller (6 inches) changed the laminate direction 90 degrees to a vertically downward orientation, and the second driven nip roller (6 inches) changed the laminate direction another 90 degrees back to a horizontal orientation. At this point, the laminate was in sheet form and collected.

[0047] [Table 2]

[0048] [Table 3]

[0049] B. Polyurethane adhesive (double curing adhesive) Example 10 Urethane acrylate 1 (hydroxy-functional aliphatic urethane triacrylate, 0.50 g) and Polyol 1 (1.368 g) were weighed into an amber glass vial. Acrylate Monomer 1 (neopentyl diglycol diacrylate, 0.110 g) and Photoinitiator 1 (0.044 g) were added and mixed thoroughly until dissolved. Polyisocyanate 2 (3.632 g) was added and mixed thoroughly. The solution was vacuum degassed until bubbling subsided. The stretched photochromic-dichroic TPE film was manually laminated to the TAC using a two-roller laminator, followed by UV (H) lamination in a Fusion at approximately 22 feet per minute per side. + The adhesive was allowed to cure for 5 days at room temperature. The adhesion of the laminate was acceptable. The laminate was clear, showed no streaking defects, and had a good DP.

[0050] Example 11 Same ingredients and conditions as in Example 10, except that Urethane Acrylate 1 was replaced with Urethane Acrylate 2 (a carboxy-functional polyester acrylate). The adhesion of the laminate was acceptable. The laminate was clear with some streaking defects observed, and the DP was good.

[0051] Example 12 The ingredients and conditions were the same as in Example 10, except that Urethane Acrylate 1 was replaced with Urethane Acrylate 3 (urethane diacrylate oligomer). The adhesion of the laminate was acceptable. The laminate had a slight milky white haze, and streaking defects were observed. The DP was good.

[0052] Example 13 The ingredients and conditions were the same as in Example 10, except that Urethane Acrylate 1 was replaced with Urethane Acrylate 4 (aliphatic urethane diacrylate oligomer). The adhesion of the laminate was acceptable. The laminate had a milky white haze, and no streaking defects were observed. The DP was good.

[0053] Example 14 The ingredients and conditions were the same as in Example 10, except that Urethane Acrylate 1 was replaced with Urethane Acrylate 5 (aliphatic polyester-based urethane diacrylate oligomer). The adhesion of the laminate was acceptable. The laminate was clear and showed no streaking defects. The DP was good.

[0054] Example 15 Same ingredients and conditions as in Example 10, except that Urethane Acrylate 1 was replaced with Urethane Acrylate 6 (urethane diacrylate oligomer). The adhesion of the laminate was acceptable. The laminate was clear and showed no streaking defects. The DP was good.

[0055] Example 16 Same ingredients and conditions as in Example 10, except Urethane Acrylate 1 was replaced with Urethane Acrylate 7 (urethane diacrylate oligomer). The laminate was opaque.

[0056] Example 17 Same ingredients and conditions as in Example 14, except the amount of Acrylate Monomer 1 was reduced to 0.50 g and the amount of Photoinitiator 1 was reduced to 0.0165 g. The adhesion of the laminate was good and no streaking defects were observed.

[0057] [Table 4]

[0058] [Table 5]

[0059] Example 18 Same ingredients and conditions as in Example 10, except a dual-cure adhesive was used on a roll-to-roll laminator. Acrylate Monomer 1 (4 g), Polyol 1 (46.4 g), Urethane Acrylate 1 (20 g), and Photoinitiator 1 (1.68 g) were weighed into a brown glass bottle and mixed until dissolved. Polyisocyanate 2 (133.6 g) was added and mixed thoroughly. All ingredients were vacuum degassed for approximately 30 minutes until foaming subsided.

[0060] TAC / TPE / TAC laminates were fabricated on a roll-to-roll laminator with a line speed of approximately 0.4-0.5 m / min. After the nip, the TAC / TPE / TAC laminate was first pre-cured by passing it through upper and lower UV lamps. The laminate was then passed through a 130°C oven (approximately 6-7.5 minutes). Upon exiting the horizontal oven, the adhesive was soft and cured and not wet. The laminate showed good adhesion and was transported over two additional 6-inch rollers before being collected. The first idler roller changed the laminate orientation from horizontal to vertical downward. The second driven nip roller further changed the laminate orientation back to horizontal. At this point, the laminate immediately sheeted without any problems and was allowed to fully cure for five days. This polyurethane-based dual-cure adhesive provides sufficient green adhesion for laminates fabricated on a roll-to-roll process.

[0061] Example 19 Same ingredients and conditions as in Example 10. Urethane acrylate 1 (0.50 g) and polyol 1 (1.130 g) were weighed into an amber glass vial. Acrylate monomer 1 (0.10 g) and photoinitiator 1 (0.042 g) were added and mixed thoroughly until dissolved. Polyisocyanate 2 (3.37 l) was added and mixed thoroughly. The solution was vacuum degassed until bubbling subsided. The PhCh TPU film was manually laminated to the TAC using a two-roller laminator, followed by two exposures per side to UV light (H) in the Fusion at approximately 24 ft / min per side. + The adhesive was allowed to cure at room temperature for 5 days. The laminate was yellow in color.

[0062] Example 20 Same ingredients and conditions as in Example 19, except that Photoinitiator 1 was replaced with an equimolar amount of Photoinitiator 2 (0.034 g). The laminate exhibited a lighter yellow color than in Example 19.

[0063] Example 21 Same ingredients and conditions as in Example 19, except that Photoinitiator 1 was replaced with an equimolar amount of Photoinitiator 3 (0.016 g). The laminate was colorless.

[0064] Example 22 Same ingredients and conditions as in Example 19, except that Photoinitiator 1 was replaced with an equimolar amount of Photoinitiator 4 (0.026 g). The laminate was colorless.

[0065] [Table 6]

[0066] The claims should not be construed as including means-plus-function or step-plus-function limitations unless such limitations are expressly recited in a given claim using the phrase "means for" or "step for," respectively. The present disclosure includes the following aspects: <Aspect 1> A functionalized optical article, comprising: an optical lens comprising at least one polymerized monomer or thermoplastic material; a functional multilayer laminate comprising a functional membrane, a first thermoplastic membrane positioned on one side of the functional membrane, and a second thermoplastic membrane positioned on an opposite side of the functional membrane; a lamination adhesive disposed between the functional film and each of the first and second thermoplastic films; The adhesive, before curing, at least one polyisocyanate, at least one polyol, and A functionalized optical article, optionally consisting of a catalyst. <Aspect 2> 2. The optical article of embodiment 1, wherein the at least one polyol has a functionality of at least 2. <Aspect 3> 2. The optical article of embodiment 1, wherein the at least one polyol is a polyester polyol, a polyether polyol, a polyol containing amide groups, a polyacrylate polyol, an epoxy polyol, a polyvinyl polyol, a urethane polyol, or a mixture of two or more such polyols. <Aspect 4> 2. The optical article of embodiment 1, wherein each of the first thermoplastic film and the second thermoplastic film independently comprises a material selected from the group consisting of cellulose triacetate, polycarbonate, polymethacrylate, polyamide, and polystyrene. <Aspect 5> 2. The optical article of embodiment 1, wherein the functional film is selected from the group consisting of a stretched thermoplastic elastomer film, a non-stretched thermoplastic elastomer film, a stretched thermoplastic urethane film, and a non-stretched thermoplastic urethane film. <Aspect 6> 2. The optical article of embodiment 1, wherein the functional film further comprises a photochromic material, a dichroic material, a photochromic-dichroic material, or a combination thereof. <Aspect 7> A functionalized optical article, comprising: an optical lens comprising at least one polymerized monomer or thermoplastic material; a functional multilayer laminate comprising a functional membrane, a first thermoplastic membrane positioned on one side of the functional membrane, and a second thermoplastic membrane positioned on an opposite side of the functional membrane; a lamination adhesive disposed between the functional film and each of the first and second thermoplastic films; The adhesive, before curing, at least one polyisocyanate, at least one polyol, at least one polymerization initiator, at least one aliphatic urethane acrylate, and comprising at least one acrylate monomer; A functionalized optical article, wherein the adhesive optionally comprises a catalyst. <Aspect 8> 8. The optical article of embodiment 7, wherein the aliphatic urethane acrylate has a functionality of at least two. <Aspect 9> 8. The optical article of embodiment 7, wherein the aliphatic urethane acrylate is a hydroxy-functionalized acrylate. <Aspect 10> 8. The optical article of embodiment 7, wherein the at least one polyol has a functionality of at least 2. <Aspect 11> 8. The optical article of embodiment 7, wherein the at least one polyol is a polyester polyol, a polyether polyol, a polyol containing amide groups, a polyacrylate polyol, an epoxy polyol, a polyvinyl polyol, a urethane polyol, or a mixture of two or more such polyols. <Aspect 12> 8. The optical article of embodiment 7, wherein the at least one acrylate monomer is selected from the group consisting of 2-phenoxyethyl acrylate, benzyl methacrylate, isobornyl acrylate, neopentyl glycol diacrylate, and 1,3-butylene glycol dimethacrylate. <Aspect 13> 8. The optical article of embodiment 7, wherein each of the first thermoplastic film and the second thermoplastic film independently comprises a material selected from the group consisting of cellulose triacetate, polycarbonate, polymethacrylate, polyamide, nylon, and polystyrene. <Aspect 14> 8. The optical article of embodiment 7, wherein the functional film is selected from the group consisting of a stretched thermoplastic elastomer film, a non-stretched thermoplastic elastomer film, a stretched thermoplastic urethane film, and a non-stretched thermoplastic urethane film. <Aspect 15> 8. The optical article of embodiment 7, wherein the functional film further comprises a photochromic material, a dichroic material, a photochromic-dichroic material, or a combination thereof.

Claims

1. 1. A functionalized optical lens, comprising: an optical lens comprising a polymer or thermoplastic material in which at least one polymerization monomer has been polymerized; a functional multilayer laminate comprising a functional membrane, a first thermoplastic membrane positioned on one side of the functional membrane, and a second thermoplastic membrane positioned on an opposite side of the functional membrane; a lamination adhesive disposed between the functional film and each of the first and second thermoplastic films; The adhesive, before curing, a thermosetting component comprising at least one polyisocyanate and at least one polyol; an ultraviolet radiation curable component comprising at least one aliphatic urethane acrylate and at least one acrylate monomer; at least one photoinitiator, and optionally, a polyurethane-forming catalyst; A functionalized optical lens comprising:

2. The functionalized optical lens of claim 1 , wherein the aliphatic urethane acrylate has a functionality of at least two.

3. 3. The functionalized optical lens of claim 1, wherein the aliphatic urethane acrylate is a hydroxy-functionalized acrylate.

4. 3. The functionalized optical lens of claim 1, wherein said at least one polyol has a functionality of at least two.

5. 3. The functionalized optical lens according to claim 1, wherein the at least one polyol is a polyester polyol, a polyether polyol, a polyol containing amide groups, a polyacrylate polyol, an epoxy polyol, a polyvinyl polyol, a urethane polyol, or a mixture of two or more such polyols.

6. 3. The functionalized optical lens of claim 1, wherein the at least one acrylate monomer is selected from the group consisting of 2-phenoxyethyl acrylate, benzyl methacrylate, isobornyl acrylate, neopentyl glycol diacrylate, and 1,3-butylene glycol dimethacrylate.

7. The functionalized optical lens of claim 1 or 2, wherein each of the first thermoplastic film and the second thermoplastic film independently comprises a material selected from the group consisting of cellulose triacetate, polycarbonate, polymethacrylate, polyamide, nylon, and polystyrene.

8. The functionalized optical lens of claim 1 or 2, wherein the functional film is selected from the group consisting of a stretched thermoplastic elastomer film, a non-stretched thermoplastic elastomer film, a stretched thermoplastic urethane film, and a non-stretched thermoplastic urethane film.

9. The functionalized optical lens of claim 1 or 2, wherein the functional film further comprises a photochromic material, a dichroic material, a photochromic-dichroic material, or a combination thereof.

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