Multilayer Optical Devices

Abstract

Disclosed herein is a multilayer optical device comprising a polymer layer disposed between and in contact with a first optical element layer and a second optical element layer, the polymer layer comprising the product of a composition comprising a self-healing component, the self-healing component consisting of or consisting essentially of molecules comprising a self-healing moiety, the composition comprising: (a) greater than 30 wt. % of the self-healing component based on the weight of the total composition; or (b) greater than 0.015 equivalents of the self-healing moiety per 100 g of composition.

Description

[Technical Field]

[0001]

[0001] The present invention relates to multilayer optical devices having at least one polymer layer capable of imparting self-healing properties and / or stress relaxation behavior to the multilayer optical device, compositions from which the polymer layer is made, and cured products produced therefrom.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 004560, filed April 3, 2020, the entire contents of which are incorporated by reference as if fully set forth herein. [Background technology]

[0003]

[003] Optical devices are devices that process or manipulate electromagnetic radiation, typically in the visible and / or UV portions of the spectrum. There are many different types of optical devices, such as eyeglasses, binoculars, lasers, microscopes, telescopes, cameras, fiber optics, etc.

[0004] In many applications, optical devices endure significant amounts of physical and / or thermal stress during installation and use, tending to degrade over time. For example, in optical fiber applications, forces involving localized axial displacements of the glass over several micrometers can induce microscopic curvatures, or microbends. Microbends are known to contribute to attenuation of optical fiber signal transmission, thereby reducing the efficiency of transmitting large amounts of data over long distances. Over time, protective polymer coating layers surrounding and in direct contact with glass fibers are designed to become softer, as softer coatings are known to be better able to relieve stress and minimize the formation of microbends in optical fibers. However, an undesirable by-product of such soft coatings is their susceptibility to damage caused by physical handling and thermal stresses during application, installation, and in situ over time. Such damage often manifests itself in the form of voids or cavitations in the polymer layers protecting the glass fibers, which also increase the attenuation levels of the optical fiber.

[0005] Other examples of multilayer structure products include those used in optical components such as beam splitters, solar panels, anti-reflective coatings, displays, lenses, optical films, polarizing optics, mirrors, windows, optical filters, lighting devices, etc. External mechanical stresses and repeated temperature cycling experienced during use can cause the various layers of the structure to delaminate, crack, or fracture, resulting in performance degradation or failure.

[0006] Another example of an optical device is a photochromic lens. Such lenses, which tend to darken upon exposure to light of a given wavelength and / or intensity, are used in the eyewear industry as a means of providing a single device that dynamically and simultaneously offers the benefits of both sunglasses and traditional eyeglasses. Photochromic lenses often consist of a glass or polymer lens with one or more coating or film layers adhered to it, at least one of which contains the photochromic molecules necessary to accommodate the intended dynamic effect. The darkening and fading behavior is controlled not only by the photochromic dye but also by the properties of the host material in which the dye resides. When the dye switches between its colored and uncolored forms, the volume of the molecule changes, leading to local stress accumulation and a change in the stress pattern around the dye molecule. The level of local stress accumulation and how the change in local stress is distributed have a significant impact on lens performance, including how dark the lens becomes after activation and how quickly the lens returns to its clear state.

[0007]

[0007] It would therefore be desirable to provide a multilayer optical device that can better withstand or balance stress differentials placed on or between, or internal stresses within, multiple associated layers. Additionally or alternatively, it would be desirable to provide a multilayer optical device that provides an amount (or an improved amount) of self-healing, such that damage actually incurred in one or more layers is reduced or eliminated over time. Summary of the Invention

[0008]

[0008] One or more of the above solutions may be provided by several aspects and embodiments of the present invention described and claimed herein. A first aspect is a composition for coating a multilayer optical device, comprising: an optional reactive monomer and / or optional reactive oligomer component; a self-healing component consisting of a molecule that may have one or more self-healing moieties and one or more polymerizable moieties; an initiator component; and an optional additive component, wherein (a) the self-healing component is present in an amount greater than 30 wt %, based on the weight of the total composition, and / or (b) the composition is present in an amount greater than 0.015 equivalents per 100 g of the composition, or 0. or 0.025 to 0.20 equivalents; or 0.037 to 0.2 equivalents, or 0.037 to 0.1 equivalents, or 0.037 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.1 equivalents, or 0.02 to 0.08 equivalents, or 0.02 to 0.05 equivalents; or 0.025 to 0.20 equivalents; or 0.037 to 0.2 equivalents, or 0.037 to 0.1 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents.

[0009] According to other embodiments of the first aspect, the composition has polymerizable moieties such as (meth)acrylate moieties, and / or the self-healing moieties can include multiple hydrogen-bonding groups or disulfides. In some embodiments, the self-healing moieties have a specific bond energy between two linked self-healing moieties. In yet another embodiment of the first aspect, the self-healing moieties include 2-ureido-4-pyrimidinone (UPy) groups and / or at least three urethane linking groups. In yet another embodiment, the overall composition and / or the self-healing components specifically have a specific value of UPy group or (meth)acrylate group equivalents per 100 g of composition.

[0010] In another embodiment of the first aspect, the self-healing component comprises a molecule according to a particular specified structure, such as structure (VI) referenced elsewhere herein. In selected embodiments of the first aspect, the self-healing component and / or the molecule according to a particular specified structure—such as structure (VI) referenced elsewhere herein—have a specified glass transition temperature, molecular weight value, and / or specific reactants. In yet other embodiments, the composition has a specified viscosity value and / or amount of monomer, oligomer, self-healing component, (photo)initiator, and / or additive.

[0011]

[0011] In yet another embodiment of the first aspect, the composition is configured to have certain self-healing properties when provided as a cured product, such as a film, as evidenced by a comparison of certain mechanical properties measured both before and after a cut or tear is applied to the cured product.

[0012] A second aspect of the present invention is a compound of structure (VII): [UPy-(D m -UD m ) (2+q) ]-[A(G) (n-1) -D m ] k -Z (VII) During the ceremony, UPy represents the UPy group, which is 2-ureido-4-pyrimidinone; U represents -NHC(O)E- or -EC(O)NH-, where E is O, NH, N(alkyl), or S; q is a number greater than or equal to 0 and less than or equal to 10; K is a number between 0 and 20; A is selected from carbon and nitrogen; n is 2 or 3, where n=3 when A is an sp3 carbon, and n=2 when A is an sp2 carbon or nitrogen; m is an integer from 0 to 500; D is, for each occurrence of m, -O-, -C(O)-, -Aryl-, -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(CT2) i -, -N(T)-, -Si(T)2(CH2) i -, -(Si(T)2O) i a divalent spacer independently selected from -, -C(T)=C(T)-, -C(T)=N-, -C(T)=, -N=, or combinations thereof; where for each instance in D of a single bond, a single bond is attached to it, and for each instance in D of a double bond, a double bond is attached to it; each T is selected at each occurrence from a monovalent unit comprising hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl; Each T can also be selected from divalent Dm and is bonded to another divalent T also selected from Dm to form a ring structure; and i is an integer from 1 to 40; Z is hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or a maleimide group; G, for each occurrence of n, is hydrogen, -Dm-Z, or the following structure (VII-b): (ZD m ) j XD m - (VII-b); (In the formula, X is a multi-hydrogen bonding group, a disulfide group, or a urea group; When X is divalent, j=1, and when X is monovalent, j=0; and the oligomer has greater than 0.022, or greater than 0.025, or greater than 0.03, or greater than 0.04, or greater than 0.05, or greater than 0.1 UPy groups per 100 grams of oligomer.

[0013] According to another embodiment of the second aspect, the oligomer according to structure (VII) is present in a composition, preferably a liquid radiation curable composition, for coating a multilayer optical device, such as a primary coating layer of an optical fiber.

[0014] A third aspect of the present invention is: 1. A multilayer optical device comprising a polymer layer disposed between a first layer of optical elements and a second layer of optical elements, each of the polymer layer, the first optical element layer, and the second optical element layer includes a first surface and a second surface, the first surface of the polymer layer being in contact with the first surface of the first optical element layer, and the second surface of the polymer layer being in contact with the first surface of the second optical element layer; The polymer layer comprises the product of a composition comprising a self-healing component, said self-healing component comprising a molecule comprising a self-healing moiety, said composition comprising: (a) greater than 30% by weight of the self-healing component, based on the weight of the total composition; or (b) greater than 0.015 equivalents of self-healing moiety per 100 g of the composition; A multilayer optical device comprising: [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 shows a layout of a multilayer optical article according to a non-limiting embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016]

[016] A first aspect of the present invention is a composition for coating a multilayer optical device, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component; Includes; (a) the self-healing component is present in an amount greater than 30 wt.%, or greater than 40 wt.%, or greater than 50 wt.%, or greater than 60 wt.%, or greater than 70 wt.%, or greater than 80 wt.%, based on the weight of the total composition; and / or (b) the composition has a self-healing moiety of greater than 0.015 equivalents, or between 0.015 and 0.2 equivalents, or between 0.015 and 0.1 equivalents, or between 0.015 and 0.08 equivalents, or between 0.015 and 0.05 equivalents, or between 0.015 and 0.045 equivalents; or between 0.02 and 0.2 equivalents, or between 0.02 and 0.1 equivalents, or between 0.02 and 0.08 equivalents, or between 0.02 and 0.05 equivalents; or between 0.025 and 0.20 equivalents; or between 0.037 and 0.2 equivalents, or between 0.037 and 0.1 equivalents, or between 0.037 and 0.08 equivalents, or between 0.037 and 0.05 equivalents.

[0017]

[0017] Compositions according to the first aspect are curable, i.e., capable of undergoing a chemical reaction, preferably a polymerization reaction, to solidify or harden the composition upon sufficient exposure to a sufficient stimulus. Such a stimulus may be by application of heat (thus rendering the composition heat-curable) or by actinic radiation of a sufficient dose and appropriate wavelength (thus rendering the composition radiation-curable). According to various embodiments, such compositions may include an optional reactive monomer component, an optional oligomer component, a self-healing component, an initiator component, and optional additive components. Such components, described in more detail below, may be equally suitably employed in other aspects of the invention, such as any of the compositions for coating a multilayer optical device according to the first aspect, compositions for use with any of the self-healing oligomers according to the second aspect, and multilayer optical devices according to the third aspect.

[0018] Monomer component

[0018] The compositions according to the first aspect of the present invention optionally comprise a monomer component; i.e., a collection of one or more individual monomers having one or more particular structures or types. Monomers are molecules of low relative molecular weight, the structure of which can be polymerized, thereby contributing building blocks to the essential structure of a polymer. In one embodiment, the monomer component has a theoretical molecular weight (MW) of about 86 g / mol to about 800 g / mol, or 100 g / mol to 350 g / mol. theo ), and theo is determined by calculating the theoretical molecular weight of the idealized structure of the monomer used (often expressed by its corresponding CAS number). For purposes of this document, an individual monomer should be construed as being part of the monomer component unless it has a self-healing moiety as described elsewhere herein; in such case, it shall be construed as being part of the self-healing component.

[0019] Monomers are typically utilized as diluents in multilayer optical device compositions. That is, they can be employed to modify—more specifically, usually reduce—the viscosity of the larger composition to which they are added. Various diluents are used to maximize the flowability, and therefore processability, of the associated multilayer optical device composition.

[0020] In addition to simply modifying the viscosity of the liquid composition, such monomers are preferably also utilized to contribute to the cure rate and / or physical properties of the coating produced therefrom. Thus, the monomers are typically reactive monomers. As used herein, "reactive" refers to the ability to form a chemical reaction, preferably a polymerization reaction, with another molecule. Thus, a reactive compound is said to have at least one reactive or functional group. When used for such purposes, a monomer is said to have at least one reactive or functional group. Preferably, such reactive or functional group is a polymerizable group. When used, the monomer component preferably comprises, consists of, or consists essentially of a reactive monomer or a reactive diluent monomer.

[0021] In one embodiment, the monomer component according to the present invention comprises, consists essentially of, or consists of reactive monomers having at least one polymerizable group. In a preferred embodiment, the monomer component consists of reactive monomers having, on average, one polymerizable group. The polymerizable group(s) of the reactive monomer(s) are preferably (co)polymerizable with other polymerizable groups present in the composition, such as those present in the self-healing component and / or any oligomeric component.

[0022] The polymerizable group of the reactive diluent can be of any known type. However, in one embodiment, the polymerizable group can comprise, consist essentially of, or consist of, for example, an acrylate, methacrylate, acrylamide, or N-vinylamide group, or any combination thereof. The reactive diluent is preferably an ethylenically unsaturated polymerizable compound containing at least one reactive olefinic double bond.

[0023] The polymerizable group(s) may occur at any feasible point along the length of the monomer, however, in preferred embodiments the polymerizable group comprises, consists essentially of, or consists of a polymerizable end group.

[0024] The monomer component according to the present invention may comprise any known type of compound or substance consistent with the definitions specified elsewhere herein, however, in preferred embodiments, the monomer comprises, consists essentially of, or consists of one or more reactive diluent monomers containing a double bond.

[0025] Typical examples of such monomers containing one double bond are alkyl or hydroxyalkyl acrylates, such as methyl, ethyl, butyl, 2-phenoxyethyl, 2-ethylhexyl, 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), and 2-hydroxyethyl acrylate, isobornyl acrylate, methyl and ethyl acrylate, lauryl acrylate, ethoxylated nonylphenol acrylate, and diethylene glycol ethylhexyl acylate (DEGEHA). Methacrylated versions of such monomers are also available, if desired. Further examples of monomers are acrylonitrile, acrylamide, N-substituted acrylamide, vinyl esters such as vinyl acetate, styrene, alkylstyrenes, halostyrenes, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl chloride, and vinylidene chloride.

[0026]

[0026] Examples of monomers containing multiple double bonds are ethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, and vinyl acrylate.

[0027] In one embodiment, the monomer component comprises, consists essentially of, or consists of one or more monofunctional monomers. As used herein, "monofunctional" means having an average of 0.5 to 1.4 polymerizable groups per molecule, as determined by NMR methods. In a preferred embodiment, the monomer component comprises, consists of, or consists essentially of functional monomers, such as (meth)acrylic monomers.

[0028] One or more of the aforementioned monomers may be selected from one or more of the types listed herein, either alone or in combination, in compositions according to the present invention to adjust the cure speed or viscosity of the formulation to which they are associated, making it suitable for manufacturing processes, such as optical fiber coating processes, according to methods well known in the art to which the present invention applies. In one embodiment, the monomer component consists of a single monomer type. In another embodiment, the monomer component consists of more than one monomer type. Regardless of whether one or more different monomers are used, in one embodiment, the monomer component is present in an amount of 10% to 65% by weight, or 10% to 55% by weight, or 10% to 50% by weight, or 10% to 40% by weight, or 10% to 30% by weight; or 20% to 65% by weight, or 20% to 55% by weight, or 20% to 50% by weight, or 20% to 40% by weight, based on the total weight of the radiation-curable composition.

[0029] Oligomer component

[0029] Compositions according to the present invention also optionally include an oligomeric component; i.e., a collection of one or more individual oligomers having one or more particular structures or types. Oligomer is used herein to mean a molecule of intermediate relative molecular weight, the structure of which includes multiple units actually or conceptually derived from a molecule of lower relative molecular weight. As used herein, a component refers to a molecule having a MW of about 1000 g / mol to about 100,000 g / mol. theo If it has a value of MW theois determined by calculating the theoretical molecular weight of the idealized oligomer used. For purposes herein, an individual oligomer shall be construed as being part of the oligomeric component unless it has a self-healing moiety as described elsewhere herein; in such case, it shall be construed as being part of the self-healing component.

[0030] In one embodiment, if used, the oligomeric component has a theoretical molecular weight of at least 2000 grams per mole (g / mol), or at least 3000 g / mol, or at least 4000 g / mol, or 2000 to 15000 g / mol, or 2000 to 13000 g / mol, or 2000 to 10000 g / mol, or 3000 to 8000 g / mol, or 3500 to 5500 g / mol, or in another embodiment at least 1000 g / mol, more preferably greater than 1200 g / mol, and even more preferably comprises, consists of, or consists essentially of one or more oligomers having a theoretical molecular weight of more than 1500 g / mol, more preferably more than 1700 g / mol, and / or less than 15000 g / mol, more preferably less than 14000 g / mol, more preferably less than 13000 g / mol, more preferably less than 12000 g / mol, or from 1500 to 12000 g / mol, or from 2000 to 12000 g / mol, or from 2500 to 12000 g / mol, or from 2500 to 11000 g / mol, or from 2500 to 10000 g / mol.

[0031] When used, the oligomeric component preferably comprises, consists of, or consists essentially of one or more reactive oligomers having at least one reactive group or functional group. Such reactive or functional groups are preferably polymerizable groups. While some non-reactive oligomers are contemplated for use in the present invention, a majority of reactive oligomers are preferred. In one embodiment, the oligomeric component consists of, or consists essentially of, reactive oligomers.

[0032] In one embodiment, the reactive oligomer component according to the present invention comprises, consists essentially of, or consists of a reactive oligomer having at least one polymerizable group. In a preferred embodiment, the reactive oligomer component consists of a reactive oligomer having at least one polymerizable group. The polymerizable group may be of any known type. However, in one embodiment, the polymerizable group can comprise, consist essentially of, or consist of an acrylate or methacrylate group, or any combination thereof. The reactive oligomer is preferably an ethylenically unsaturated polymerizable compound containing one or more reactive olefinic double bonds.

[0033]

[0033] Polymerizable groups can occur at any feasible point along the length of the reactive oligomer, including polymerizable backbone groups or polymerizable end groups. Polymerizable backbone groups are present along a linear chain or branched from a linear chain along the length of the oligomer, while polymerizable end groups are polymerizable groups present at the end of the oligomer. Polymerizable groups can be present in isolation from other polymerizable groups or directly or indirectly adjacent to other polymerizable groups, such as in a branched or branched pattern at the end of the oligomer (interchangeably referred to herein as "end points"). In preferred embodiments, the polymerizable group comprises, consists essentially of, or consists of polymerizable end groups.

[0034]

[0034] Reactive oligomers according to the present invention may be of any known type consistent with the definitions specified elsewhere herein. Multilayer optical device compositions typically utilize reactive urethane oligomers for the desirable properties they can impart to related articles cured therefrom. In one embodiment, the oligomeric component comprises, consists of, or consists essentially of one or more urethane oligomers, preferably reactive urethane oligomers. The reactive urethane oligomer comprises at least one urethane group or moiety, preferably comprising a backbone, a polymerizable group, and at least a urethane group connecting the backbone to the polymerizable group. According to a first aspect, the reactive urethane oligomer comprises the reaction product of a polyol, a polyisocyanate, and an isocyanate-reactive (meth)acrylate.

[0035] Examples of suitable polyol compounds preferably used to form the backbone of the oligomer include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and other polyols. These polyols can be used alone or in combination of two or more. In a preferred embodiment, the backbone of the urethane oligomer comprises a reaction product of a polyether polyol. In one embodiment, the backbone comprises a reaction product of polypropylene glycol (PPG). As used herein, compounds derived from polypropylene glycol include end-capped PPGs, such as PPGs end-capped with EO. There are no particular limitations on the polymerization mode of the structural units in these polyols. Random polymerization, block polymerization, and graft polymerization are all acceptable. As used herein, polyol is intended to include organic compounds containing two or more hydroxyl functional groups per molecule.

[0036] As used herein, a block copolymer refers to a portion of an oligomer or polymer, comprising many constitutional units, at least one of which contains a characteristic not present in adjacent portions. As used herein, mono-, di-, and tri-block copolymers refer to the average amount of a particular block present in the oligomer. In preferred embodiments, the particular block refers to a polyether block derived from one or more polyols, preferably polyether polyols, described elsewhere herein. In one embodiment, the block referred to in mono-, di-, and / or tri-block copolymers is a polyether block derived from one or more polyols described elsewhere herein. In one embodiment, a monoblock copolymer can be described as a copolymer having an average of about 1 unit, or about 0.9 to 1.5 units, of a particular block, such as a polyether block. In one embodiment, a diblock copolymer can be described as a copolymer having an average of about 2 units, or at least 1.5 to 2.5 units, of a particular block, such as a polyether block. In one embodiment, a triblock copolymer may be described as a copolymer having an average of about 3 units of a particular block, such as a polyether block, or at least 2.5 to less than 3.5 units. The number of polyether units in a given oligomer may be determined by the number of polyether polyol molecules utilized in the synthesis of a single oligomer.

[0037] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol obtained by ring-opening copolymerization of two or more ionically polymerizable cyclic compounds, polydecamethylene glycol, and polyether diol. Examples of ionically polymerizable cyclic compounds include cyclic ethers such as ethylene oxide, propylene oxide, isobutene oxide, tetrahydrofuran, and 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monoxide, vinyloxetane, vinyltetrahydrofuran, vinylcyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ionically polymerizable cyclic compounds include combinations for producing binary copolymers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydrofuran, and 2-methyltetrahydrofuran; and combinations for producing terpolymers such as combinations of tetrahydrofuran, 2-methyltetrahydrofuran, and ethylene oxide, and combinations of tetrahydrofuran, butene-1-oxide, and ethylene oxide. The ring-opening copolymers of these ionically polymerizable cyclic compounds may be random copolymers or block copolymers.

[0038]

[0038] These polyether polyols include, for example, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), PEG#1000 (manufactured by Nippon Oil and Fats Co., Ltd.), PTG650(SN), PTG1000(SN), PTG2000(SN), PTG3000, PTGL1000, and PEG6000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), P710R, P1010, P2010, 1044 Included are the Pluracol® P series (by BASF), the Acrol® and Acclaim® series, which include PPG 725, PPG 1000, PPG 2000, PPG 3000, PPG 4000, and PPG 8000, and the Multranol® series (by Covestro), which includes PO / EO polyether diols with Mw of 2800 or 40000. Additionally, AGC Chemicals offers diols under the trade name Preminol®, such as Preminol S 4013F (Mw 12,000), Preminol 4318F (Mw 18,000), and Preminol 5001F (Mw 4,000).

[0039]

[0039] Examples of polyester polyols include polyester diols obtained by reacting polyhydric alcohols with polybasic acids. Examples of polyhydric alcohols include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. Examples of polybasic acids include phthalic acid, dimer fatty acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid / anhydride, etc. Preferably, the polybasic acid is selected so that the resulting polyester polyol is unsaturated.

[0040]

[0040] These polyester polyol compounds are commercially available under trade names such as MPD / IPA500, MPD / IPA1000, MPD / IPA2000, MPD / TPA500, MPD / TPA1000, MPD / TPA2000, Kurapol (registered trademark) A-1010, A-2010, PNA-2000, PNOA-1010, and PNOA-2010 (manufactured by Kuraray Co., Ltd.).

[0041] Triols, such as polyester or polyether triols, are also known. Oligotriols having the following general formula are particularly preferred: A(-----OH)3, where A is a chemical organic structure such as an aliphatic, cycloaliphatic, aromatic, or heterocyclic structure, "----" is an oligomeric chain such as a polyether chain, a polyester chain, a polyhydrocarbon chain, or a polysiloxane chain, to name a few, and "OH" is a terminal hydroxyl group. In one embodiment, the triol comprises, consists of, or essentially consists of a polyether triol, a PO homopolymer, a PE homopolymer, a PO-EO block copolymer, a random copolymer, or a hybrid block-random copolymer. In practice, polyether triols are generally made of glycerin or trimethylolpropane, with EO in the terminal or internal blocks, and with MW theo They can be based on PO, EO, or copolymers of PO and EO with molecular weights of about 500-15,000 g / mol. Another type of polyether triol is a glycerol or trimethylolpropane-based copolymer, such as THF-PO, THF-EO, THF-PO-EO, or THF-EO-PO, with a molecular weight between about 500 and 15,000. In a preferred embodiment, the triol is derived from biobased or natural reactants, such as certain vegetable oils and fats.

[0042]

[0042] Commercially available examples of suitable triols include related propylene oxide-based polyether triols available from Carpenter under the Carpol (registered trademark) GP designation, such as GP-1000, GP-1500, GP-1500-60, GP-3000, GP-4000, GP-5017, GP-5017-60, GP-5171, GP-6015, GP-6015-60, GP-6037-60, and GP-700. Additional triols are available under the Arcol® brand, such as Arcol LHT-240 (described by the manufacturer as having a molecular weight "Mw" of about 700), Arcol LHT-112 (Mw 1500), Arcol LHT LG-56 (Mw 3000), and Arcol LHT-42 (Mw 4200), under Multranol® trade names such as Multranol 9199 (Mw 4525), Multranol 3900 (Mw 4800), Multranol 3901 (Mw 6000), and Multranol 9139 (Mw 6000), and under Multranol® trade names such as Acclaim 703 (Mw 700), Acclaim 3300N (Mw 3000), Acclaim 6300 (Mw 6000), and Acclaim Commercially available triols include those sold under the Acclaim® trade name, such as Preminol S 3011 (Mw 10,000), Preminol 7001K (Mw 7,000), and Preminol 7012 (Mw 10,000), available from Covestro.

[0043]

[0043] The theoretical molecular weight derived from the hydroxyl value of these polyols is usually about 50 to about 15,000, preferably about 500 to 12,000, or about 1,000 to about 8,000.

[0044]

[0044] The reaction product of a (poly)isocyanate compound, preferably a diisocyanate compound, can be utilized to produce the urethane groups or moieties in the reactive urethane oligomer according to the first aspect of the present invention. As used herein, an isocyanate compound is defined as any organic compound having at least one isocyanate group per molecule. Examples of suitable isocyanates are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (hydrogenated) xylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), Included are diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, 2,4- and / or 4,4'-methylenedicyclohexyl diisocyanate, methylenediphenyl diisocyanate, tetramethylxylylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, and the like.

[0045]

[0045] These diisocyanate compounds can be used alone or in combination of two or more. In various embodiments, the diisocyanate includes isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, 2,4-tolylene diisocyanate, and / or 2,6-tolylene diisocyanate (mixtures of the two aforementioned diisocyanates are commercially available under the generic name "TDI"). Particularly preferred diisocyanates include trimethylhexamethylene diisocyanate (TMDI) compounds and isophorone diisocyanate (IPDI) compounds.

[0046]

[0046] As used herein, the term "polyisocyanate" refers to an isocyanate compound having two or more isocyanate moieties per molecule. In one embodiment, the oligomeric component comprises, consists essentially of, or consists of a urethane oligomer, which is the reaction product of one or more polyisocyanates. In addition to the diisocyanates mentioned above, polyisocyanates having three isocyanate groups per molecule, i.e., triisocyanates, can also be used. Known triisocyanates include biurets made from hexamethylene diisocyanate (HDI) or HDI trimer, which are commercially available from Covestro under the trade name Desmodur®, including, but not limited to, Desmodur N 3200, Desmodur N 3300, Desmodur N 3390, Desmodur N 3600, Desmodur N 3800, Desmodur N 3900, Desmodur N XP 2580, Desmodur XP 2599, Desmodur XP 2675, Desmodur XP 2731, Desmodur XP 2714 and Desmodur XP 2803.

[0047] Further commercially available triisocyanates include the Vestanat® T (IPDI trimer) and HT (HDI trimer) series of polyisocyanate crosslinkers for 2k systems, available from Evonik.

[0048] In one embodiment, the reactive urethane oligomer also includes the reaction product of an isocyanate-reactive (meth)acrylate. Any suitable (meth)acrylate, including monomers and oligomers, can be used, although (meth)acrylate monomers are preferred. Such isocyanate-reactive (meth)acrylates preferably include hydroxyl-containing (meth)acrylate compounds, as such compounds are known to react with isocyanates, including polyisocyanates. Hydroxyl group-containing (meth)acrylates include epoxies and (meth)acrylates, including (meth)acrylates and alkylene oxides derived from (meth)acrylates, more specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and hydroxyethyl caprolactone acrylate, ethoxylated trimethylolpropane diacrylate, glycerol di(meth)acrylate, and glycerin acrylate methacrylate (i.e., 3-(acryloyloxy)-2-hydroxypropyl methacrylate).

[0049] In one embodiment, the urethane oligomer also includes the reaction product of a non-functional end capper. Such compounds, when reacted with the oligomer via a (poly)isocyanate compound and / or an isocyanate-reactive (meth)acrylate, form a distal terminus along at least one arm or chain of the urethane oligomer that would otherwise yield a polymerizable group. Non-functional end cappers can include non-UV-curable compounds having active hydrogen groups, such as mercapto-group-containing (—SH) compounds, amino-group-containing (—NH) compounds, and hydroxyl-group-containing (—OH) compounds.

[0050] In a preferred embodiment, the urethane oligomer comprises the reaction product of a monohydric alcohol having no (meth)acrylic moieties. Such compounds are preferably reactive with the aforementioned (poly)isocyanates. The monohydric alcohol having no (meth)acrylic moieties can end-cap the oligomer with hydroxyl groups, rendering the arms or chains non-polymerizable.

[0051] In one embodiment, the monohydric alcohol compound having no (meth)acrylic moiety is a C1-C 18 , also C2-C 12 , also C4-C 10 The alcohols are aliphatic compounds such as linear or branched monohydric alcohols.

[0052]

[0052] Any suitable monohydric alcohol without a (meth)acrylic moiety can be used, but in preferred embodiments, the monohydric alcohol without a (meth)acrylic moiety comprises, consists of, or consists essentially of methanol, ethanol, isopropyl alcohol, butanol, pentanol, 2-ethylhexanol, cetyl alcohol, allyl alcohol, geraniol, propargyl alcohol, inositol, menthol, or any combination thereof.

[0053]

[0053] One or more urethanization catalysts are also preferably used in the reaction of the components used to make the urethane oligomer. Examples of such catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, and triethylenediamine-2-methyltriethyleneamine. The catalyst can be used in any suitable amount, or, for example, from about 0.01 to about 1 weight percent of the total amount of reactants. The reaction can be carried out at any suitable temperature, such as between 10 and 150°C, or from about 10 to about 90°C, or from about 30 to about 80°C.

[0054] In one embodiment, the urethane oligomer comprises a difunctional reactive urethane oligomer. As used herein, difunctionality means having an average of between 1.5 and 2.5 polymerizable groups per molecule, as determined by nuclear magnetic resonance spectroscopy (NMR). However, in other embodiments, the oligomeric component comprises, consists essentially of, or consists of a trifunctional reactive urethane oligomer, or an oligomer having an average of greater than 2.5 to 3.5 polymerizable groups per molecule. In another embodiment, the oligomeric component comprises a tetrafunctional oligomer, or an oligomer having an average of greater than 3.5 to 4.5 polymerizable groups per molecule. In preferred embodiments, the oligomeric component comprises, consists essentially of, or consists of one or more reactive urethane oligomers having an average (meth)acrylate functionality between 1.5 and 4.2, or 1.8 to 3.8, or 1.8 to 3.2, or 1.8 to 2.8. In one embodiment, the average (meth)acrylate functionality of the oligomeric component is between 1.5 and 4.2, or from 1.8 to 3.8, or from 1.8 to 3.2, or from 1.8 to 2.8.

[0055]

[0055] One or more of the aforementioned reactive urethane oligomers can be used in the compositions according to the present invention in any suitable amount and can be selected from any one or more of the types listed herein in combination. Thus, in one embodiment, the oligomeric component or reactive urethane oligomer is present in an amount of less than 65 wt%, or 10-65 wt%, or 10-55 wt%, or 10-50 wt%, or 10-40 wt%; or 15-65 wt%, or 15-55 wt%, or 15-50 wt%, or 15-40 wt%; or 20-65 wt%, or 20-55 wt%, or 20-50 wt%, or 20-40 wt%; or 25-65 wt%, or 25-55 wt%, or 25-50 wt%, or 25-40 wt%; or 30-65 wt%, or 30-55 wt%, or 30-50 wt%, or 30-40 wt%, based on the total weight of the composition.

[0056] In one embodiment, at least one of a monomeric component and an oligomeric component is present in the composition. In another embodiment, both a monomeric component and an oligomeric component are present. However, in another embodiment, neither a monomeric component nor an oligomeric component is present. In such cases, it is preferred that the properties and functionality desired in the polymer layers of a multilayer optical device typically imparted by the monomers and oligomers described herein are primarily satisfied via the self-healing component, as further described below.

[0057] self-healing ingredients According to a first aspect, a composition includes a self-healing component, i.e., a collection of one or more individual components having self-healing moieties. The self-healing component may comprise, consist of, or consist essentially of a monomer and / or oligomer having at least one self-healing moiety or group. As used herein, "moiety" and "group" are used interchangeably. A self-healing moiety is a collection of atoms that together facilitate a reversible interaction or covalent reaction with other self-healing moieties within a particular composition, without the explicit need for an external stimulus, such as the application of radiant energy, such as UV or heat. Of course, it will be understood that such a reversible interaction or covalent reaction may still be achieved or accelerated by an external stimulus. Through this process, also known as self-assembly, the self-healing moiety contributes to enabling the polymeric material to exhibit self-healing and / or improved stress relaxation properties. It is not necessary for the cured product of a composition including the self-healing moiety of the present invention to exhibit a particular minimum degree of self-healing and / or stress relaxation, and it will be understood that the degree of self-healing and / or stress relaxation will vary depending on the particular formulation and end-use requirements and environmental conditions involved.

[0058]

[0058] However, in preferred embodiments, a sufficient amount of the self-healing material should be present in the composition from which the polymer layers of the multilayer optical device are formed or cured to produce the desired amount of stress relaxation or self-healing at the temperatures and time scales required for the end use. The inventors have found that self-healing and / or stress relaxation may be optimized when the composition has a sufficient amount of the self-healing component and / or when the composition has more than the appropriate minimum amount of the self-healing moiety.

[0059]

[0059] Thus, according to a first aspect of the present invention, the self-healing component is present in an amount greater than 30 wt. % based on the weight of the total composition, and / or the composition has greater than 0.015 equivalents of self-healing moiety per 100 g of composition. As used herein, the "equivalent amount" of self-healing moiety for a given composition is determined by summing the molar amounts of the self-healing moiety in the self-healing component (Z) according to the following formula: TIFF0007795474000001.tif11170In formula, TIFF0007795474000002.tif8170=Amount by weight of each component Z per 100 g of the total relevant composition; TIFF0007795474000003.tif8170 = The number of self-repairing moieties present in one molecule of component Z; and TIFF0007795474000004.tif8170Theoretical molecular weight of component Z.

[0060]

[0060] If the complete formulation of the composition is unknown, the equivalent weight of the self-healing portion can be analytically determined by any suitable method understood by those skilled in the art to which this invention applies, such as size exclusion chromatography (SEC) or nuclear magnetic resonance (NMR) methods.

[0061] In other embodiments, depending on the nature and type of self-healing moiety used, the composition may contain from 0.015 to 0.5 equivalents, alternatively from 0.015 to 0.2, alternatively from 0.015 to 0.15, alternatively from 0.015 to 0.1, alternatively from 0.015 to 0.08, alternatively from 0.015 to 0.05, alternatively from 0.015 to 0.045; alternatively from 0.02 to 0.2, alternatively from 0.02 to 0.15, alternatively from 0.02 .... or 0.022 to 0.15, or 0.022 to 0.1, or 0.022 to 0.08, or 0.022 to 0.05, or 0.022 to 0.045; or 0.025 to 0.20; or 0.037 to 0.15, or 0.037 to 0.1, or 0.037 to 0.08, or 0.037 to 0.05 equivalents. For the avoidance of doubt, unless otherwise specified, all "equivalent weight" values ​​expressed herein relate to the equivalent weight of the moiety of interest (UPy, self-healing, (meth)acrylate, etc.) per 100g of the total composition.

[0062] Various types of self-healing moieties are known. One class of self-healing moieties includes hydrogen-bonding groups. Hydrogen-bonding groups are groups that form hydrogen bonds during polymerization or while the composition remains in an uncured liquid state. In one embodiment, the hydrogen-bonding group is a multiple hydrogen-bonding group. As used herein, a "multiple hydrogen-bonding group" is configured to provide at least three hydrogen bonds to a dimer formed from two molecules containing the same or different self-healing moieties. A preferred type of multiple hydrogen-bonding group includes a 2-ureido-4-pyrimidinone (UPy) group. UPy groups, or moieties (such terms are used interchangeably herein), are desirable because they are self-complementary and are known to produce a strong multiple hydrogen-bonding effect of approximately 14 kcal / mol when calculated based on the direct addition of hydrogen bond energies, without considering secondary interaction effects. This is much smaller than the bond dissociation energy between a single covalent bond (such as a carbon-carbon bond, which is on the order of about 100 kcal / mol), but exceeds the bond dissociation energy of other hydrogen-bonding groups such as NH---:O and NH---:N (estimated at 2-8 kcal / mol). Therefore, the UPy moiety can create a so-called "super" hydrogen-bonding effect. A non-limiting example of a UPy group is 6-methyl-2-ureido-4-pyrimidinone, which has the following chemical structure: TIFF0007795474000005.tif48170

[0063] UPy groups can be formed as the reaction product of a multiple hydrogen bonding group precursor. A non-limiting example of such a multiple hydrogen bonding group precursor is 2-amino-4-hydroxy-6-methyl-pyrimidine, which has the following chemical structure: TIFF0007795474000006.tif41170

[0064]

[0064] UPy groups can be formed as reaction products of other multiple hydrogen bonding group precursors such as 2-amino-4-hydroxy-pyrimidine, 2-amino-4-hydroxy-6-ethyl-pyrimidine, 2-amino-4-hydroxy-6-propyl-pyrimidine, 2-amino-4-hydroxy-6-butyl-pyrimidine, 2-amino-4-hydroxy-6-hexyl-pyrimidine, 2-amino-4-hydroxy-6-octyl-pyrimidine and 2-amino-4-hydroxy-6-(2-hydroxyethyl)-pyrimidine.

[0065] In one embodiment, the self-healing moiety comprises, consists of, or consists essentially of multiple hydrogen-bonding groups. In one embodiment, the self-healing moiety comprises, consists of, or consists essentially of UPy groups.

[0066] In various embodiments of the first aspect, the self-healing component is configured to include at least a first molecule having a first self-healing portion and a second molecule having a second self-healing portion, the first self-healing portion of the first molecule bonded to the second self-healing portion of the second molecule. In one embodiment, the bond dissociation energy formed between the first self-healing portion and the second self-healing portion is between 9 kcal / mol and 100 kcal / mol, or between 9 kcal / mol and 80 kcal / mol, or between 10 kcal / mol and 50 kcal / mol, or between 12 kcal / mol and 50 kcal / mol, or between 12 kcal / mol and 90 kcal / mol, or between 9 kcal / mol and 30 kcal / mol, or between 9 kcal / mol and 20 kcal / mol. Bond dissociation energies can be determined by a variety of suitable methods, non-limiting examples of which can be found in Table 1 of The Scientific World Journal (2004) 4, 1074-082; and in Nature 2002, volume 3, 836-847, through a summary of direct addition of all bonds of the self-healing moiety.

[0067] While the first and second self-healing moieties can be different, in preferred embodiments, they are the same. In one embodiment, the first and second self-healing moieties are the same and are configured to dimerize. Dimerization is an addition reaction in which two molecules of the same compound react with each other to produce an adduct. Upon forming a dimer, the two molecules align and preferably form multiple hydrogen bonds. In preferred embodiments, the dimer has at least three, or at least four, or between three and four hydrogen bonds. In one embodiment, the formed dimer also includes a first linear chain connected to each of the hydrogen bonds on the first self-healing moiety and a second linear chain connected to each of the three or four hydrogen bonds on the second self-healing moiety, each of the first linear chain and the second linear chain containing fewer than seven covalent bonds.

[0068] The complete molecular structure into which the self-healing moiety is incorporated can be of any suitable type. However, in one embodiment, the self-healing moiety is incorporated into a monomer or oligomer, including the types listed elsewhere herein. In a preferred embodiment, the self-healing moiety is incorporated into a reactive urethane oligomer. Such oligomers, as specifically described elsewhere herein, can be utilized and constructed in a similar manner as described above, with the further addition of a self-healing moiety via known reaction mechanisms to produce a structure that is incorporated into the self-healing component. In embodiments in which the UPy group is incorporated into a urethane oligomer as described elsewhere herein, the diisocyanate used can comprise, consist of, or consist essentially of trimethylhexamethylene diisocyanate (TMDI) and / or isophorone diisocyanate (IPDI) compounds. This is because the inventors have found that, depending on the stoichiometry and other reactants used, the reaction of precursors to UPy groups and some other diisocyanate compounds (such as hexamethylene diisocyanate) can produce solid products at room temperature. This tends to make the overall oligomer synthesis more expensive and / or difficult, especially on a commercial scale.

[0069]

[0069] The inventors have surprisingly found that many of the self-healing oligomers described herein, particularly those containing at least three urethane linkages, tend to produce oligomers with lower viscosity values ​​and / or that are more easily processable, particularly in optical fiber coating applications, thereby allowing for increased loadings of the self-healing component in the associated coating composition. The addition of a large amount of the self-healing component is important, among other things, to facilitate the creation of formulations suitable for use in producing self-healing and / or stress-relieved cured products that are readily processable in the manufacture of coated optical fibers.

[0070] In one embodiment, the self-healing component comprises, consists of, or consists essentially of one or more molecules according to structure (VI) below: [A(G) n -D m ]-[A(G) n-1- D m ] k -Z (VI) During the ceremony, A is carbon or nitrogen; where n=3 when A is an sp3 carbon, and n=2 when A is an sp2 carbon or nitrogen; m is an integer from 0 to 500; k is a number between 0 and 20; D for each occurrence of m is a divalent spacer independently selected from -O-; -O-;-C(O)-;-Aryl-;-C≡C-;-N=N-;-S-;-S(O)-;-S(O)(O)-; -(CT2) i -;-N(T)-;-Si(T)2(CH2) i -;-(Si(T)2O) i -;-C(T)=C(T)-; a bivalent spacer independently selected from -C(T)=N-; -C(T)=; -N=; or combinations thereof; where for each instance in D of a single bond, a single bond is attached to it, and for each instance in D of a double bond, a double bond is attached to it; each T is selected at each occurrence from a monovalent unit comprising hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl; Each T may also be selected from divalent Dm and may be bonded to another divalent T also selected from Dm to form a ring structure; i is an integer from 1 to 40; Each group in each of the m, n, and k units may be the same or different; Z is hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or a maleimide group; G, for each occurrence of n, is hydrogen, -Dm-Z, or has the following structure (VI-b): (ZD m ) j XD m - (VI-b); (In the formula, X is a multi-hydrogen bonding group, a disulfide group, or a urea group; When X is divalent, j=1, and when X is monovalent, j=0; For at least one occurrence of n, G is a self-repairing moiety according to structure (VI-b).

[0071] In one embodiment, X comprises, consists of, or consists essentially of a disulfide group and / or a urea group. In a preferred embodiment, X is a 2-ureido-4-pyrimidinone group (UPy) where j=0. The UPy group can be the reaction product of any suitable compound, but in one embodiment, comprises the reaction product of 2-amino-4-hydroxy-6-methyl-pyrimidine. In one embodiment, X comprises, consists of, or consists essentially of the following structure (VI-c): TIFF0007795474000007.tif47170, wherein D, m, and Z are as defined above for structure (VI), and R represents the remainder of structure (VI).

[0072] In certain embodiments, D comprises a urethane group, the urethane group being the reaction product of a diisocyanate compound. In certain embodiments, D further or alternatively comprises a polyol component. The polyol component may be of any suitable type, including, but not limited to, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, other polyols, and / or combinations thereof. Suitable diisocyanate compounds and polyols are described elsewhere herein above.

[0073] In certain embodiments, Z comprises a (meth)acrylate group. Such functionality renders molecules according to structure (VI) polymerizable in a manner consistent with many current conventional coatings, such as those for use in optical fibers and / or other polymer layers in multilayer optical devices.

[0074] In one embodiment, the self-healing component has a theoretical molecular weight (MW) of 500 to 100,000 g / mol. theoIn a preferred embodiment, the self-healing component comprises, consists of, or consists essentially of molecules according to structure (VI), wherein structure (VI) also has a molecular weight of between 500 and 8000; between 500 and 5000; between 500 and 4000; between 500 and 3000; or between 500 and 2000; or between 500 and 1500; or between 500 and 1000; or between 500 and 900; or between 500 and 700; or between 700 and or between 700 and 3000; or between 700 and 2000; or between 700 and 1500; or between 700 and 1000; or between 900 and 4000; or between 900 and 3000; or between 900 and 2000; or between 900 and 1500; or between 1000 and 4000; or between 1000 and 3000; or between 1000 and 2000; or between 1000 and 1500 theo ) (in g / mol).

[0075] Depending on the needs of the application, it may be important to tailor the self-healing component to maximize its effectiveness in promoting self-healing properties and / or stress relaxation behavior at a particular temperature. For example, it may be preferable to tailor the composition so that the glass transition temperature (Tg) of the self-healing component is lower than room temperature, in order for the composition to most effectively impart self-healing properties and / or stress relaxation behavior at room temperature. Indeed, although not necessarily required, the self-healing configuration may comprise, consist of, or consist essentially of molecules having a Tg value lower than the temperature at which self-healing and / or stress relaxation capabilities are desired. Thus, for example, oligomers having self-healing moieties may not crystallize (or, in the case of amorphous materials, not enter a glassy state) at operating temperatures, thereby maximizing the ability of the self-healing moieties to self-assemble, dimerize, bond, or otherwise interact in the manner necessary to achieve self-healing and / or stress relaxation.

[0076] Thus, in one embodiment, the self-healing component(s) and / or molecule(s) according to structure (VI) above have a glass transition temperature (Tg) that is less than 150° C., or less than 25° C., or less than 0° C., or less than −10° C., or less than −20° C., or less than −30° C., or between −30 and 20° C., or between −25 and 20° C., or between −20 and 10° C. All else being equal, a lower glass transition temperature would theoretically tend to be preferable as it would facilitate self-healing and / or stress relaxation functionality over a wider range of operating temperatures.

[0077] Regardless of the nature of the self-healing portion or the overall structure to which it is associated, the self-healing component optionally comprises, consists of, or consists essentially of molecules that also have polymerizable moieties. When such polymerizable moieties are present, molecules in the self-healing component can therefore undergo polymerization and / or cross-linking reactions with other molecules in the self-healing component, as well as molecules in the optional monomeric and / or oligomeric components. In this way, the self-healing component will be capable of bonding both for the purpose of building a "permanent" set of cross-linked polymer chains to impart the necessary physical properties to a polymer layer of a multilayer optical device, such as an optical fiber coating, as well as for the purpose of "reversible" interactions or covalent bonds that facilitate its self-healing and / or stress relaxation. The polymerizable moieties can include, but are not limited to, radiation-curable moieties, heat-curable moieties, or both radiation-curable and heat-curable moieties, such as, for example, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydrido, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimide groups.

[0078] Preferably, the polymerizable portion of the self-healing component comprises a radiation-curable moiety such as an acrylate or methacrylate group.

[0079] The inventors have also discovered that the effectiveness and usefulness of the self-healing coating in various applications, including coating optical fibers, can be improved if the amount of polymerizable groups in the self-healing component is maintained within certain values. Thus, in one embodiment, the self-healing component has from 0.015 to 0.1 equivalents, or from 0.03 to 0.1 equivalents, or from 0.037 to 0.1 equivalents, or from 0.03 to 0.08 equivalents, or from 0.03 to 0.05 equivalents, or from 0.037 to 0.08 equivalents, or from 0.037 to 0.05 equivalents, or from 0.037 to 0.05 equivalents, of polymerizable moieties and / or (meth)acrylate groups per 100 grams of composition.

[0080] In a broader context, regardless of whether all such polymerizable moieties are included in the self-healing component, the inventors have found that it can also be useful to control the number of polymerizable moieties throughout the composition. Thus, in one embodiment, the composition has from 0.1 to 0.4 equivalents, or from 0.1 to 0.3 equivalents, or from 0.1 to 0.25 equivalents, or from 0.15 to 0.4 equivalents, or from 0.15 to 0.3 equivalents, or from 0.15 to 0.25 equivalents, or from 0.15 to 0.2 equivalents of polymerizable moieties and / or (meth)acrylate groups per 100 g of composition.

[0081]

[0081] Furthermore, the inventors have found that it may be helpful to tailor the amounts of self-healing moieties and polymerizable moieties relative to one another. Without wishing to be bound by any theory, it is believed that an excessive number of polymerizable moieties relative to the self-healing moieties may produce a highly crosslinked cured product that does not promote sufficient internal reorientation of the relative lack of self-healing groups to self-assemble or reach each other to provide repair. Conversely, if the number of polymerizable groups is insufficient, the composition may not cure sufficiently (or may not cure quickly enough), thereby either rendering such compositions unsuitable for processing and / or increasing the likelihood that cured coatings made therefrom will have poor mechanical performance properties.

[0082]

[0082] Thus, in one embodiment, the composition has an equivalent ratio of polymerizable groups to equivalents of self-healing groups, preferably comprising, consisting of, or consisting essentially of UPy groups in the composition, of less than 14, or less than 10, or less than 8, or less than 6, or less than 5, or from 1 to 14, or from 1 to 10, or from 1 to 8, or from 1 to 6, or from 1 to 5, or from 3 to 10, or from 3 to 8, or from 3 to 5. In preferred embodiments, the aforementioned ratios are applicable to scenarios where the polymerizable groups comprise, consist of, or consist essentially of (meth)acrylate groups and the self-healing moieties comprise, consist of, or consist essentially of UPy groups.

[0083]

[0083] The self-healing component can be present in any suitable amount, but in various embodiments, it is present in an amount of greater than 30% to 100% by weight, or greater than 30% to 75% by weight, or greater than 30% to 70% by weight, or greater than 30% to 60% by weight; or 40% to 80% by weight, or 40% to 75% by weight, or 40% to 70% by weight, or 40% to 60% by weight, based on the weight of the total composition.

[0084] Initiator Component According to a first aspect, the composition comprises an initiator component, i.e., a group of one or more individual initiators having one or more specific structures or types. Initiators are compounds that undergo a chemical change upon the action of an external stimulus, such as heat or light, to generate at least one radical, acid, or base. Initiators can be used to promote polymerization reactions by several mechanisms, including free radical polymerization and cationic polymerization. In a preferred embodiment, the initiator component comprises, consists of, or consists essentially of an initiator that promotes free radical polymerization; i.e., it comprises, consists of, or consists essentially of a free radical initiator.

[0085] In one embodiment, the composition comprises, consists of, or consists essentially of one or more photoinitiators. A photoinitiator is a compound that undergoes a chemical change under the action of light, or a synergistic action between the action of light and the electronic excitation of a sensitizing dye, to preferably promote a polymerization reaction in a composition with which it is associated. Well-known types of photoinitiators include cationic photoinitiators and free-radical photoinitiators. According to one embodiment of the present invention, the photoinitiator comprises, consists of, or consists essentially of a free-radical photoinitiator.

[0086] In one embodiment, the photoinitiator component comprises, consists of, or consists essentially of one or more acylphosphine oxide photoinitiators. Acylphosphine oxide photoinitiators are known and are disclosed, for example, in U.S. Patent Nos. 4,324,744, 4,737,593, 5,942,290, 5,534,559, 6,020,529, 6,486,228, and 6,486,226. Preferred types of acylphosphine oxide photoinitiators for use in the photoinitiator component include bisacylphosphine oxide (BAPO) or monoacylphosphine oxide (MAPO). More specifically, examples include 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (CAS# 84434-11-7) or 2,4,6-trimethylbenzoyldiphenylphosphine oxide (CAS# 127090-72-6).

[0087] The photoinitiator component may also optionally comprise, consist of, or consist essentially of an α-hydroxyketone photoinitiator. For example, suitable α-hydroxyketone photoinitiators are α-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)phenyl]propanone.

[0088] In another embodiment, the photoinitiator component is an α-aminoketone such as 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(4-methylbenzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-(dimethylamino)-1-[3,4-dimethoxyphenyl]-1-butanone; benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2-methylbenzophenone, 2-methoxycarbonylbenzophenone, 4,4′-bis(chloromethyl)-benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone benzophenones such as phenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl 2-benzoylbenzoate, 3,3'-dimethyl-4-methoxybenzophenone, 4-(4-methylphenylthio)benzophenone, 2,4,6-trimethyl-4'-phenyl-benzophenone or 3-methyl-4'-phenyl-benzophenone; ketal compounds, for example 2,2-dimethoxy-1,2-diphenyl-ethanone; and monomeric or dimeric phenylglyoxylates such as methylphenylglyoxylate, 5,5'-oxo-di(ethyleneoxydicarbonylphenyl) or 1,2-(benzoylcarboxy)ethane.

[0089] Yet another suitable photoinitiator for use in the photoinitiator component includes oxime esters such as those disclosed in U.S. Patent No. 6,596,445. Yet another class of suitable photoinitiators for use in the photoinitiator component includes phenylglyoxalates such as those disclosed in U.S. Patent No. 6,048,660.

[0090]

[0090] In another embodiment, the photoinitiator component can comprise, consist of, or consist essentially of one or more alkyl-, aryl-, or acyl-substituted compounds not mentioned above in this specification.

[0091] According to another embodiment, the composition can include a photoinitiator that is an alkyl-, aryl-, or acyl-substituted compound. In one embodiment, the alkyl-, aryl-, or acyl-substituted photoinitiator has or is centered around a carbon (group 14) atom. In such instances, upon excitation (by absorption of radiation), the group 14 atom present in the photoinitiator compound forms a radical. Thus, such compounds can generate radicals having or centered on an atom selected from the group consisting of silicon, germanium, tin, and lead. In one embodiment, the alkyl-, aryl-, or acyl-substituted photoinitiator is an acylgermanium compound. Such photoinitiators are described in U.S. Pat. No. 9,708,442, assigned to DSM IP Assets BV, the entire contents of which are incorporated herein by reference. Known specific acylgermanium photoinitiators include benzoyltrimethylgermane (BTG), tetracylgermanium, or bisacylgermanoyl (commercially available as Ivocerin® from Ivoclar Vivadent AG, 9494 Schaan / Liechtenstei).

[0092] Photoinitiators according to the present invention can be used singly or in combination as a blend. Suitable photoinitiator blends are disclosed, for example, in U.S. Pat. No. 6,020,528 and U.S. patent application Ser. No. 60 / 498,848. According to one embodiment, the photoinitiator component comprises a photoinitiator blend of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (CAS#162881-26-7) and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (CAS#84434-11-7), for example, in a weight ratio of about 1:11, 1:10, 1:9, 1:8, or 1:7.

[0093] Another particularly suitable photoinitiator blend is, for example, a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-1-propanone (CAS#7473-98-5) in a weight ratio of about 3:1:15, 3:1:16, 4:1:15, or 4:1:16. Another suitable photoinitiator blend is, for example, a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone in a weight ratio of about 1:3, 1:4, or 1:5.

[0094] In one embodiment, the composition can include a thermal initiator. In a preferred embodiment, the thermal initiator comprises, consists of, or consists essentially of a thermal free radical polymerization initiator. Examples of thermal free radical polymerization initiators include, but are not limited to, azo compounds such as azoisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanenitrile), 1,1'-azobis(2,4,4-trimethylpentane), and the like, CC labile compounds such as benzopinacol, peroxides, and mixtures thereof.

[0095] In one embodiment, the thermal initiator comprises a peroxide. Potentially suitable peroxides include organic and inorganic peroxides. In one embodiment, the thermal initiator is soluble in the composition.

[0096] Examples of peroxides include, for example, percarbonates (of formula -OC(O)O-), peroxyesters (of formula -C(O)OO-), diacyl peroxides (also known as peranhydrides) (of formula -C(O)OOC(O)-), dialkyl peroxides or perethers (of formula -OO-), hydroperoxides (of formula -OOH), etc. Peroxides may also be oligomeric or polymeric in nature.

[0097]

[0097] Thermal free radical polymerization initiators can include, for example, percarbonates, peresters, or peranhydrides. Peranhydrides include, for example, benzoyl peroxide (BPO) and lauroyl peroxide (commercially available as Laurox®). Peresters include, for example, t-butyl perbenzoate and 2-ethylhexyl perlaurate. Percarbonates include, for example, di-t-butyl percarbonate and di-2-ethylhexyl percarbonate or monopercarbonate.

[0098] One or more of the aforementioned initiators can be used in any suitable amount for use in the initiator component in the composition according to the first aspect of the present invention, and can be selected singly or in combination of one or more of the types listed herein. In a preferred embodiment, the initiator component comprises, consists of, or consists essentially of a free radical photoinitiator. In one embodiment, the initiator component is present in an amount of 0.01 wt. % to 10 wt. %, or about 0.01 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. %, or 0.1 wt. % to about 10 wt. %, or about 0.1 wt. % to about 5 wt. %, or about 1 wt. % to about 5 wt. %, based on the total weight of the composition.

[0099] additives

[0099] Compositions according to the present invention optionally include additive components; i.e., a group of one or more individual additives having one or more particular structures or types. Typically, additives are also added to the composition to achieve certain desired properties, such as improved adhesion to the glass layer(s) of a multilayer optical device, improved shelf life, or improved oxidative and hydrolytic stability of the coating. There are many different types of desirable additives, and the invention discussed herein is not intended to be limited thereby, but they are included in contemplated embodiments because of their desirable effects.

[0100]

[0100] Examples of additives for use in the additive component include thermal inhibitors intended to prevent premature polymerization, examples being hydroquinone, hydroquinone derivatives, p-methoxyphenol, beta-naphthol, or sterically hindered phenols such as 2,6-di(tert-butyl)-p-cresol. Shelf life in the dark can be increased by using, for example, copper compounds such as copper naphthenate, copper stearate, or copper octoate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite, or tribenzylphosphite, or quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride.

[0101] To block atmospheric oxygen during polymerization, additives such as paraffin or similar waxy substances can be added; due to their low solubility in the polymer, they migrate to the surface at the start of polymerization and form a transparent surface layer that prevents air from entering. Similarly, an oxygen barrier layer can be applied.

[0102] Further potentially suitable additives include light stabilizers. Light stabilizers include UV-absorbers such as well-known commercially available UV absorbers of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. It is possible to use such compounds individually or in mixtures with or without sterically hindered, relatively non-basic amine light stabilizers (HALS). Sterically hindered amines are, for example, based on 2,2,6,6-tetramethylpiperidine. UV absorbers and sterically hindered amines include, for example:

[0103] 2-(2-hydroxyphenyl)-2H-benzotriazoles, such as the known, commercially available hydroxyphenyl-2H-benzotriazoles and benzotriazoles disclosed in U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; No. 278,589; No. 4,315,848; No. 4,347,180; No. 4,383,863; No. 4,675,352; No. 4,681,905; No. 4,853,471; No. 5,268,450; No. 5,278,314; No. 5,280,124; No. 5,319,091; No. 5,410,071; No. 5,436,349; No. 5,516,914; No. 5,554,760; No. 5,563,242; No. 5,574,166; No. 5,607,98 Nos. 5,977,219 and 6,166,218, for example, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-t-butylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy))carbonyl-ethyl)-,phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole azole, dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-methoxyphenyl)-2H-benzotriazole 2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-2H-benzotriazole azole, 2,2'-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol), 2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole, methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t- Butyl-4-hydroxyhydrocinnamate, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

[0104] Another class of examples are 2-hydroxybenzophenones, such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and Includes 2'-hydroxy-4,4'-dimethoxy derivatives.

[0105]

[0105] Yet another class of examples includes, for example, esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0106]

[0106] Additional additives suitable for use in the additive component include compounds that accelerate photopolymerization, such as so-called photosensitizers, which shift or broaden the spectral sensitivity of the composition into which they are incorporated. Photosensitizers include, in particular, aromatic carbonyl compounds, such as benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, 3-acylcoumarin derivatives, and also 3-(aroylmethylene)thiazolines, and also eosin, rhodamine dyes, and erythrosine dyes. Alternatively, non-aromatic carbonyl compounds can be used. An example of a non-aromatic carbonyl is dimethoxyanthracene.

[0107] The curing procedure can be aided by the use of additives that, in particular, produce or facilitate the production of colored compositions. Such additives include azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazosulfides, pentaazadienes, or peroxy compounds such as hydroperoxides or peroxycarbonates, e.g., t-butyl hydroperoxide, as described, for example, in U.S. Pat. No. 4,753,817, pigments such as titanium dioxide, and also additives that form free radicals under thermal conditions. Further suitable materials for this purpose include benzopinacol compounds.

[0108] The additive component may include photoreducible dyes, such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin, or acridine dyes, and / or trihalomethyl compounds cleavable by radiation. Such additives are described, for example, in U.S. Patent No. 5,229,253.

[0109]

[0109] Other conventional additives may be used depending on the intended use. Examples include optical brighteners, fillers, pigments, dyes, wetting agents, leveling aids, etc. Thick pigmented coatings may also include glass microbeads or powdered glass fibers, as described, for example, in U.S. Patent No. 5,013,768.

[0110]

[0110] One or more of the foregoing additives can be used in the compositions according to the present invention in any suitable amount, and can be selected alone or in combination with one or more of the types listed herein. In preferred embodiments, the additive component is present in an amount of 0% to 59.99% by weight, or about 0% to 40% by weight, or 0% to 30% by weight, or 0% to 20% by weight, or 0% to 10% by weight, or 0% to 5% by weight; or 0.01% to 40% by weight; or 0.01% to 30% by weight, or 0.01% to 20% by weight, or 0.01% to 10% by weight, or 0.01% to 5% by weight, or 0.1% to 2% by weight, based on the total weight of the composition.

[0111] Compositions according to the first aspect of the present invention are desirably free of additives or ingredients that tend to inhibit polymerization and / or self-assembly reactions. Specifically, it is desirable to maintain the composition substantially free of reagents that tend to inhibit free radical polymerization or hydrogen bonding. Such ingredients may include so-called superacids and / or superbases, as will be understood by those skilled in the art.

[0112]

[0112] Compositions according to the first aspect of the present invention can be prepared so that they contain various amounts of the aforementioned components in various amounts relative to each other. In one embodiment, the monomer and / or oligomer component is present from 10% to 65% by weight, or from 10% to 55% by weight, or from 10% to 50% by weight, or from 10% to 40% by weight, or from 10% to 30% by weight; or from 20% to 65% by weight, or from 20% to 55% by weight, or from 20% to 50% by weight, or from 20% to 40% by weight; the self-healing component is present from greater than 30% to 100% by weight, or from greater than 30 to 75% by weight, or from greater than 30 to 70% by weight, or from greater than 30 to 60% by weight; the initiator is present from 0.01% to 10% by weight, or from 0.05% to 5% by weight, or from 0.1% to 3% by weight; and the additive is present from 0% to 59.99% by weight, each component added to add up to 100% by weight.

[0113] To be suitable for use in a variety of typical coating applications, such as optical fiber coating applications, a composition must have an appropriate viscosity value. Viscosity can be adjusted, as desired, according to methods known in the art, particularly by incorporating various types of reactive diluent monomers or oligomers. Furthermore, as described elsewhere herein, certain self-healing components, such as those having three or more, or four or more urethane linkages, and / or those according to structure (VI), can surprisingly enhance the viscosity and / or solubility properties to make their associated formulations suitable for use in a variety of coating applications, while still retaining a sufficient number of self-healing moieties to impart the desired self-healing properties and / or stress relaxation behavior to the cured coating. Thus, in one embodiment, the composition has a viscosity of 50 s -1 and a temperature of 25°C, of ​​a viscosity of less than 40 Pascal seconds (Pa·s), or less than 30 Pa·s, or less than 15 Pa·s, or less than 10 Pa·s, or less than 1 Pa·s, or from 1 Pa·s to 20 Pa·s, or from 1 Pa·s to 15 Pa·s, or from 1 Pa·s to 10 Pa·s, or from 0.05 to 5 Pa·s, or from 0.05 to 1 Pa·s.

[0114] As discussed, compositions according to the present invention may have self-healing properties and / or stress relaxation behavior. In various embodiments, it is desirable to formulate a composition that exhibits measurable self-healing properties. It is often impractical to directly measure the magnitude of the self-healing effect of a coating in its liquid state before curing. Therefore, it is preferable to determine the self-healing effect of a composition by measuring certain physical properties of a cured product made from the composition. Specifically, it is possible to evaluate the self-healing ability of a given amount of uncured composition when subjected to a predefined set of curing conditions, and then measure the certain physical properties both after initial curing and after damaging the cured product in a controlled manner and allowing a period of time for the cured product to self-heal.

[0115] In one embodiment, self-healing can be observed visually, such as by qualitative assessment of the disappearance of cavitation over time. Visual detection of cavitation is described in U.S. Patent No. 7,067,564, assigned to DSM IP Assets BV.

[0116] In various embodiments, curing any of the compositions according to any of the embodiments of this first aspect involves exposing the composition to 1 J / cm of energy from a radiation source emitting a peak spectral output between 360 nm and 400 nm. 2 and (c) subjecting the film to a dose of 55° C., preferably 25° C., whereby self-healing of the 3 mil film is observed, whereby if at least one cut damage is formed in the film, the film is configured to repair <80% of the cut damage area formed within a period of 8 hours or less, or preferably 1 hour or less, or preferably 5 minutes or less, or preferably 1 minute or less, while maintaining the film at a temperature of 55° C., preferably 25° C. In other embodiments, the foregoing test can alternatively be constructed by applying a composition having self-healing components to a fiber or wire and curing to more closely simulate the shape and load, and the resulting self-healing coating functioning in a multilayer optical device such as a coated optical fiber.

[0117] In one embodiment, the composition is prepared by subjecting the composition to 1 J / cm 2 radiation from a radiation source emitting a peak spectral output between 360 nm and 400 nm. 2 and wherein the post-cut tensile strength is measured within 10 minutes, or within 30 minutes, or within 2 hours, or within 4 hours, or within 8 hours, or within 12 hours after subjecting the film to the above cutting procedure, and the self-healing multilayer optical device is maintained at a temperature of 25°C or less; and the post-cut tensile strength is greater than 50%, or greater than 60%, or greater than 85%, or greater than 90%, or greater than 95% of the pre-cut tensile strength.

[0118] The above pre-cut and post-cut tensile strengths are preferably measured according to ASTM D638, with some modifications where applicable to allow for measurement of softer materials, as will be understood by those skilled in the art to which this invention applies. Specifically, such modifications include applying a 3 mil thick coating of talc, cutting them into 0.5 inch wide strips, and then conditioning them overnight at 50±5% relative humidity and 23.0±1.0°C. The strips can then be loaded into a mechanical testing machine with a 2 lb load cell, a crosshead speed of 25.4 mm / min, and a gauge length of 2.00 inches, and stretched to break.

[0119] A second aspect of the present invention is a compound having the following structure (VII): [UPy-(D m -UD m ) (2+q) ]-[A(G) (n-1) -D m ] k -Z (VII); [In the formula, UPy represents the UPy group, which is 2-ureido-4-pyrimidinone; U represents -NHC(O)E- or -EC(O)NH-, where E is O, NH, N(alkyl), or S; q is a number greater than or equal to 0 and less than or equal to 10; preferably, q is greater than 0, or 2+q is a number greater than 2 and less than or equal to 4, or a number greater than 4 and less than or equal to 10. K is a number between 0 and 20; A is selected from carbon and nitrogen; n is 2 or 3, where n=3 when A is an sp3 carbon, and n=2 when A is an sp2 carbon or nitrogen; m is an integer from 0 to 500; D is, for each occurrence of m, -O-, -C(O)-, -Aryl-, -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(CT2) i -, -N(T)-, -Si(T)2(CH2) i -, -(Si(T)2O) i a divalent spacer independently selected from -, -C(T)=C(T)-, -C(T)=N-, -C(T)=, -N=, or combinations thereof; where for each instance in D of a single bond, a single bond is attached to it, and for each instance in D of a double bond, a double bond is attached to it; each T is selected at each occurrence from a monovalent unit comprising hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl; Each T may also be selected from divalent Dm and may be bonded to another divalent T also selected from Dm to form a ring structure; i is an integer from 1 to 40; Z is hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or a maleimide group; G, for each occurrence of n, is hydrogen, -Dm-Z, or the following structure (VII-b): (ZD m) j XD m - (VII-b); (In the formula, X is a multi-hydrogen bonding group, a disulfide group, or a urea group; When X is divalent, j=1, and when X is monovalent, j=0. and the oligomer has greater than 0.022, or greater than 0.025, or greater than 0.03, or greater than 0.04, or greater than 0.05, or greater than 0.1 UPy groups per 100 grams of oligomer.

[0120] The oligomer according to structure (VII) can be used to impart self-healing properties and / or stress relaxation behavior to coatings or compositions into which it is incorporated. It can be used to impart such properties in a variety of end uses, such as coatings, adhesives, build materials for 3D printing applications, or multilayer optical devices. Such multilayer optical devices include, but are not limited to, optical films, polarizers, electronic displays, lighting devices, ophthalmic lenses, photochromic lenses, microscope lenses, laser mirrors, imaging lenses, or optical fibers. In one embodiment, the oligomer according to structure (VII) is used in a composition for forming a polymer layer in a photochromic lens or optical fiber. In one embodiment, when used in a composition for forming a polymer layer in an optical fiber, the composition includes optional reactive monomer and / or oligomer components, a photoinitiator component, and a self-healing component comprising, consisting of, or consisting essentially of an oligomer according to structure (VII).

[0121]

[0121] In accordance with various embodiments of the second aspect of the present invention, as described above with respect to the compositions of the first aspect, the self-healing oligomer according to structure (VII) is included in related compositions, optical fiber coating compositions, and the like, and a sufficient amount of the self-healing component should be present. Thus, in one embodiment, the self-healing component comprising, consisting of, or consisting essentially of a self-healing oligomer according to structure (VII) is present in an amount greater than 30 wt%, or greater than 40 wt%, or greater than 50 wt%, or greater than 60 wt%, or greater than 70 wt%, or greater than 80 wt%, or greater than 30 wt% to 100 wt%, or greater than 30 wt% to 90 wt%, or greater than 70 wt%, or greater than 80 wt%, or greater than 30 wt% to 100 wt%, or greater than 30 wt% to 90 wt%, or 40 wt% to 80 wt%, or 40 wt% to 70 wt%, or 50 wt% to 100 wt%, or 50 wt% to 80 wt%, or 50 wt% to 75 wt%, based on the weight of the relevant total composition.

[0122] In other embodiments according to the second aspect, the composition in which the self-healing oligomer according to structure (VII) is associated has more than a certain minimum amount of self-healing moieties. 24. The self-healing oligomer according to structure (VII) has a UPy group as the self-healing moiety, such that in one embodiment the composition has greater than 0.015 equivalents, or from 0.015 to 0.2 equivalents, or from 0.015 to 0.1 equivalents, or from 0.015 to 0.08 equivalents, or from 0.015 to 0.05 equivalents, or from 0.015 to 0.045 equivalents; or from 0.02 to 0.2 equivalents, or from 0.02 to 0.1 equivalents, or from 0.02 to 0.08 equivalents, or from 0.02 to 0.05 equivalents; or from 0.025 to 0.20 equivalents; or from 0.037 to 0.2 equivalents, or from 0.037 to 0.1 equivalents, or from 0.037 to 0.08 equivalents, or from 0.037 to 0.05 equivalents of the self-healing moiety per 100 g of composition.

[0123] The amounts of the various components used in the formulations in which the self-healing oligomer according to structure (VII) is associated can be adjusted to various amounts to meet the requirements of the particular intended application. However, in one embodiment, the reactive monomer and / or oligomer component is present from 10% to 65% by weight, or from 10% to 55% by weight, or from 10% to 50% by weight, or, in one embodiment, the reactive monomer and / or oligomer component is present from 10% to 65% by weight, or from 10% to 55% by weight, or from 10% to 50% by weight, or from 20% to 40% by weight; and the self-healing component is present from 30% to 100% by weight, or from 30% to 80% by weight, or from 30 to 75% by weight. or 30 to 70% by weight, or 30 to 60% by weight; or 40 to 80% by weight, or 40 to 75% by weight, or 40 to 70% by weight, or 40 to 60% by weight; the photoinitiator is present from 0.01% to 5% by weight, or from 0.1% to 3% by weight; and the additive is present from 0% to 59.99% by weight; each component being added up to 100% by weight.

[0124] Similarly, depending on the requirements of the particular application in which the self-healing oligomer of structure (VII) is associated, the viscosity of the accompanying composition may vary significantly. However, in embodiments such as those in which the self-healing oligomer of structure (VII) is incorporated, i.e., in optical fiber coating compositions, the composition may be 50 s -1 The composition should have an overall viscosity of less than 40 Pascal-seconds (Pa·s), or less than 30 Pa·s, or less than 15 Pa·s, or less than 10 Pa·s, or less than 1 Pa·s, or 1 Pa·s to 20 Pa·s, or 1 Pa·s to 15 Pa·s, or 1 Pa·s to 10 Pa·s, or 0.05 to 5 Pa·s, or 0.05 to 1 Pa·s, measured at a shear rate of 100°C and a temperature of 25°C. If the viscosity is too low, the composition may not adequately adhere to adjacent layers, such as glass fibers, during optical fiber coating processes; conversely, if the viscosity is too high, the composition may not be able to be applied to adjacent layers, such as glass fibers, quickly enough at the processing speeds required by conventional manufacturing operations.

[0125] One way to properly adjust the viscosity of the composition is to control the molecular weight of the self-healing oligomer according to structure (VII). By formulating a self-healing oligomer according to structure (VII) with a specific number of linking urethane groups, the inventors are able to maintain both the viscosity and / or solubility of the self-healing oligomer according to structure (VII) at a desired level. Thus, in one embodiment, the self-healing oligomer according to structure (VII) has at least three urethane linking groups, or at least four urethane linking groups, or three to six urethane linking groups, or three to five urethane linking groups, or four to five urethane linking groups. When the self-healing oligomer according to structure (VII) is configured to have three to four urethane linking groups, the oligomer will ideally have a MW of 500 to 4500, or 1000 to 4500 g / mol. theo On the other hand, when the self-healing oligomer according to structure (VII) has 4-5 urethane linking groups, the oligomer has a MW of 500-8000, or 1000-8000 g / mol. theo It has.

[0126]

[0126] Regardless of the presence or number of urethane linking groups, in various embodiments, the self-healing oligomer according to structure (VII) has a molecular weight of between 500 and 8000; or between 500 and 5000; or between 500 and 4500; or between 500 and 4000; or between 500 and 3000; or between 500 and 2000; or between 500 and 1500; or between 500 and 1000; or between 500 and 900; or between 500 and 700; or between 700 and 4000; or between 700 and 3000; or between 700 and 2000; or between 700 and 1500; or between 700 and 1000; or between 900 and 4000; or between 900 and 3000; or between 900 and 2000; or between 900 and 1500; or between 1000 and 4000; or between 1000 and 3000; or between 1000 and 2000; or between 1000 and 1500 theo) (g / mol). If the molecular weight of the self-healing oligomer according to structure (VII) is too high, it may have the effect of inhibiting the dissolution of the self-healing oligomer in the associated composition and / or dilute the content of the self-healing moiety to an extent that the self-healing and / or stress relief effects of the cured article associated with the composition may be impaired. On the other hand, if the molecular weight is too low, the curability and / or mechanical properties of the associated composition may be adversely affected.

[0127] In a preferred embodiment, the self-healing oligomeric UPy according to structure (VII) is represented by either of the following structures (VIII-a) or (VIII-b): TIFF0007795474000008.tif99170 wherein R represents the remainder of structure (VII), and D, m, and Z are as defined above for structure (VII).

[0128] In addition to the specific UPy group, the self-healing oligomer according to structure (VII) can have additional self-healing groups. These groups can include additional UPy groups, other hydrogen-bonding groups, or other self-healing moieties, such as disulfide and / or urea groups, as described elsewhere herein. In one embodiment, X is a multi-hydrogen-bonding group, a disulfide group, or a urea group. The hydrogen-bonding groups described above can be UPy groups.

[0129]

[0129] Several specific examples of self-healing oligomers according to structure (VII) are contemplated, including linear or branched structures, those with various linking groups and / or three or more urethane linking groups, and those terminated with acrylate, hydroxyl, amine, cyanate, and / or UPy groups. Two non-limiting examples of such specific potential oligomer structures according to structure (VII) include, but are not limited to: TIFF0007795474000009.tif54170In the formula, n is the MW of the structure theo is an integer such that the molecular weight is maintained between 500 and 8000 g / mol, preferably between 500 and 4500 g / mol.

[0130] As seen above, the self-healing oligomer according to structure (IX) is linear, has three linked urethane groups (for purposes of this specification, the urethane group adjacent to the UPy group is assumed to be associated with it), and terminates in an acrylate group at the chain end opposite the UPy group. Other variations on this can be contemplated by one skilled in the art to which the present invention is applied, following guidelines consistent with the self-healing oligomer according to structure (VII).

[0131] Further examples of specific self-healing oligomers according to structure (VII) and according to the second aspect of the present invention are as follows: TIFF0007795474000010.tif171170In the formula, n is the MW of the structure theo is an integer such that the molecular weight is maintained between 500 and 4500 g / mol.

[0132] Still further specific examples of self-healing oligomers according to structure (VII) include branched structures, such as one or more of the following: TIFF0007795474000011.tif177170In the formula, n is the MW of the structure theo is an integer such that the molecular weight is maintained between 500 and 18000 g / mol, or between 500 and 4500 g / mol.

[0133] The foregoing exemplary structures (IX) through (XXI) are not intended to be limiting examples. Other variations of the above structures (IX) through (XXI) will be apparent to those skilled in the art, provided the present invention is adapted in accordance with the broader guidance of the self-healing oligomers according to structure (VII) described elsewhere herein.

[0134] In various embodiments, the self-healing oligomer according to structure (VII) also includes a polymerizable moiety. When present, the polymerizable moiety preferably includes a radiation-curable moiety such as a vinyl group, an acryloyloxy group, a methacryloyloxy group, a maleimide group, or the like, although other reactive groups can also be used, such as, but not limited to, hydroxy, amino, alkynyl, azide, aziridino, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanatonate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or similar groups.

[0135] In one embodiment, the self-healing oligomer according to structure (VII) comprises (meth)acrylate groups. When the self-healing oligomer according to structure (VII) is present as part of a composition that forms part or all of a self-healing component, the self-healing component can have any suitable amount of (meth)acrylate groups, such as, for example, from 0.015 to 0.1 equivalents of (meth)acrylate groups per 100 grams of composition, or from 0.03 to 0.1 equivalents, or from 0.037 to 0.1 equivalents, or from 0.03 to 0.08 equivalents, or from 0.03 to 0.05 equivalents, or from 0.037 to 0.08 equivalents, or from 0.037 to 0.05 equivalents.

[0136] In other embodiments, the polymerizable groups can also, or alternatively, be present in other components of the overall formulation. In one embodiment, a composition incorporating a self-healing oligomer according to structure (VII) has (meth)acrylate groups, such (meth)acrylate groups being present in the self-healing component, the monomer component, and the oligomer component; or in the self-healing component and the monomer component; or in the self-healing component and the oligomer component; or in the monomer component and the oligomer component; or simply in the monomer component; or simply in the oligomer component. In such embodiments, the composition can have any suitable amount of (meth)acrylate functionality, such as, for example, 0.1 to 0.4 equivalents, or 0.1 to 0.3 equivalents, or 0.1 to 0.25 equivalents, or 0.15 to 0.4 equivalents, or 0.15 to 0.3 equivalents, or 0.15 to 0.25 equivalents, or 0.15 to 0.2 equivalents, of (meth)acrylate groups per 100 grams of composition.

[0137] The present inventors have discovered that the effectiveness and utility of coatings (such as optical fiber coatings) comprising self-healing oligomers according to structure (VII) can be improved if the amount of polymerizable groups in the composition relative to the self-healing moieties is maintained within certain ratios relative to each other. Thus, in one embodiment, the composition has a ratio of equivalents of polymerizable groups to equivalents of self-healing groups in the composition of less than 14, or less than 10, or less than 8, or less than 6, or less than 5, or from 1 to 14, or from 1 to 10, or from 1 to 8, or from 1 to 6, or from 1 to 5, or from 3 to 10, or from 3 to 8, or from 3 to 5.

[0138]

[0138] To effectively quantify the specific effectiveness of any self-healing oligomer or oligomer according to structure (VII), it may be preferable to measure the self-healing and / or stress relaxation properties of a cured product of a composition incorporating said self-healing oligomer or oligomer according to structure (VII).

[0139]

[0139] Specifically, if a quantity of uncured composition is treated according to a predetermined set of curing conditions, and certain physical properties are then measured after the initial cure, then at a subsequent time, the cured product can be damaged in some controlled manner, and the self-healing and / or stress relaxation capabilities of the cured product can be evaluated after allowing a period for the cured product to self-heal, as described elsewhere herein above.

[0140] A third aspect of the present invention is: 1. A multilayer optical device comprising a polymer layer disposed between a first layer of optical elements and a second layer of optical elements, Each of the polymer layer, the first optical element layer, and the second optical element layer comprises a first surface and a second surface, the first surface of the polymer layer being in contact with the first surface of the first optical element layer, and the second surface of the polymer layer being in contact with the first surface of the second optical element layer, the polymer layer comprising the product of a composition comprising a self-healing component, the self-healing component consisting of molecules comprising a self-healing moiety, the composition comprising: (a) greater than 30 wt% of the self-healing component based on the weight of the total composition; or (b) greater than 0.015 equivalents of the self-healing moiety per 100 g of composition.

[0141] A non-limiting example of a multilayer optical device according to the third embodiment is shown in Figure 1. Referring to Figure 1, the multilayer optical device 1 includes a polymer layer 2, which may be a film, coating, adhesive, or primer, sandwiched between two optical element layers, preferably composed of glass or polymeric materials, or vapor-deposited coatings of metals and / or metal oxides. The first optical element layer 3 has a first surface 5 and a second surface 6, where the first surface 5 is in contact with, and preferably chemically bonded to, the first surface 8 of the polymer layer 2, while the second surface 7 of the polymer layer 2 is in contact with, and preferably chemically bonded to, the first surface 10 of the second optical element layer 4. The optical element layer 4 further includes a second surface 9.

[0142]

[0142] Multilayer optical devices are preferably constructed such that the polymer layers can be cut or separated into multiple portions and then reintegrated under appropriate mechanical, thermal, or UV conditions. This can be achieved by constructing the polymer layers from the compositions described according to any of the embodiments of the first aspect of the invention, and / or using any of the oligomers described according to any of the embodiments of the second aspect of the invention.

[0143] In one embodiment, the composition from which the polymer layer is formed optionally includes a monomer component; optionally an oligomer component; an initiator component; and / or additives. Examples of suitable components for the monomer component, oligomer component, initiator component, and additives are described elsewhere herein.

[0144]

[0144] Special additives may be used in the multilayer optical device according to the third aspect. Such additives include adhesion promoters, photochromic dyes, thermochromic dyes, liquid crystals, laser dyes, fluorescent dyes, OLED dyes, dichroic dyes, or fillers. The fillers may include thermally or electrically conductive fillers.

[0145] In one embodiment, as in many applications of multilayer optical devices according to this third aspect, the polymer layers, and optionally the entire multilayer optical device, are preferably substantially transparent, and light transmission should be efficient and unimpeded through the entire device. Thus, in one embodiment, the polymer layers are configured to have a light transmittance of 80% or greater, or greater than 90%, or greater than 95%, or greater than 98%, when tested according to ISO 13468-1:2019. However, the polymer layers need not have high light transmittance in all embodiments; for example, in fiber optic configurations, this is not necessarily the case.

[0146] The polymer layer can vary in thickness by any suitable amount depending on the needs of the application, however, in many embodiments, the polymer layer has a thickness of 500 microns (μm) or less, or less than 250 μm, or less than 100 μm, or less than 50 μm, and / or 1 μm or more, or more than 5 μm, or more than 15 μm, or more than 20 μm.

[0147] The multilayer optical device may be a self-healing coated optical fiber. While a self-healing coated optical fiber can include any number of coating layers surrounding the glass optical fiber, in preferred embodiments, the self-healing coated optical fiber includes at least two layers. In such embodiments, the layer disposed around and in contact with the fiber is the primary coating, while the layer disposed around and in contact with the primary coating is referred to as the secondary coating. In such embodiments, the layer disposed around and in contact with the fiber is the primary coating, while the layer disposed around and in contact with the primary coating is referred to as the secondary coating. If an ink layer is present, it is preferably the outermost layer of the self-healing coated optical fiber. Other multilayer coating systems are known and are disclosed, for example, in WO2017173296, incorporated herein by reference.

[0148]

[0148] Although not required, it is typically desirable for a self-healing optical fiber to be configured such that the self-healing coating layer has a glass transition temperature lower than the temperature at which repair is desired. Without wishing to be bound by any theory, it is believed that the self-healing ability of the coating is essentially linked to segmental motion of the polymer chains. Therefore, it is preferable to avoid the coating being in a crystalline or glassy state (in the case of non-crystalline, amorphous resins), as this is believed to minimize the ability of the self-healing moieties present in the coating to migrate and / or rearrange. Thus, in one embodiment, the glass transition temperature of the coating layer and / or primary coating layer is less than 25°C, or less than 20°C, or less than 10°C, or less than 0°C, or less than -10°C, or less than -20°C, or less than -30°C.

[0149]

[0149] The improved self-healing coatings of the present invention, such as coatings for optical fibers, can be formulated through the selection of ingredients specified herein above, and can be readily prepared by those skilled in the art to which the present invention is applied by following the formulation guidelines herein and by extrapolating from the general approach taken in the embodiments shown in the following examples. Such examples below further illustrate the present invention but, of course, should not be construed as limiting its scope.

[0150] Example These examples illustrate embodiments of the present invention. Table 1 lists the various components of the compositions used in these examples. Table 2 lists various additional aspects of oligomers made from the reagents in Table 1, the synthesis of which is further described below. Tables 3A-3D show test results for all formulations made from the components set forth in Table 1 and the oligomers characterized in Table 2. TIFF0007795474000012.tif191170

[0151] Oligomer synthesis The oligomers used herein were engineered to result in mixtures having a statistical distribution of molecular weights that would be readily recognizable by one skilled in the art. Structures in this section and elsewhere herein represent designed average or "ideal" structures only, unless otherwise noted.

[0152] Specifically, to prepare Oligomer 1, a mixture of AHMP (2-amino-4-hydroxy-6-methyl-pyrimidine, 12.5 g, 0.1 mol) and TMDI (42 g, 0.2 mol) was placed in a four-neck flask (500 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 145° C. for 3.5 hours before the addition of PPG-1000 (100 g, 0.1 mol) and 0.03 g of dibutyltin dilaurate (DBTDL, 0.03 g, 0.0475 mmol). The resulting mixture was further stirred at 90° C. for 3 hours and then cooled to 80° C. The resulting reaction mixture was then purged with a gas mixture consisting of air / nitrogen in a volume ratio of 1:3. Next, DBTDL (0.05 g, 0.079 mmol), BHT (0.24 g, 1.1 mmol), and 2-hydroxyethyl acrylate (HEA, 11.6 g, 0.1 mol) were added sequentially. The reaction mixture was further stirred at 80° C. for an additional 2 hours while under a 1:3 air / nitrogen gas purge to give the final product mixture having the average structure (XXII) shown below as a viscous liquid. The product could then be used in subsequent formulations without further purification. The designed structure (XXII) is shown below: TIFF0007795474000013.tif47170

[0153] To make Oligomer 2, the procedure for obtaining the synthesis of Oligomer 1 above was followed, except that 2-hydroxyethyl methacrylate (HEMA) was used instead of HEA. The viscous liquid product was a mixture of oligomers with the average structure (XXIII). The product could then be used in subsequent formulations without further purification. The designed structure (XXIII) is shown below: TIFF0007795474000014.tif48170

[0154] To make Oligomer 3, the procedure used to obtain the synthesis of Oligomer 1 above was followed, except that 2-ethyl-1-hexylamine was used instead of AHMP. The resulting viscous liquid product was provided as a mixture of oligomers without further purification and had the average structure (XXIV) as shown below. TIFF0007795474000015.tif39170

[0155] To prepare oligomer 4, a mixture of AHMP (12.5 g, 0.1 mol) and IPDI (44.4 g, 0.2 mol) was placed in a four-neck flask (500 ml) and purged with nitrogen. The resulting mixture was stirred under nitrogen at 155°C for 3 hours, after which PPG-1000 (100 g, 0.1 mol) and 0.03 g of dibutyltin dilaurate (DBTDL, 0.03 g, 0.0475 mmol) were added. The resulting mixture was stirred at 115°C for 3 hours and then cooled to 90°C. The reaction mixture was then purged with a gas mixture consisting of air and nitrogen in a volume ratio of 1:3. DBTDL (0.05 g, 0.079 mmol), BHT (0.24 g, 1.1 mmol), and HEA (11.6 g, 0.1 mol) were added sequentially. The reaction mixture was further stirred at 90° C. for an additional 2 hours while under a 1:3 air / nitrogen mixture purge to give the final product mixture as a viscous liquid with average structure (XXV). The product could then be used in subsequent formulations without further purification. The designed structure (XXV) is shown below: TIFF0007795474000016.tif48170

[0156] To make oligomer 5, the procedure for obtaining the synthesis of oligomer 4 above was followed, except that HEMA was used instead of HEA. The viscous liquid product was a mixture of oligomers with the average structure (XXVI). The product could then be used in subsequent formulations without further purification. The designed structure (XXVI) is shown below. TIFF0007795474000017.tif44170

[0157] To prepare oligomer 6, a mixture of AHMP (8.75 g, 0.07 mol) and IPDI (44.4 g, 0.2 mol) was placed in a four-neck flask (250 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 155°C for 3 hours, after which PPG-1000 (100 g, 0.1 mol) and 0.03 g of DBTDL (0.03 g, 0.0475 mmol) were added. The resulting mixture was stirred at 115°C for 3 hours and then cooled to 90°C. The reaction mixture was then purged with a 1:3 volumetric air / nitrogen gas mixture. DBTDL (0.05 g, 0.079 mmol), BHT (0.24 g, 1.1 mmol), and HEA (15.08 g, 0.13 mol) were then added, in order. The reaction mixture was then stirred at 90° C. for an additional 2 hours while still under a 1:3 air / nitrogen purge to give the final oligomer mixture as a viscous liquid having the average structure (XXVII) shown below. The product was then ready for use in the next formulation without further purification: TIFF0007795474000018.tif91170

[0158] To make Oligomer 7, the procedure used to synthesize Oligomer 6 above was followed, except that 2-ethyl-1-hexylamine was used instead of AHMP. The resulting viscous liquid product was provided without further purification as a mixture of oligomers having the average structure (XXVIII) shown below: TIFF0007795474000019.tif87170

[0159] To make Oligomer 8, the procedure for obtaining the synthesis of Oligomer 1 above was followed, except that PPG-600 was used instead of PPG-1000. The viscous liquid product was a mixture of oligomers with the average structure (XXIX). The product could then be used in subsequent formulations without further purification. The designed structure (XXIX) is shown below: TIFF0007795474000020.tif44170

[0160] To make Oligomer 9, the procedure for obtaining the synthesis of Oligomer 1 above was followed, except that PPG-2000 was used instead of PPG-1000. The viscous liquid product was a mixture of oligomers with the average structure (XXX). The product could then be used in subsequent formulations without further purification. The designed structure (XXX) is shown below: TIFF0007795474000021.tif43170

[0161] To prepare oligomer 10, a mixture of AHMP (15.2 g, 0.12 mol) and TMDI (51.58 g, 0.24 mol) was placed in a four-neck flask (250 mL) and purged with nitrogen. The mixture was then stirred under nitrogen at 145°C for 3.5 hours, after which disulfide diol (2-hydroxyethyl disulfide, 18.82 g, 0.12 mol), DBTDL (0.02 g, 0.0317 mmol), and butyl acetate (40 g) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a gas mixture consisting of air / nitrogen in a volume ratio of 1:3. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (14.2 g, 0.12 mol) were then added sequentially. The reaction mixture was further stirred at 90° C. for an additional 2 hours while under a 1:3 air / nitrogen gas purge to give the final product mixture having the average structure (XXXI) shown below as a viscous liquid. The product could then be used in subsequent formulations without further purification. The designed structure (XXXI) is shown below: TIFF0007795474000022.tif37170

[0162] To make oligomer 11, the procedure for obtaining the synthesis of oligomer 1 above was followed, except that 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AMG) was used instead of HEA. The viscous liquid product was a mixture of oligomers with the average structure (XXXII). The product could then be used in subsequent formulations without further purification. The designed structure (XXXII) is shown below: TIFF0007795474000023.tif48170

[0163] To prepare oligomer 12, a mixture of AHMP (7.42 g, 0.059 mol) and TMDI (25.19 g, 0.12 mol) was placed in a four-neck flask (250 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 145°C for 3.5 hours, after which PPG-1000 (59.8 g, 0.0598 mol) and DBTDL (0.02 g, 0.0317 mmol) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a gas mixture consisting of air / nitrogen in a volume ratio of 1:3. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), IEA (2-isocyanatoethyl acrylate, 4.64 g, 0.03 mol), and glycerin (2.75 g, 0.03 mol) were then added sequentially. The reaction mixture was further stirred at 90 °C for an additional 2 hours while under a 1:3 air / nitrogen gas purge to yield the final product mixture with the average structure (XXXIII) shown below as a viscous liquid. The product could then be used in subsequent formulations without further purification. The designed structure (XXXIII) is shown below. TIFF0007795474000024.tif62170

[0164] To prepare oligomer 13, a mixture of AHMP (7.71 g, 0.062 mol) and TMDI (26.16 g, 0.124 mol) was placed in a four-neck flask (250 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 145°C for 3.5 hours, after which PPG-1000 (62.1 g, 0.062 mol) and DBTDL (0.02 g, 0.0317 mmol) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a gas mixture consisting of air / nitrogen in a volume ratio of 1:3. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and ethylene glycol (3.83 g, 0.062 mol) were added sequentially. The reaction mixture was further stirred at 90° C. for an additional 2 hours while under a 1:3 air / nitrogen gas purge to give the final product mixture as a viscous liquid with the average structure (XXXIV) shown below. The product could then be used in subsequent formulations without further purification. The designed structure (XXXIV) is shown below: TIFF0007795474000025.tif43170

[0165] To prepare oligomer 14, a mixture of AHMP (7.58 g, 0.06 mol) and TMDI (25.68 g, 0.12 mol) was placed in a four-neck flask (250 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 145°C for 3.5 hours, after which PPG-1000 (57.8 g, 0.0578 mol), PDMS-Diol 550 (hydroxy-terminated poly(dimethylsiloxane), Mn = 550, 1.67 g, 0.003 mol), and DBTDL (0.02 g, 0.0317 mmol) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a gas mixture consisting of air / nitrogen in a volume ratio of 1:3. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (7.07 g, 0.06 mol) were then added sequentially. While still under a 1:3 air / nitrogen gas mixture purge, the reaction mixture was further stirred at 90° C. for an additional 2 hours to give the final oligomer mixture as a viscous liquid, having the average structure (XXXV) shown below. The product could then be used in subsequent formulations without further purification. The designed structure (XXXV) is shown below: TIFF0007795474000026.tif79170

[0166] To make oligomer 15, the procedure for synthesizing oligomer 14 above was followed, except that PDMS-diol 2500 (bis(3-aminopropyl)-terminated poly(dimethylsiloxane), Mn=2500) was used instead of PDMS-diol 550. The viscous liquid product was a mixture of oligomers with the average structure (XXXVI). The product could then be used in subsequent formulations without further purification. The designed structure (XXXVI) is shown below: TIFF0007795474000027.tif70170

[0167] To prepare oligomer 16, a mixture of AHMP (5.89 g, 0.047 mol) and TMDI (19.95 g, 0.094 mol) was placed in a four-neck flask (250 ml) and purged with nitrogen. The mixture was then stirred under nitrogen at 145°C for 3.5 hours, after which PPG-1000 (33.05 g, 0.033 mol), PDMS-diol 2500 (35.43 g, 0.014 mol), and DBTDL (0.02 g, 0.0317 mmol) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a 1:3 volumetric air / nitrogen mixture. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (5.48 g, 0.047 mol) were then added sequentially. While still under a 1:3 air / nitrogen gas purge, the reaction mixture was further stirred at 90° C. for an additional 2 hours to yield the final oligomer mixture as a viscous liquid, having the average structure (XXXVII) shown below. The product could then be used in subsequent formulations without further purification. The designed structure (XXXVII) is shown below: TIFF0007795474000028.tif70170

[0168] To prepare oligomer 17, a mixture of 2-ethyl-1-hexylamine (15.66 g, 0.121 mol) and TMDI (51.29 g, 0.243 mol) was placed in a four-neck flask (250 mL) and purged with nitrogen. The mixture was then stirred under nitrogen at 125-145°C for 3.5 hours, after which disulfide diol (18.77 g, 0.121 mol) and DBTDL (0.02 g, 0.0317 mmol) were added. The resulting mixture was further stirred at 100°C for 3 hours and then cooled to 90°C. The resulting reaction mixture was then purged with a 1:3 volumetric air / nitrogen mixture. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (14.08 g, 0.121 mol) were then added sequentially. While still under a 1:3 air / nitrogen gas purge, the reaction mixture was further stirred at 90° C. for an additional 2 hours to yield the final product mixture having the average structure (XXXVIII) shown below as a viscous liquid. The product could then be used in subsequent formulations without further purification. The designed structure (XXXVIII) is shown below: TIFF0007795474000029.tif31170

[0169]

[0169] The specific oligomer reactants described above are shown in Table 2 below. TIFF0007795474000030.tif242170

[0170] For purposes of this specification, oligomers having self-healing groups (such as, but not limited to, oligomers 1-2, 4-6, and 8-17) may be considered part of the self-healing component, while oligomers not having self-healing groups (such as, but not limited to, oligomers 3 and 7) are not so characterized.

[0171] The synthesis of the above oligomers, which can be considered part of a self-healing component, is expected to be useful in compositions for coating optical fibers, such as primary coating compositions for coating optical fibers. To further demonstrate this, a subset of these oligomers was used to make various compositions, which were formulated and evaluated as described below. The following such compositions are formulated along with appropriate controls utilizing the above selected oligomers that do not contain self-healing groups. [Example]

[0172] Compounds 1-22 Each of the formulations listed in Tables 3A-D was prepared by mixing a 100g sample in a 100ml mixing cup suitable for use in a SpeedMixer™. Specifically, the oligomer and monomer components, in addition to other ingredients, were mixed as specified in Tables 3A-D below. The mixture was then manually premixed to ensure the oligomer was thoroughly mixed with the monomer used, after which the cup was closed and mixed in a SpeedMixer™ DAC150FVZ at 3500 rpm for 3 minutes. After this, the mixing operation was stopped, and the resulting mixture was transferred to a suitable container and heated to 75°C in an oven and maintained at this temperature for approximately 1 hour to completely dissolve all components. The sample was then removed from the oven and mixed again in the SpeedMixer in the same manner for an additional 3 minutes, after which the silyl acrylate was added to obtain a total of 100g. Finally, the mixture was mixed again in the SpeedMixer in the same manner for an additional 3 minutes.

[0173] These formulations were then characterized according to their respective UPy and (meth)acrylate group contents, according to the methods described below. All formulations were then tested according to the methods described below to measure their tensile strength, elongation, segmental modulus, toughness, viscosity, film self-healing ability at multiple temperatures, and stress relaxation percentage. Unless otherwise indicated, values ​​for UPy equivalent, (meth)acrylate equivalent, and disulfide equivalent are reported herein rounded to three decimal places. Meanwhile, values ​​for segmental modulus and toughness are rounded to two decimal places, and tensile strength is rounded to one decimal place. Viscosity is reported to the nearest centipoise. Film healing results are reported as a qualitative binary "yes" or "no." Finally, values ​​for stress relaxation and film mechanical recovery are reported to the nearest 1%. The values ​​for each of these measured properties are reported below in Tables 3A-3D.

[0174] UPy equivalent The "UPy equivalent weight" for a given composition was determined by first calculating the molar amount of UPy groups in each UPy-containing component (Z) according to the following formula: TIFF0007795474000031.tif11170In formula, TIFF0007795474000032.tif8170=Amount by weight of each component Z per 100 g of the total relevant composition; TIFF0007795474000033.tif7170 = The number of 2-ureido-4-pyrimidinone groups present in the component Z1 molecule; and TIFF0007795474000034.tif8170 is the theoretical molecular weight (g / mol) of component Z. The theoretical molecular weight values ​​of reactants used in making the oligomers (including UPy-containing oligomers) of the formulations herein are reported in Table 2.

[0175] The UPy equivalent value for the overall composition is then calculated by adding the molar value of UPy groups for each UPy-containing component according to the following formula: TIFF0007795474000035.tif19170where n represents the number of UPy-containing components present in the formulation.

[0176]

[0176] Although UPy equivalent values ​​can optionally be expressed as "UPy milliequivalents" by multiplying the total by 1000, values ​​herein are not reported in this manner unless otherwise noted. For clarity, when "equivalents" or "milliequivalents" are specified herein, the value should be interpreted as relating to 100 g of the composition to which it pertains, unless otherwise specified. The UPy equivalent values ​​for each formulation are shown in Table 3A below.

[0177]

[0177] If the complete formulation of the composition is not known in advance, the equivalent weight of the self-healing moiety can be determined analytically via any suitable method, such as size exclusion chromatography (SEC), infrared spectroscopy, HPLC, MALDI-TOF mass spectrometry, or nuclear magnetic resonance (NMR) as will be understood by those skilled in the art to which this invention applies.

[0178] (Meth)acrylate equivalent and disulfide equivalent

[0178] The (meth)acrylate equivalent and disulfide equivalent values ​​are determined in the same manner as "UPy equivalent" above, except for the fact that instead of evaluating UPy groups or components containing UPy, now (meth)acrylate groups (or disulfide groups, if applicable) are counted. If a given composition has both acrylate and methacrylate groups, the values ​​are considered to be summed for purposes of this specification.

[0179] viscosity Viscosity was measured using an Anton Paar Rheolab QC. The instrument was set up for the previous Z3 system used. For each measurement, 14.7 ± 0.2 g of sample was placed in a disposable aluminum cup. The sample in the cup was inspected, and if visual inspection determined that it contained air bubbles, the sample and cup were either centrifuged or allowed to stand long enough for the bubbles to escape from the bulk of the liquid. Bubbles appearing on the top surface of the liquid were considered acceptable.

[0180] Next, the bob was gently placed into the liquid in the measuring cup, after which the cup and bob were attached to the instrument. The sample temperature was allowed to equilibrate with the temperature of the circulating liquid (which itself was maintained at 25 degrees Celsius) by waiting 5 minutes. Then, for 50 seconds, -1 The rotation speed was set to a specific value to generate a desired shear rate of .

[0181]

[0181] After this, measurements were taken. The instrument panel displayed the viscosity value, and if the viscosity value changed slightly (less than 2% relative change) over 15 seconds, the measurement was discontinued. If a relative variation of more than 2% was observed, the sample was allowed to equilibrate for an additional 5 minutes, and the test was resumed immediately thereafter. If sample variability remained during the additional equilibration period, the shear rate was varied according to methods well known in the art to which this invention is applied in order to more accurately capture the viscous properties of the sample. Reported results represent the average viscosity value of three separate test samples. Unless otherwise specified, values ​​are in millipascal seconds (mPa·s) and 50 s -1 The values ​​expressed as shear rates were recorded. The results for each example are reported below in Tables 3A-3D, as appropriate.

[0182] Preparation of film samples To create films that could be tested for various physical properties, each sample was subjected to a 1 J / cm 2The UV-dose was cured under a constant flow of nitrogen gas using a Conveyor Fusion Unit Model DRS-10 / 12 QN, a 600W UV-lamp system with a 1600M radiator (600W / inch, equivalent to 240W / cm, hence a total of 600W), one H-bulb and one D-bulb UV lamp mounted in an R500 reflector. The UV-dose was then measured with an International Light IL390 radiometer.

[0183] Individual test strips approximately 1.27 cm (0.5 in. ± 1 / 32 in.) wide and approximately 12.7 cm (5 in. ± 1 / 8 in.) long were then cut from the film. The exact thickness of each test strip was measured with a calibrated micrometer.

[0184] Tensile strength, elongation, segment modulus, toughness test methods The method for determining segmental modulus used herein is found in EP 2089333 B1, assigned to DSM IP Assets BV, the relevant portions of which are incorporated herein by reference in their entirety. Tensile properties (tensile strength, elongation at break, and segmental modulus) were determined on an MTS Criterion™ Model 43.104 for specimens of 3 mil thick cured film of each sample, prepared according to the "Film Sample Preparation" procedure above.

[0185] Due to these relatively soft coatings (e.g., those with moduli less than about 10 MPa), the coatings were drawn onto glass plates, cured, and after applying a thin layer of talc, individual test specimens were cut from the glass plates with a scalpel. The moduli were calculated at 2.5% elongation using a 0.9 kg (2 lb) load cell on an Instron 4442 Tensile Tester using a least-squares fit of the stress-strain plot. The cured films were conditioned for 16-24 hours at 23.0 ± 0.1 °C and 50.0 ± 0.5% relative humidity before testing.

[0186] The gauge length of the specimens was 5.1 cm (2 inches) and the crosshead speed was 25.4 mm / min. All tests were performed at a temperature of 23.0±0.1°C and a relative humidity of 50.0±0.5%. All measurements were determined from the average of at least six specimens.

[0187]

[0187] Tensile strength values ​​were determined as the maximum stress experienced by the sample before fracture. Toughness values ​​were determined as the total area under the stress-strain curve.

[0188] Film Modification Test First, for each formulation listed in the tables below, 3-mil thick specimens of cured film were prepared according to the "Film Sample Preparation" procedure described above. Next, according to the schematic diagram shown in Figure 1, each specimen was cut under a microscope objective (40x magnification) using a properly sharpened (i.e., brand new) scalpel with a blade thickness of 0.018 inches or less, to visualize the self-healing of the cut specimens in real time. Each specimen was then maintained at room temperature (25°C) for 5 minutes, after which the repair was visually evaluated. A qualitative assessment of repair in this manner is reported in the entire line headed by the phrase "Film Repair, 25°C"; if an observable amount of repair occurred under these conditions, the specimen was rated "Yes"; if no observable repair occurred, the specimen was rated "No," as reported in Tables 3A-3D below.

[0189] Each sample not rated "Yes" was then further heated to 55°C and further visually evaluated with a microscope objective (40x magnification) using a Linkham LTS120 temperature stage. Each sample was maintained at a temperature of 55°C for 5 minutes, after which repair was visually and qualitatively determined. In this example, the same criteria for determining "Yes" and "No" were applied to the samples as for the room temperature repair test. Results are reported appropriately in Tables 3A, 3B, and 3D under the row headed "Film Heat, 55°C," with the further understanding that samples that exhibited self-healing at room temperature were automatically graded with a "YES" designation in the 55°C condition test (not measured), with the understanding that the repair behavior at 55°C exceeds that at room temperature.

[0190] Stress relaxation test First, for each formulation listed in the table below, 3-mil thick cured film specimens were prepared according to the "Film Sample Preparation" procedure described above. The specimens were then conditioned overnight at 50% relative humidity and 23°C. The exact thickness was measured with a calibrated micrometer, and the exact width was measured with an optical microscope at 4x magnification. The specimens were tested in a Dynamic Mechanical Analyzer (DMA) in the "wide specimen" configuration with a test length of 0.79 inches, using a 1-gram pretension held by a screw and clamped to 20 cN.m with a torque driver. The specimens were tested isothermally at room temperature, held at the specified strain (2% for Tables 3A and 3D, 1.5% for Tables 3B and 3C) for 100 seconds, and the stress was measured at a sampling rate of 8 points per second. Samples were run in duplicate and averaged. The total percentage stress reduction values ​​from 1 second to 10 seconds are reported in Tables 3A-3D below.

[0191] Film mechanical recovery test First, for each formulation shown in Table 3D below, two 3 mil thick cured films were prepared according to the "Film Sample Preparation" procedure above, except that the test specimens were not immediately cut from the film. For the avoidance of doubt, in each test, both films were prepared not only from the same formula, but also from the same actual batch of prepared starting material. One film was then cut according to the procedure outlined in "Film Repair Testing" above. The other film was not cut.

[0192] Both films were either left overnight (12-14 hours) at 50% relative humidity and 23° C. or cured in a 55° C. oven (specified in Table 3D). The cut films were not treated or altered in any other way after the cut pieces were made.

[0193] After the 12-14 hour healing period was completed, the film was cut into test specimens according to the "Film Sample Preparation" procedure described above. The tensile strength of the sections obtained from the uncut film was then measured according to the method described above, and the values ​​recorded (referred to herein as "pre-cut tensile strength"). The tensile strength of the cut test specimens was then measured according to the procedure outlined elsewhere herein. If the sample was left to heal at 55°C, it was first allowed to equilibrate to room temperature (for approximately 30 minutes) before the tensile strength measurement was made. The resulting values ​​were then recorded (referred to herein as "post-cut tensile strength").

[0194]

[0194] The film mechanical recovery values ​​reported in Table 3D below represent the measured post-cut tensile strength value divided by the measured pre-cut tensile strength value for each composition, expressed as a percentage to the nearest whole percent. If a sample showed no healing and the post-cut tensile strength could not be measured, the value was simply reported as 0%. TIFF0007795474000036.tif245155 TIFF0007795474000037.tif227159 TIFF0007795474000038.tif134166

[0195]

[0195] Unless otherwise specified, wt % refers to the amount by weight of a particular component relative to the total liquid radiation curable composition in which it is incorporated.

[0196]

[0196] In the context of describing the present invention (particularly in the context of the claims that follow), the use of the terms "a," "an," and "the" and similar referents should be construed to cover both the singular and the plural unless otherwise stated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referencing each individual value falling within the range, unless otherwise stated herein, and each individual value is incorporated into the specification as if set forth individually herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended merely to better clarify the invention and does not pose a limitation on the scope of the invention unless otherwise defined in the claims. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0197] Preferred embodiments of the present invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect that such variations will be adopted by those skilled in the art as appropriate, and the inventors intend the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein or clearly contradicted by context.

[0198] Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as claimed.

Claims

1. 1. A multilayer optical device comprising a polymer layer disposed between a first layer of optical elements and a second layer of optical elements, each of the polymer layer, the first optical element layer, and the second optical element layer includes a first surface and a second surface, the first surface of the polymer layer being in contact with the first surface of the first optical element layer, and the second surface of the polymer layer being in contact with the first surface of the second optical element layer; The polymer layer comprises the product of a composition comprising a self-healing component, said self-healing component consisting of or consisting essentially of molecules comprising a self-healing moiety, said composition comprising: (a) greater than 30 wt. % of a self-healing component, based on the weight of the total composition; or (b) greater than 0.015 equivalents of any of the self-healing moieties per 100 g of the composition; the self-healing component consists of, or consists essentially of, an oligomer having at least one self-healing moiety, the oligomer including at least three urethane linkages; the self-healing component comprises a polymerizable group that is an acrylate or methacrylate group; The self-healing moiety comprises a 2-ureido-4-pyrimidinone (UPy) group.

2. The multilayer optical device of claim 1 , wherein the first optical element layer and / or the second optical element layer is made of a material selected from the group consisting of glass, organic materials containing polymers, and organometallic materials.

3. 3. The multilayer optical device of claim 1 or 2, wherein the first optical element layer, the second optical element layer, or both, are coatings from vapor deposition comprising metals and metal oxides.

4. 4. The multilayer optical device of claim 1, wherein a first surface of the polymer layer is chemically bonded to a first surface of the first optical element layer, and a second surface of the polymer layer is chemically bonded to a first surface of the second optical element layer.

5. The multilayer optical device of claim 1 , wherein the polymer layer is a film, a coating, an adhesive, or a primer.

6. 6. The multilayer optical device of claim 1, wherein the polymer layer can be cut or separated into multiple portions and then reintegrated under appropriate mechanical, thermal, or UV conditions.

7. 7. The multilayer optical device of any one of claims 1 to 6, wherein the polymer layers are configured to have a light transmission of 80% or greater, or greater than 90%, or greater than 95%, or greater than 98%, when tested according to ISO 13468-1:2019.

8. 8. The multilayer optical device of claim 1, wherein the polymer layer has a thickness of 500 microns (μm) or less, or less than 250 μm, or less than 100 μm, or 50 μm or less, and / or 1 μm or more, or more than 5 μm, or more than 15 μm, or more than 20 μm.

9. 9. The multilayer optical device of any one of claims 1 to 8, wherein the composition has a glass transition temperature of less than 150°C, or less than 25°C, or less than 0°C, or less than -10°C, or less than -20°C, or less than -30°C, or from -30 to 20°C, or from -25 to 20°C, or from -20 to 10°C.

10. The multilayer optical device of claim 1 , wherein the composition is UV-curable or thermally curable.

11. The composition comprises: Optionally, a monomer component; Optionally, an oligomeric component; an initiator component; and / or further comprising an additive, Based on the weight of the entire composition, The monomeric and / or oligomeric components are present from 10% to 65% by weight, or from 10% to 55% by weight, or from 10% to 50% by weight, or from 10% to 40% by weight, or from 10% to 30% by weight; or from 20% to 65% by weight, or from 20% to 55% by weight, or from 20% to 50% by weight, or from 20% to 40% by weight; the self-healing component is present from greater than 30% to 100% by weight, or greater than 30 to 75% by weight, or greater than 30 to 70% by weight, or greater than 30 to 60% by weight; or from 40% to 80% by weight, or from 40% to 75% by weight, or from 40% to 70% by weight, or from 40% to 60% by weight; the initiator is present from 0.01% to 10% by weight, or from 0.05% to 5% by weight, or from 0.1% to 3% by weight; and the additive is present from 0% to 59.99% by weight; 11. The multilayer optical device of claim 1, wherein the total of each component equals 100% by weight.

12. The multilayer optical device of claim 11 , wherein the initiator comprises a photoinitiator.

13. 13. The multilayer optical device of claim 11 or 12, wherein the additive comprises an adhesion promoter, a UV absorber, a hindered amine stabilizer, an antioxidant, a photochromic dye, a thermochromic dye, a liquid crystal, a laser dye, a fluorescent dye, an OLED material, a dichroic dye, or a filler.

14. 14. The multilayer optical device of claim 11, wherein the filler comprises a thermally or electrically conductive filler.

15. A multilayer optical device described in any one of claims 1 to 14, wherein the composition has an equivalent ratio of equivalents of polymerizable groups to equivalents of self-healing portions of less than 5.

16. 16. The multilayer optical device of any one of claims 1 to 15, wherein the self-healing moieties consist of or consist essentially of 2-ureido-4-pyrimidinone (UPy) groups.

17. The composition has from 0.015 to 0.5 equivalents, or from 0.015 to 0.2 equivalents, or from 0.015 to 0.1 equivalents, or from 0.015 to 0.08 equivalents, or from 0.015 to 0.05 equivalents, or from 0.015 to 0.045 equivalents; or from 0.02 to 0.2 equivalents, or from 0.02 to 0.1 equivalents, or from 0.02 to 0.08 equivalents, or from 0.02 to 0.05 equivalents; or from 0.022 to 0.05 equivalents; 17. The multilayer optical device of any one of claims 1 to 16, having 0.1 equivalents, or 0.022 to 0.08 equivalents, or 0.022 to 0.05 equivalents, or 0.022 to 0.045 equivalents; or 0.025 to 0.20 equivalents; or 0.037 to 0.2 equivalents, or 0.037 to 0.1 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents of self-healing groups.

18. The multilayer optical device is flat, curved, or cylindrical; and 18. The multilayer optical device of any one of claims 1 to 17, wherein the multilayer optical device is an optical fiber, a beam splitter, a solar panel, an anti-reflective coating, an electronic display, an optical lens, an optical film, a polarizing optic, a window, an optical filter, a lighting device, an ophthalmic lens, a photochromic lens, a microscope lens, a laser mirror, or an imaging lens.

19. 19. The multilayer optical device of claim 1, further comprising a third or more optical element layers, at least one of the optical element layers being in contact with either the second surface of the first optical element layer or the second surface of the second optical element layer.

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