Self-healing optical fiber and compositions used in its manufacture - Patents.com

Abstract

Disclosed herein is a composition for coating an optical fiber, comprising an optional reactive monomer and / or oligomer, a self-healing component having a self-healing moiety, an initiator component, and optionally an additive component. The self-healing component preferably comprises a polymerizable moiety. Such compositions comprise greater than 30 wt. % of the self-healing component per 100 g of the composition and / or greater than 0.015 equivalents of the self-healing moiety. Also disclosed herein is a coated optical fiber having a glass fiber, at least one coating layer, and an optional ink layer configured to have self-healing properties and / or stress relaxation behavior. Also disclosed are methods for coating a self-healing optical fiber and optical fiber cables comprising one or more self-healing coated optical fibers.

Description

[Technical Field]

[0001]

[0001] The present invention relates to optical fibers having self-healing properties and / or stress relaxation behavior, methods for coating such optical fibers, compositions used to make such optical fibers, and cured products produced therefrom.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 004553, filed April 3, 2020, and is incorporated by reference in its entirety as if fully set forth herein. [Background technology]

[0003]

[0003] Optical fibers provide a reliable and efficient means of facilitating telecommunications and computer networking. By using light-based technology, fiber optic cables can carry large amounts of broadband data over enormous distances with minimal signal loss. This makes them the preferred communications medium over other means, such as wire and coaxial cable.

[0004]

[0004] Optical fibers are composed of glass fibers obtained by hot-melt spinning of glass and one or more coating layers disposed on the glass fibers for added protection. For example, optical fibers are first coated with a flexible primary coating layer on the surface of the glass fiber, and then a harder secondary coating layer, called a secondary coating, is formed on top of the primary coating. Optical fiber ribbons or optical fiber cables are also known, each containing multiple optical fibers with coating layers bonded together with an adhesive or "matrix" material.

[0005]

[0005] The relatively soft primary coating provides resistance to microbending. Microbending, also known as attenuation, is an undesirable phenomenon that contributes to the reduction or loss of signal transmission in optical fibers. Microbending is a microscopic curvature of an optical fiber that involves a local axial displacement of a few micrometers and a spatial wavelength of a few millimeters. Microbending can be caused by thermal stresses and / or mechanical lateral forces. Coatings can provide protection against lateral forces that protect optical fibers from microbending, but as coating thickness decreases, the amount of protection provided tends to decrease.

[0006]

[0006] It is desirable for the primary coating to have a higher refractive index than the cladding of the associated optical fiber so that it can remove erroneous optical signals from the optical fiber core. The primary coating must maintain adequate adhesion to the glass fiber during thermal and hydrolytic aging and be removable therefrom for splicing purposes. Primary coatings typically have thicknesses in the range of 20 to 50 μm (e.g., about 25 or 32.5 μm), or 15 to 25 μm for 200 μm fibers.

[0007] The harder secondary coating provides resistance to handling forces such as those encountered when the coated optical fiber is ribboned or cabled. Both the primary and secondary coatings are formed primarily from radiation-curable compositions. Such compositions generally comprise a mixture of ethylenically unsaturated compounds, including one or more acrylate-functional oligomers, dissolved or dispersed in a liquid ethylenically unsaturated diluent and a photoinitiator. The coating composition is typically applied to the optical fiber in liquid form and then cured by exposure to actinic radiation.

[0008]

[0008] It has long been desirable to provide coatings, particularly primary coatings, capable of minimizing attenuation due to microbending in the optical fiber to which they are applied. Historically, it has been found that there is room for improvement in the design of primary coatings for optical fibers, as they often fail to adequately limit signal loss due to the fact that they are too stiff to dissipate most of the stresses that reach the associated glass fiber. Furthermore, to the extent that they absorb certain stresses, such primary coatings have not had a significant ability to participate in stress relaxation, balancing localized stresses over time.

[0009] To adequately minimize attenuation due to microbending, primary coating layers began to be designed with lower modulus values. It was thus discovered that more flexible primary coatings could absorb microstresses and better buffer the optical fiber. However, more flexible coatings tend to have lower structural integrity and are therefore more susceptible to damage during processing and / or handling. This tends to lead to an increase in undesirable voids or defects known as cavitation, which can also contribute to reduced optical fiber performance. The risk of cavitation in soft primary coatings is particularly acute during the fiber coating, winding, or cabling process, but it can also occur during fiber installation or spontaneously due to thermal stresses caused by temperature cycling after installation.

[0010]

[0010] Efforts have been made to mitigate the tendency of flexible optical fiber coatings to form cavitations. Such approaches have historically focused on increasing the toughness, structural rigidity, or minimizing the thermal expansion coefficient of the flexible primary coating.

[0011]

[0011] However, to date, it is believed that no known solution exists that allows a coating to fully rearrange its internal polymer structure in situ after it has been applied and cured on an optical fiber. It would therefore be desirable to provide a composition that can impart self-healing properties to coated optical fibers produced therefrom, such that the formation of certain defects is minimized or even reversed under various ambient conditions. Alternatively or additionally, it would be desirable to provide a composition that can impart excellent stress relaxation behavior to coated optical fibers produced therefrom, potentially reducing the need to rely on overly flexible, cavitation-prone coatings to improve microbending performance. Summary of the Invention

[0012]

[0012] Described herein are several aspects and embodiments of the present invention. A first aspect is a composition for coating optical fiber comprising an optional reactive monomer and / or optional reactive oligomer component; a self-healing moiety comprised of a molecule having one or more self-healing moieties and optionally 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 weight percent, based on the weight of the total composition, and / or (b) the composition has greater than 0.015 equivalents of the self-healing moiety per 100 grams of composition.

[0013] 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 disulfide groups. 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 equivalents of UPy groups or (meth)acrylate groups per 100 g of composition.

[0014] 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 specific viscosity value and / or amount of monomer, oligomer, self-healing component, (photo)initiator, and / or additive.

[0015]

[0015] 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.

[0016] A second aspect of the present invention is a self-healing oligomer according to the following 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 -O- for each occurrence of m, -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 a combination thereof; 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 selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydrido, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, F, Cl, Br, I, or a maleimide group; and G, for each occurrence of n, is independently selected from hydrogen, -Dm-Z, or a self-healing moiety according to the following structure (VII-b): (ZD m ) j XD m - (VII-b); (In the formula, X is a multiple hydrogen bonding group or a disulfide group; (When X is divalent, j=1, and when X is monovalent, j=0).

[0017] According to another embodiment of the second aspect, the oligomer according to structure (VII) is present in a composition for coating an optical fiber, such as a primary coating composition, preferably a liquid radiation curable composition.

[0018]

[0018] A third aspect of the present invention is a self-healing coated optical fiber comprising a coating layer which is a cured product of either the composition described in the first aspect of the present invention and / or the oligomer described in the second aspect.

[0019]

[0019] According to various potential embodiments of the third aspect, the coating layer is a primary coating layer, and the self-healing coated optical fiber also has a secondary coating layer disposed around and in contact with the primary coating layer.

[0020]

[0020] A fourth aspect of the present invention is a method of coating an optical fiber, comprising coating the glass fiber with a primary coating composition, which is a cured product of any of the compositions described in any of the embodiments according to the first aspect, and / or comprises any self-healing oligomer according to any of the embodiments according to the second aspect.

[0021] A fifth aspect of the present invention is a fiber optic cable having a plurality of optical fibers disposed therein, at least one optical fiber being a self-healing optical fiber according to any of the embodiments of the third aspect, optionally treated according to any of the embodiments of the fourth aspect, being a cured product of a composition according to any of the embodiments of the first aspect, and / or comprising any of the self-healing oligomers according to the second aspect. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 shows a schematic layout of the cutting procedure for determining the self-healing effect of cured films, as described elsewhere in this document. [Figures 2A-2E]

[0023] 2A, B, C, D, and E show the progression of cavitation elimination in a self-healing primary coating according to the present invention applied in an on-fiber configuration over time, exposed to various ambient temperatures. [Figure 3A-3B]

[0024] Figure 3, A and B, show plots of stress relaxation tests for two different formulations, as described elsewhere in this paper. DETAILED DESCRIPTION OF THE INVENTION

[0023]

[0025] A first aspect of the present invention is a composition for coating an optical fiber, 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 and 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 greater than 0.015 equivalents of self-healing moieties per 100 g of the composition;

[0024]

[0026] 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 stimulus may be through the application of heat (thus rendering the composition heat-curable) or 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 equally be employed in other aspects of the invention, such as the optical fiber coating composition according to the second aspect, the self-healing coated optical fiber described in the third aspect, the method for coating an optical fiber described in the fourth aspect, or the optical fiber cable described in the fifth aspect, as appropriate.

[0025] Monomer component

[0027] The composition according to the first aspect of the present invention optionally comprises 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 small relative molecular weight, the structure of which can be polymerized, thereby contributing the building blocks to the essential structure of the 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.

[0026]

[0028] Monomers are typically utilized as diluents in optical fiber coating compositions. That is, they can be employed to modify—more specifically, typically reduce—the viscosity of the larger composition to which they are added. Various diluents are used to maximize the flowability, and thus processability, of the associated optical fiber coating composition.

[0027]

[0029] In addition to simply varying the viscosity of the liquid composition, such monomers are preferably also utilized to contribute to the cure speed 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.

[0028]

[0030] 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 an average of 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.

[0029]

[0031] 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.

[0030]

[0032] 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.

[0031]

[0033] The monomer component according to the present invention can 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.

[0032]

[0034] 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 as needed. 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.

[0033]

[0035] 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.

[0034]

[0036] 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.

[0035]

[0037] One or more of the aforementioned monomers can 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 relate, making it suitable for 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.

[0036] Oligomer component

[0038] The 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 comprises 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 theo is 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.

[0037]

[0039] 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, more preferably greater than 1500 g / mol. The polymer may comprise, consist of, or consist essentially of one or more oligomers having a theoretical molecular weight of more than 1000 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.

[0038]

[0040] 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.

[0039]

[0041] 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.

[0040]

[0042] The polymerizable group can occur at any feasible point along the length of the reactive oligomer, including a polymerizable backbone group or a polymerizable end group. A polymerizable backbone group is present along a linear chain along the length of the oligomer or is branched from a linear chain, while a polymerizable end group is a polymerizable group present at the end of the oligomer. The polymerizable group 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 the "end point"). In a preferred embodiment, the polymerizable group comprises, consists essentially of, or consists of a polymerizable end group.

[0041]

[0043] Reactive oligomers according to the present invention may be of any known type consistent with the definitions specified elsewhere herein. Optical fiber coating compositions typically utilize reactive urethane oligomers for the desirable properties they can impart to associated 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 at least a backbone, a polymerizable group, and 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.

[0042]

[0044] 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.

[0043]

[0045] 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.

[0044]

[0046] 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.

[0045]

[0047] 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).

[0046]

[0048] 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, and 2-methyl-1,8-octanediol. Examples of polybasic acids include phthalic acid, dimer fatty acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and hexahydrophthalic acid / anhydride. Preferably, the polybasic acid is selected so that the resulting polyester polyol is unsaturated.

[0047]

[0049] 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.).

[0048]

[0050] 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 typically made from glycerin or trimethylolpropane, with EO in the terminal or internal blocks, and a 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.

[0049]

[0051] Commercially available examples of suitable triols include related propylene oxide-based polyether triols available from Carpenter under the Carpol® 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 Acclaim 703 (Mw 700), Acclaim 3300N (Mw 3000), Acclaim 6300 (Mw 6000), and Acclaim 6320 (Mw 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), both of which are commercially available from Covestro. Additionally, AGC Chemicals offers triols under the trade name Preminol®, such as Preminol S 3011 (Mw 10,000), Preminol 7001K (Mw 7,000), and Preminol 7012 (Mw 10,000).

[0050]

[0052] The theoretical molecular weight derived from the hydroxyl number 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.

[0051]

[0053] The reaction product of a (poly)isocyanate compound, preferably a diisocyanate compound, can be utilized to generate 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.

[0052]

[0054] 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 aforementioned two diisocyanates are commercially available under the generic name "TDI"). Particularly preferred diisocyanates include trimethylhexamethylene diisocyanate (TMDI) compounds and isophorone diisocyanate (IPDI) compounds.

[0053]

[0055] 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.

[0054]

[0056] Further commercially available triisocyanates include the Vestanat® T (IPDI trimer) and HT (HDI trimer) series of polyisocyanate crosslinkers for 2k systems, available from Evonik.

[0055]

[0057] 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).

[0056]

[0058] 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 with active hydrogen groups, such as mercapto-group-containing (-SH) compounds, amino-group-containing (-NH) compounds, and hydroxyl-group-containing (-OH) compounds.

[0057]

[0059] In a preferred embodiment, the urethane oligomer comprises the reaction product of a monohydric alcohol that does not have a (meth)acrylic moiety. Such compounds are preferably reactive with the aforementioned (poly)isocyanates. The monohydric alcohol that does not have a (meth)acrylic moiety can end-cap the oligomer with a hydroxyl group, making the arms or chains non-polymerizable.

[0058]

[0060] In one embodiment, the monohydric alcohol compound having no (meth)acrylic moiety is a C-C 18 , also C2-C 12 , also C4-C 10 The alcohols are aliphatic compounds such as linear or branched monohydric alcohols.

[0059]

[0061] While any suitable monohydric alcohol without a (meth)acrylic moiety can be used, 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.

[0060]

[0062] 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, for example, from about 0.01 to about 1 wt.% 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.

[0061]

[0063] 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 (NMR) spectroscopy. 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.

[0062]

[0064] One or more of the foregoing 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 combination of one or more of the types listed herein. 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.

[0063]

[0065] 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 an optical fiber coating generally imparted by the monomers and oligomers described herein are primarily satisfied via the self-healing component, as further described below.

[0064] self-healing ingredients

[0066] According to a first aspect, the composition comprises a self-healing component, i.e., a collection of one or more individual components having a self-healing moiety. 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 group of atoms that together promote 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 specific minimum degree of self-healing and / or stress relaxation; of course, the degree of self-healing and / or stress relaxation will vary depending on the specific formulation and end-use requirements and environmental conditions involved.

[0065]

[0067] However, in preferred embodiments, a sufficient amount of the self-healing material should be present in the composition from which the optical fiber coating is formed or cured to produce the desired amount of stress relaxation or self-healing at the temperatures and time scales required for optical fiber applications. 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 a suitable minimum amount of the self-healing moiety.

[0066]

[0068] 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: TIFF0007744922000001.tif12170In formula, TIFF0007744922000002.tif7170=Amount by weight of each component Z per 100 g of the total relevant composition; TIFF0007744922000003.tif7170 = The number of self-repairing moieties present in one molecule of component Z; and TIFF0007744922000004.tif8170Theoretical molecular weight of component Z.

[0067]

[0069] If the complete formulation of the composition is not known, the equivalent weight of the self-healing moiety can be determined analytically 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.

[0068]

[0070] 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, or from 0.015 to 0.15, or from 0.015 to 0.1, or from 0.015 to 0.08, or from 0.015 to 0.05, or from 0.015 to 0.045; alternatively from 0.02 to 0.2, or from 0.02 to 0.15, or from 0.02 to 0.1, or 0.02 to 0.08, or 0.02 to 0.05; 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.

[0069]

[0071] 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 2-ureido-4-pyrimidinone (UPy) groups. 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: TIFF0007744922000005.tif54170

[0070]

[0072] UPy groups can be formed as the reaction product of multiple hydrogen bonding group precursors. 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: TIFF0007744922000006.tif45170

[0071]

[0073] 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.

[0072]

[0074] In one embodiment, the self-healing portion comprises, consists of, or consists essentially of multiple hydrogen-bonding groups. In one embodiment, the self-healing portion comprises, consists of, or consists essentially of UPy groups. In one embodiment, at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 99%, or 100% of the equivalent weight of the self-healing portion of the composition consists of UPy groups.

[0073]

[0075] In addition to UPy groups, other self-healing moieties are known. One class of self-healing moieties involves the use of some hydrogen bonds, but not enough to be construed as "multiple hydrogen bonds" as defined and explained above. One such example includes urea groups. The use of urea groups as suitable self-healing moieties is known and is described in Applied Materials Today 19 (2020) 100542. The two hydrogen bonds formed between two urea groups are responsible for the self-healing properties. The hydrogen bonds between urea groups are weaker than the multiple hydrogen bonds of UPy moieties and are therefore undesirable for use as self-healing moieties for purposes herein. Furthermore, because monomers and / or oligomers containing urea groups without larger UPy groups are difficult to compatibilize in optical fiber coating compositions, in preferred embodiments, the self-healing component is substantially free of urea groups, apart from any urea groups that are substituents on UPy moieties.

[0074]

[0076] Other self-healing moieties are known that use reversible chemistries that do not involve hydrogen bonding. Examples such as Diels-Alder chemistry typically require high temperatures to achieve self-healing or stress-relaxation behavior, making them less practical for use in optical coating applications. However, as described in Macromolecules 2011, 44, 2536-2541, the weak covalent bonds inherent in disulfide groups are believed to facilitate the self-healing and / or stress-relaxation behavior of coatings at low temperatures. Indeed, self-healing and / or stress-relaxation are the result of exchange reactions of disulfide groups even at moderate temperatures.

[0075]

[0077] Thus, in one embodiment, the self-healing moiety comprises a disulfide group, which, if properly controlled, may be suitable for use in optical fiber coating applications, since it should not significantly inhibit the radiation curability of the associated composition or substantially deleteriously affect the physical properties of coatings produced therefrom.

[0076]

[0078] 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 being 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. The bond dissociation energy can be determined by various suitable methods, non-limiting examples of which can be found through a summary of direct addition of all bonds of self-repairing moieties according to Table 1 in The Scientific World Journal (2004) 4, 1074-082; and Nature 2002, volume 3, 836-847. However, in practice, the bond dissociation energy may be higher than that obtained by direct addition due to synergistic effects.

[0077]

[0079] 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 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 a preferred embodiment, the dimer has at least three, or at least four, or three to 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 which includes fewer than seven covalent bonds. Some non-limiting examples of such dimeric configurations of a UPy moiety having four hydrogen bonds and six adjacent covalent bonds on either side of the hydrogen bond are shown in structures (I) to (IV) below: TIFF0007744922000007.tif138170

[0078]

[0080] Similarly, a non-limiting example of such a dimeric configuration of a UPy moiety having three hydrogen bonds and four adjacent covalent bonds on either side of the hydrogen bonds is shown below in structure (V): TIFF0007744922000008.tif84170

[0079]

[0081] As seen in structures (I)-(V) above, the dimer may have a ring structure or a fused ring structure. In various embodiments, for each of structures (I)-(V), R may be selected from organic substituents optionally having a reactive group attached thereto. In one embodiment, the reactive group comprises an acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydrido, thio, isocyanato, protected isocyanate, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimide group.

[0080]

[0082] In one embodiment, the self-healing component comprises, consists of, or consists essentially of self-healing moieties configured to dimerize according to any of structures (I), (II), (III), (IV), and / or (V) above.

[0081]

[0083] 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 generate the 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 a trimethylhexamethylene diisocyanate (TMDI) compound and / or an isophorone diisocyanate (IPDI) compound. 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.

[0082]

[0084] Due to the natural tendency of self-healing moieties to self-assemble and / or dimerize, conventional small molecules or oligomers containing self-healing moieties exhibit poor solubility and / or miscibility with other monomers and / or oligomers typically present in coatings. To increase solubility, the molecular weight of the oligomer can be increased, as disclosed in Progress in Organic Coatings 113 (2017) 160-167. However, in this case, the concentration of the self-healing moiety is inevitably reduced to a level that adversely affects the self-healing and / or stress relief effects, potentially to the point where they may be insufficient for the requirements and conditions experienced in various applications, including optical fiber coatings. Furthermore, conventional self-healing components typically require large amounts of solvent to synthesize, and in any case, very often result in crystalline or solid materials with high melting points or glass transition temperatures (Tg). Therefore, conventional selection of self-healing components is limited to those with low solubility, low self-healing moiety content, and / or those requiring large amounts of solvent to synthesize.

[0083]

[0085] The inventors have surprisingly found that many of the self-healing oligomers described herein, such as those containing at least three urethane linkages, tend to produce oligomers with lower viscosity values ​​and / or are more easily processable in optical fiber coating applications, thereby eliminating the need for process-hindering solvents and allowing for increased usage of the self-healing component in the associated optical fiber coating composition. The addition of a large amount of the self-healing component is important to facilitate the creation of formulations suitable for use in producing self-healing and / or stress-relieved optical fiber that are readily processable in the production of coated optical fiber.

[0084]

[0086] As mentioned, in various embodiments, it is desirable to minimize the use of solvents. The inclusion of solvents is undesirable because such reagents tend to introduce processing difficulties and / or safety issues in optical fiber coating applications. Some non-limiting examples of common solvents include 2-propanol, acetone, acetonitrile, chloroform (CHCl), dichloromethane, dimethyl sulfoxide ((CH)SO), ethyl acetate, hexane, methanol, tetrahydrofuran, toluene, propylene glycol, methyl ethyl ketone, and water, to name a few. To distinguish from reactive diluents commonly used in UV-curable compositions, for purposes of this specification, a reagent is not considered a solvent if it has one or more acrylate or methacrylate functional groups. The presence of these compounds can be determined by any suitable method, such as size-exclusion chromatography (SEC) and HPLC; water can also be easily quantified by Karl Fischer titration. Self-healing components according to aspects of the present invention facilitate the minimization or elimination of such reagents that are not otherwise useful in promoting the formation of the cure, self-healing performance, or physical properties required for many optical fibers. Thus, in one embodiment, the composition contains less than 5% by weight of solvent, or less than 1% by weight of solvent, or less than 0.1% by weight of solvent, or is substantially free of solvent.

[0085]

[0087] Notwithstanding the above, in one embodiment, the self-healing component comprises, consists of, or consists essentially of one or more compounds according to the following structure (VI): [A(G) n -D m ]-[A(G) n-1 -D m ] k -Z (VI); [In the formula, 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 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 -;-C(T)=C(T)-; a bivalent spacer independently selected from -C(T)=N-; -C(T)=; -N=; or combinations thereof; (In the formula, 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; where each T also represents a divalent D m You can choose from the same D m and forms a ring structure with another divalent T selected from: 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 selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or a maleimide group; G, for each occurrence of n, is independently selected from hydrogen, -Dm-Z, or a self-healing moiety according to the following structure (VI-b): (ZD m ) j XD m - (VI-b); (In the formula, X is a multiple hydrogen bonding group or a disulfide group; When X is divalent, j=1, and when X is monovalent, j=0; where, for at least one occurrence of n, G is a self-repairing moiety according to structure (VI-b).

[0086]

[0088] In one embodiment, X comprises, consists of, or consists essentially of a disulfide 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): TIFF0007744922000009.tif47170 wherein D, m, and Z are as defined above for structure (VI), and R represents the remainder of structure (VI).

[0087]

[0089] 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.

[0088]

[0090] In certain embodiments, Z comprises a (meth)acrylate group. Such functionality allows molecules according to structure (VI) to be polymerized in a manner consistent with many current conventional optical fiber coatings.

[0089]

[0091] 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).

[0090]

[0092] 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 so that the composition most effectively imparts 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 with a Tg value lower than the temperature at which self-healing and / or stress relaxation capabilities are desired. In this way, 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.

[0091]

[0093] 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 tends to be preferable as it theoretically promotes self-healing and / or stress relaxation functionality over a wider range of operating temperatures.

[0092]

[0094] 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 the 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.

[0093]

[0095] Preferably, the polymerizable portion of the self-healing component comprises a radiation-curable moiety such as an acrylate or methacrylate group.

[0094]

[0096] The inventors have also discovered that the effectiveness and utility of self-healing coatings for 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.

[0095]

[0097] 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.

[0096]

[0098] Furthermore, the inventors have found that it may be helpful to adjust 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, which does not promote sufficient internal reorientation of the relative lack of self-healing groups to self-assemble or reach each other to provide healing. Conversely, if the number of polymerizable groups is insufficient, the composition may not cure sufficiently (or may not cure quickly enough), thereby making such compositions unsuitable for processing in optical fiber coating operations and / or increasing the likelihood that cured coatings made therefrom may have inadequate mechanical performance properties.

[0097]

[0099] 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.

[0098]

[0100] 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.

[0099] Initiator Component

[0101] 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 chemical changes 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 essentially consists of an initiator that promotes free radical polymerization; i.e., it comprises, consists of, or essentially consists of a free radical initiator.

[0100]

[0102] 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 the 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.

[0101]

[0103] 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).

[0102]

[0104] 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-hydroxycyclohexyl phenyl 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-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)phenyl]propanone.

[0103]

[0105] 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 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.

[0104]

[0106] 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.

[0105]

[0107] 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 herein above.

[0106]

[0108] 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 an example, 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 US9708442, assigned to DSM IP Assets BV, the entire contents of which are incorporated herein by reference. Known specific acylgermanium photoinitiators include benzoyl trimethylgermane (BTG), tetracylgermanium, or bisacylgermanoyl (commercially available as Ivocerin® from Ivoclar Vivadent AG, 9494 Schaan / Liechtenstei).

[0107]

[0109] The photoinitiators of the present invention can be used alone or in combination as a blend. Suitable photoinitiator blends are disclosed, for example, in U.S. Patent No. 6,020,528 and U.S. Patent Application 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.

[0108]

[0110] 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.

[0109]

[0111] 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), CC unstable compounds such as benzopinacol, peroxides, and mixtures thereof.

[0110]

[0112] 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.

[0111]

[0113] 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.

[0112]

[0114] 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.

[0113]

[0115] 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 alone or in combination with 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.

[0114] additives

[0116] Compositions according to the present invention optionally include additive components; i.e., a group of one or more individual additives having one or more specific structures or types. Additives are also typically added to optical fiber coatings to achieve certain desired properties, such as, for example, improved adhesion to glass optical fibers, 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.

[0115]

[0117] 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.

[0116]

[0118] 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, oxygen barrier layers can be applied.

[0117]

[0119] 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:

[0118]

[0120] 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 No. 4,127,586; No. 4,226,763; No. 4,275,004; No. 4,278,589; No. 4,315,848; No. 4,347,180; No. 4,383, No. 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. 5,31 9,091; 5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987; 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-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.

[0119]

[0121] 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.

[0120]

[0122] Yet another class of examples includes, for example, esters of substituted and unsubstituted benzoic acid, 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.

[0121]

[0123] 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.

[0122]

[0124] The curing procedure can be assisted by the use of additives that specifically produce or facilitate the production of colored compositions. Such additives include, for example, 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 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.

[0123]

[0125] The additive component may include photoreducible dyes, such as xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin, or acridine dyes, and / or trihalomethyl compounds that can be cleaved by radiation. Such additives are described, for example, in U.S. Patent No. 5,229,253.

[0124]

[0126] 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.

[0125]

[0127] In one embodiment, the additive component comprises one or more of a variety of additives used to enhance one or more properties of the primary coating, including antioxidants (such as Irganox 1035, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or tert-butylhydroquinone), adhesion promoters, inhibitors (such as acrylic acid), photosensitizers, carrier surfactants, tackifiers, catalysts, stabilizers, surface agents, and optical brighteners.

[0126]

[0128] In a preferred embodiment, the additive component comprises, consists of, or consists essentially of one or more adhesion promoter compounds. The adhesion promoter provides the bond between the polymer primary coating and the surface of the optical glass fiber. Hydrolyzable silane coupling agents have been commonly used as glass adhesion promoters. Silane coupling agents are described, for example, in U.S. Pat. No. 4,932,750. In one embodiment, the adhesion promoter is a hydrolyzable silane compound containing a mercapto group and / or multiple alkoxy groups. Such adhesion promoters are known and are described in U.S. Patent Application No. 20020013383, the relevant portions of which are incorporated herein by reference.

[0127]

[0129] In one embodiment, the adhesion promoter comprises gamma-mercaptopropyltrimethoxysilane, trimethoxysilylpropyl acrylate, or 3-trimethoxysilylpropane-1-thiol.

[0128]

[0130] Rather than being used as a standalone compound in an additive component, silane coupling groups—or other adhesion-promoting groups—can also be reacted with other compositional components, such as oligomers, monomers, or even self-healing components. For purposes of understanding herein, in such cases, they are considered to be part of the respective component with which they react, rather than as an additive. Thus, in one embodiment, the composition includes adhesion-promoting functional groups as part of an oligomer component, a monomer component, or a self-healing component.

[0129]

[0131] 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.

[0130]

[0132] Compositions according to the first aspect of the present invention are desirably free of additives or components that tend to inhibit polymerization and / or self-assembly reactions. In particular, it is desirable to maintain the composition substantially free of reagents that tend to inhibit free radical polymerization or hydrogen bonding. Such components may include so-called superacids and / or superbases, as will be understood by those skilled in the art.

[0131]

[0133] Compositions according to the first aspect of the present invention may be prepared so that they contain varying amounts of the aforementioned components in varying 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.

[0132]

[0134] To be suitable for use in typical optical fiber coating applications, the composition should have a particular 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 optical fiber 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 can be prepared in a 50s or 60s solution. -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.

[0133]

[0135] 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 specific 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 specific 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.

[0134]

[0136] 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.

[0135]

[0137] The effectiveness of the self-healing behavior can be determined by subjecting any of the compositions according to any of the embodiments of this first aspect to a radiation source emitting a peak spectral output of 1 J / cm from a radiation source emitting a peak spectral output of 360 nm to 400 nm. 2The self-healing effect can also be observed by curing a 3 mil film by exposing it to a dose of energy of 1000 kJ / min, and wherein upon the formation of at least one cut in the film, the film repairs to a visually detectable extent 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 the film is maintained at a temperature of 55°C, preferably 25°C, and the repair of the film is determined visually by microscopic imaging at 40x or 100x magnification. 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 it to more closely simulate the shape and load, and the resulting self-healing coating functions on the coated optical fiber.

[0136]

[0138] In other embodiments, the self-healing properties of a composition may be determined in other ways, such as by comparing the physical properties of the cured product of the coating before and after the cured product is subjected to a controlled fracture event. The controlled fracture event may be induced cavitation, tearing, or cutting into a cured product, such as a film, according to a specific, controlled procedure. In one embodiment, the controlled fracture event is a cutting procedure, whereby a cut is made through a substantially flat film having a substantially rectangular cross-section and a substantially flat surface formed from the coating at a 45° angle toward the substrate, according to the orientation shown in FIG. 1. As shown in FIG. 1, cut 1 is made at a 45° angle 2; such a cut can be made using a sufficiently sharp razor, X-acto® knife, or similar device having a blade thickness of about 0.018 inches or less, starting from the top surface 3 of the cured film 4 and extending downward to the substrate 5. While substrate 5 can be composed of any suitable material, in a preferred embodiment it is glass. The cut 3 is made substantially perpendicular to the side of the cured film 4 so that the angle 6 is maintained at approximately 90°.

[0137]

[0139] In one embodiment, the composition, when cured into a first film and a second film according to the sample preparation methods described elsewhere herein, has a pre-cut tensile strength for the first film and a post-cut tensile strength for the second film, where the pre-cut tensile strength and post-cut tensile strength are determined after the second film is subjected to the cutting procedure described elsewhere herein, and then maintained at a temperature of about 25°C or about 55°C for 12 to 14 hours; 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.

[0138]

[0140] The pre-cut and post-cut tensile strengths described above are preferably measured according to ASTM D638, with some modifications, where applicable, to allow for measurement of softer materials, as would be understood by one 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.

[0139]

[0141] A second aspect of the present invention is a self-healing oligomer according to 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; 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 a combination thereof; 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; where each T also represents a divalent D m You can choose from the same D m and forms a ring structure with another divalent T selected from: i is an integer from 1 to 40; Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or a maleimide group; and G, for each occurrence of n, is independently selected from hydrogen, -Dm-Z, or a self-healing moiety according to the following structure (VII-b): (ZD m ) j XDm - (VII-b); (In the formula, X is a multiple hydrogen bonding group or a disulfide group; When X is divalent, j = 1, and when X is monovalent, j = 0.

[0140]

[0142] 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, microscope lenses, laser mirrors, imaging lenses, or fiber optic applications. In a preferred embodiment, the oligomer according to structure (VII) is used in a composition for coating optical fiber. In a preferred embodiment, the optical fiber coating composition comprises an optional reactive monomer and / or oligomer component, a photoinitiator component, and a self-healing component comprising, consisting of, or consisting essentially of an oligomer according to structure (VII).

[0141]

[0143] According to 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 associated with an associated composition, preferably an optical fiber coating composition, such that a sufficient amount of the self-healing component is 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.

[0142]

[0144] In another embodiment 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. Because the self-healing oligomer according to structure (VII) has a UPy group as the self-healing moiety, in one embodiment, the composition has more than 0.015 equivalents per 100 g of composition, or 0.015 to 0.5 equivalents, or 0.015 to 0.2 equivalents, or 0.015 to 0.15 equivalents, or 0.015 to 0.1 equivalents, or 0.015 to 0.5 equivalents, or 0.015 to 0.2 equivalents, or 0.015 to 0.15 equivalents, or 0.015 to 0.1 equivalents, or 0.02 to 0.2 equivalents, or 0.015 to 0.15 equivalents, or 0.015 to 0.2 equivalents, or 0.015 to 0.15 equivalents, or 0.015 to 0.2 equivalents, or 0.015 to 0.15 equivalents, or 0.02 to 0.2 ... or 0.022 to 0.15, or 0.02 to 0.1, or 0.02 to 0.08, or 0.02 to 0.05; 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 of UPy groups.

[0143]

[0145] 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 suit 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; 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.

[0144]

[0146] 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 coating 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 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, measured at a shear rate of 100°C and a temperature of 25°C. If the viscosity is too low, the optical fiber coating composition may not adhere properly to the glass fiber during the coating process; conversely, if the viscosity is too high, the draw speed of conventional optical fiber coating processes may not allow the coating composition to be applied to the glass fiber fast enough.

[0145]

[0147] One way to appropriately adjust the viscosity of a 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.

[0146]

[0148] 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 8000; 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.

[0147]

[0149] 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): TIFF0007744922000010.tif103170wherein R represents the remainder of structure (VII), and D, m, and Z are as defined above for structure (VII).

[0148]

[0150] In addition to the specific UPy group, the self-healing oligomer according to structure (VII) can have additional self-healing groups. These groups can collectively include additional UPy groups, other hydrogen-bonding groups, or other self-healing moieties such as disulfide groups as described elsewhere herein. In one embodiment, X is a multi-hydrogen-bonding group or a disulfide group. The hydrogen-bonding group can be a UPy group.

[0149]

[0151] 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: TIFF0007744922000011.tif61170In 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.

[0150]

[0152] 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).

[0151]

[0153] Further examples of specific self-healing oligomers according to structure (VII) and according to the second aspect of the present invention are as follows: TIFF0007744922000012.tif154170In 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.

[0152]

[0154] Still further specific examples of self-healing oligomers according to structure (VII) include branched structures, such as one or more of the following: TIFF0007744922000013.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.

[0153]

[0155] The foregoing exemplary structures (IX) through (XXI) are not intended to be limiting examples, and other variations of the above structures (IX) through (XXI) may be readily 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.

[0154]

[0156] 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.

[0155]

[0157] 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 0.03 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.

[0156]

[0158] 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 g of composition.

[0157]

[0159] The 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.

[0158]

[0160] 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).

[0159]

[0161] 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 assessed after allowing a period of time for the cured product to self-heal, as described elsewhere herein above.

[0160]

[0162] A third aspect of the present invention is a self-healing coated fiber comprising a glass fiber optionally comprising a core layer and a cladding layer; a first coating layer disposed about and in contact with the glass fiber; an ink layer may be disposed about and in contact with the first coating layer or the second coating layer; and the first coating layer comprises: (a) an oligomer according to any of the embodiments of the first aspect, and / or (b) an oligomer according to any of the embodiments of the second aspect.

[0161]

[0163] In one embodiment, the self-healing optical fiber is configured to repair cavitations formed in more than 20%, or more than 50%, or more than 75%, or more than 90% of the coating layer within 48 hours, or preferably within 8 hours, or preferably within 1 hour, or preferably within 5 minutes, or preferably within 1 minute, as determined visually via microscopic imaging at 40x or 100x magnification, while the self-healing coated optical fiber is maintained at a temperature below 80°C, or preferably below 60°C, or preferably below 50°C, or preferably below 25°C.

[0162]

[0164] Although a self-healing coated optical fiber can include any number of coating layers surrounding the glass optical fiber, in a preferred embodiment, the self-healing coated optical fiber includes at least two layers. In such an embodiment, the layer disposed around and in contact with the fiber is referred to as the primary coating, while the layer disposed around and in contact with the primary coating is referred to as the secondary coating. In such an embodiment, the layer disposed around and in contact with the fiber is referred to as 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, for example, as disclosed in WO2017173296, which is incorporated herein by reference.

[0163]

[0165] According to this third aspect, the coating layer or primary coating layer is preferably the cured product of a radiation curable composition incorporating a self-healing oligomer of any of the first aspect of the invention and / or the second aspect of the invention.

[0164]

[0166] In embodiments of the third aspect of the present invention, any type of optical fiber can be used, however in preferred embodiments the coated optical fiber has a mode field diameter of 8-10 μm at a wavelength of 1310 nm, or a mode field diameter of 9-13 μm at a wavelength of 1550 nm, and / or a mode field diameter of 20-200 μm. 2 Such fibers may be single-mode and / or large-effective-area fibers, given the expected demand for coating processes for these fibers to utilize higher line or processing speeds. However, other fiber types, such as multimode fibers, may be used as well.

[0165]

[0167] In field applications, a self-healing optical fiber according to the third aspect of the present invention may exhibit fewer cavitations than conventional optical fibers during initial fiber processing. Furthermore, after cable installation and field use, it may exhibit a reduced number of cavitations over time. This is because additional stresses or cavitations are induced by physical and / or thermal forces applied to the coated optical fiber, and the self-healing properties and / or stress relaxation behavior of the coating according to the present invention allow for structural rearrangement, thereby reducing and / or balancing the internal stresses of the coating. Over time, depending in part on the temperature of the environment in which the self-healing coated optical fiber is placed, it may be possible to reduce or even eliminate at least some or all of the associated cavitations. In one embodiment, cavitations in the primary coating of a self-healing coated optical fiber according to the third aspect of the present invention are visibly reduced and / or eliminated within a few days, within a day, within 10 minutes, within 5 minutes, or within 1 minute while the fiber is maintained at 50°C or 25°C. In preferred embodiments, the cavities in the primary coating decrease and / or disappear within 1 hour, or within several days, or within 1 day, or within 30 minutes, or within 10 minutes, or within 5 minutes, or within 1 minute while the fiber is maintained at 30°C or 25°C.

[0166]

[0168] The elimination of cavitation in a simulated optical fiber coated with a self-healing primary coating composition according to the present invention is illustrated by the photographs (taken at 100x magnification) shown in Figures 2A-2E. In these figures, the wire appears as an opaque, dark layer. A coating composition according to the present invention was applied to a stainless steel wire and cured thereon to form a primary coating. This primary coating is visible in Figures 2A-2E as the first translucent layer in contact with the stainless steel wire. The primary coating was then further coated with a secondary coating, which appears as the outermost translucent layer, to create a self-healing coated wire in a manner that simulates the geometry of a coated optical fiber. Just prior to the photograph shown in Figure 2A, a section of the self-healing coated wire shown was struck with a hammer to induce a severe cavitation event in the primary coating. Such cavitation is visible as a ring-shaped bubble with a shadowed ring around a (usually) transparent core. The same section of the self-healing coated wire was left at room temperature for two hours, after which the photograph in Figure 2B was taken. As can be seen, the amount of cavitation had already significantly decreased at this point, indicating self-healing behavior. Next, the same section of the self-healing coated wire was heated to 30°C and held at that temperature for 30 minutes, after which the photograph shown in Figure 2C was taken. At this point, the amount of cavitation present in the primary coating had significantly decreased—by at least 40%. The same section of the self-healing coated wire was then heated to 60°C and held at that temperature for 60 minutes, after which the photograph shown in Figure 2D was taken. By this time, all cavitation had been eliminated by visual inspection. Finally, to ensure that cavitation would not reform upon cooling, as is known to occur in conventionally coated optical fiber, the same section of the self-healing coated wire was cooled to -30°C and held at this temperature for 10 minutes, after which the photograph shown in Figure 2E was taken. As can be seen, the cavitation did not re-emerge, suggesting that the polymer network had reorganized and not simply expanded.

[0167]

[0169] 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 inherently linked to segmental motion of the polymer chains. Therefore, it is preferable to avoid having the coating 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.

[0168]

[0170] A fourth aspect of the present invention is a method of coating an optical fiber, comprising coating the glass fiber with a coating composition, optionally a primary coating composition, which is a cured product of any of the compositions described according to any of the embodiments of the first aspect, and / or uses any of the self-healing oligomers according to the second aspect.

[0169]

[0171] Methods for coating optical fibers are well known. In one embodiment, the method includes: providing a glass optical fiber, preferably by drawing the glass optical fiber through a draw tower; applying a primary coating composition onto a surface of the glass optical fiber; optionally providing a dose of radiation energy, including UV light, sufficient to at least partially cure the primary coating composition; applying a secondary coating composition to the primary coating composition; and exposing the primary coating composition and the secondary coating composition to at least one radiation source capable of emitting ultraviolet light to affect curing of the primary coating composition and the secondary coating composition to form a cured primary coating on the surface of the optical fiber and a cured secondary coating on the surface of the cured primary coating.

[0170]

[0172] A fifth aspect of the present invention is a fiber optic cable, wherein the optical fiber comprises at least one optical fiber according to any of the embodiments of the third aspect of the invention, and / or the optical fiber is a cured product of a composition according to any of the embodiments of the first aspect of the invention, and / or utilises any of the self-healing oligomers of the second aspect, and / or the optical fiber is coated according to any of the embodiments of the fourth aspect of the invention.

[0171]

[0173] The improved self-healing coated optical fiber of the present invention can be formulated through the selection of the components identified herein above, and is 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, which further illustrate the present invention but, of course, should not be construed as limiting its scope. [Example]

[0172]

[0174] 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 syntheses of which are further described below. Tables 3A-3D show test results for all formulations made from the components listed in Table 1 and the oligomers characterized in Table 2. TIFF0007744922000014.tif181170

[0173] Oligomer synthesis

[0175] 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.

[0174]

[0176] 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 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 with 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. TIFF0007744922000015.tif48170

[0175]

[0177] 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: TIFF0007744922000016.tif38170

[0176]

[0178] To make Oligomer 3, the procedure for obtaining 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. TIFF0007744922000017.tif29170

[0177]

[0179] 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 then 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 then 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: TIFF0007744922000018.tif35170

[0178]

[0180] 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: TIFF0007744922000019.tif34170

[0179]

[0181] 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. Next, DBTDL (0.05 g, 0.079 mmol), BHT (0.24 g, 1.1 mmol), and HEA (15.08 g, 0.13 mol) were added sequentially. 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: TIFF0007744922000020.tif74170

[0180]

[0182] 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: TIFF0007744922000021.tif66170

[0181]

[0183] 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: TIFF0007744922000022.tif37170

[0182]

[0184] 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: TIFF0007744922000023.tif35170

[0183]

[0185] To produce 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 h, 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 h 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 (14.2 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 with 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. TIFF0007744922000024.tif26170

[0184]

[0186] 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: TIFF0007744922000025.tif47170

[0185]

[0187] 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 h, 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 h 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. TIFF0007744922000026.tif67170

[0186]

[0188] 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 h, 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 h 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 ethylene glycol (3.83 g, 0.062 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 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: TIFF0007744922000027.tif37170

[0187]

[0189] 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 h, 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 h 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 (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: TIFF0007744922000028.tif71170

[0188]

[0190] 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: TIFF0007744922000029.tif72170

[0189]

[0191] 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 h, 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 h 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: TIFF0007744922000030.tif72170

[0190]

[0192] 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 h, 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 h 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 mixture purge, the reaction mixture was further stirred at 90° C. for an additional 2 hours to give the final product mixture as a viscous liquid with the average structure (XXXVIII) shown below. The product could then be used in subsequent formulations without further purification. The designed structure (XXXVIII) is shown below: TIFF0007744922000031.tif33170

[0191]

[0193] The specific oligomer reactants described above are shown in Table 2 below. TIFF0007744922000032.tif255170

[0192]

[0194] For purposes herein, 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 characterized as such.

[0193]

[0195] 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.

[0194] Compounds 1-22

[0196] 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 were mixed, in addition to other ingredients, as identified in Tables 3A-D below. The mixture was then premixed by hand 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.

[0195]

[0197] 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, segment 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 segment 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.

[0196] UPy equivalent

[0198] 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: TIFF0007744922000033.tif12170In formula, TIFF0007744922000034.tif8170=The amount by weight of each component Z per 100 g of the total relevant composition; TIFF0007744922000035.tif7170 = The number of 2-ureido-4-pyrimidinone groups present in one molecule of the Z component; and TIFF0007744922000036.tif7170 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.

[0197]

[0199] The UPy equivalent value for the entire composition is then calculated by adding the molar value of UPy groups for each UPy-containing component according to the following formula: TIFF0007744922000037.tif19170where n represents the number of UPy-containing components present in the formulation.

[0198]

[0200] The UPy equivalent values ​​can optionally be expressed as "UPy milliequivalents" by multiplying the total by 1000, although 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.

[0199]

[0201] 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) methods, as will be understood by those skilled in the art to which this invention applies.

[0200] (Meth)acrylate equivalent and disulfide equivalent

[0202] 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.

[0201] viscosity

[0203] 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 for a sufficient time for the bubbles to escape from the bulk of the liquid. Bubbles appearing on the top surface of the liquid were considered acceptable.

[0202]

[0204] Next, the bob was gently placed into the liquid in the measuring cup, and then 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°C) by waiting 5 minutes. Then, the sample was allowed to cool for 50 seconds. -1 The rotation speed was set to a specific value to generate a desired shear rate of .

[0203]

[0205] 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 changed 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.

[0204] Preparation of film samples

[0206] To create films that could be tested for various physical properties, each sample was subjected to 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.

[0205]

[0207] Individual test specimens approximately 1.27 cm (0.5 in. ± 1 / 32 in.) wide and 12.7 cm (5 in. ± 1 / 8 in.) long were then cut from the film. The exact thickness of each test specimen was measured with a calibrated micrometer.

[0206] Tensile strength, elongation, segment modulus, toughness test methods

[0208] The method for determining segment modulus used herein can be 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 segment modulus) were determined on an MTS Criterion™ Model 43.104 for 3 mil thick cured film specimens of each sample, prepared according to the "Film Sample Preparation" procedure above.

[0207]

[0209] Due to these relatively soft coatings (e.g., those with moduli less than approximately 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. Using a 0.9 kg (2 lb) load cell in an Instron 4442 Tensile Tester, modulus was calculated at 2.5% elongation using a least-squares fit of the stress-strain plot. Cured films were conditioned for 16–24 hours at 23.0 ± 0.1 °C and 50.0 ± 0.5% relative humidity before testing.

[0208]

[0210] The gauge length of the specimen 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.

[0209]

[0211] Tensile strength values ​​were determined as the maximum stress experienced by the specimen before fracture, and toughness values ​​were determined as the total area under the stress-strain curve.

[0210] Film Modification Test

[0212] 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. 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 assessed. The 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.

[0211]

[0213] 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. After each sample was maintained at 55°C for 5 minutes, 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 appropriately reported in Tables 3A, 3B, and 3D under the row headed "Film Repair, 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 repair behavior at 55°C exceeds that at room temperature.

[0212] Stress relaxation test

[0214] 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 a "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 values ​​of the total percentage stress reduction from 1 second to 100 seconds are reported in Tables 3A and 3D below. The total percentage stress reduction from 1 to 10 seconds is given by: Tables 3B and 3C has been reported.

[0213] Film mechanical recovery test

[0215] 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 films. For the avoidance of doubt, in each test, both films were prepared not only from the same formulation, 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.

[0214]

[0216] Both films were 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.

[0215]

[0217] After completion of the 12-14 hour healing period, 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 (over approximately 30 minutes) before measuring the tensile strength. The resulting values ​​were then recorded (referred to herein as "post-cut tensile strength").

[0216]

[0218] The film mechanical recovery values ​​reported in Table 3D below represent the measured post-break tensile strength value divided by the measured pre-break tensile strength value for each composition, expressed as a percentage to the nearest whole percent. If a sample showed no healing and the post-break tensile strength could not be measured, the value was simply reported as 0%. TIFF0007744922000038.tif217139 TIFF0007744922000039.tif228160 TIFF0007744922000040.tif123153

[0217] Discussion of results

[0219] As can be seen, compositions according to various aspects of the present invention tend to have properties that make them particularly suitable for use in optical fiber coating applications, and in particular for use as primary coatings on self-healing optical fibers, providing desirable viscosity, tensile strength, elongation, modulus, toughness, self-healing, and / or stress relaxation test results.

[0218]

[0220] Specifically, according to Table 3A, various compositions according to various embodiments of the present invention, including but not limited to the compositions of Examples 1, 3, 7, and 9, exhibit self-healing properties at 25° C. and / or 55° C. This is shown despite such compositions having a wide range of physical and / or rheological properties, such as viscosity and modulus. Example 7 exhibited self-healing behavior despite a measured segment modulus value of nearly 4 megapascals.

[0219]

[0221] Additionally, plots showing the stress relaxation performance of two compositions containing self-healing moieties (Examples 3 and 50)—as well as their analogs without self-healing moieties (Examples 4 and 6)—are provided in Figures 3A and 3B, respectively. Turning to Figure 3A, Example 3 demonstrates significant stress relaxation behavior compared to Example 4. Similarly, turning to Figure 3B, Example 5 is shown to have similar performance advantages over its control analog, Example 6. While Example 5 did not demonstrate significant self-healing behavior under the conditions referenced herein and reported in Table 3A above, it still demonstrated significant performance advantages with respect to stress relaxation behavior when compared to compositions without any self-healing moieties. While many viscoelastic polymeric materials may exhibit some form of stress relaxation behavior, the examples shown in Figures 3A, 3B, and Table 3C demonstrate significant stress reductions between 1 and 100 seconds attributed to the self-healing moieties, particularly the UPy groups. The stress relaxation behavior suggests the use of higher modulus, cavitation-resistant coatings, which tend to minimize attenuation due to microbending in optical fibers.

[0220]

[0222] Tables 3B-3C show that additional compositions containing additional sequences of oligomers that form the self-healing component still exhibit such beneficial properties. Specifically, compositions containing self-healing oligomers with disulfide groups as functional groups still exhibited some beneficial stress relaxation behavior. Formulation 16, which contained a self-healing oligomer containing both UPy and disulfide groups (oligomer 10), exhibited film healing at 25°C and demonstrated the best stress relaxation results in the series. Table 3C also demonstrates the beneficial effects of compositions containing both self-healing oligomers and oligomers that are not part of the self-healing component (e.g., Formulations 19-21).

[0221]

[0223] Finally, Table 3D shows that certain compositions containing self-healing oligomers (such as Oligomer 1 and Oligomer 6) may also exhibit self-healing via film mechanical recovery testing, in contrast to Control Formulation 4 and Control Formulation 10.

[0222]

[0224] Formulation 3 and Formulation 18 are recognized to have identical chemical formulations. Nevertheless, they are reported separately because they contained different lots of raw materials (although the same batch of Oligomer 1 was used). Variations in the measured properties are believed to be explained by batch variations in the raw materials used.

[0223] Additional Exemplary Embodiments

[0225] The first additional exemplary aspect includes the following embodiments.

[0226] 1. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule further having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Includes; (a) the self-healing component comprises, by weight of the total composition, more than 30%, or more than 40%, or more than 50%, or more than 60%, or more than 70%, or more than 80%; or 30-80%, or 30-70%, or 40-80%, or 40-70%, or 50-80%, or 50-70%; and / or (b) The composition contains more than 0.015 equivalents, or between 0.015 and 0.5 equivalents, or between 0.015 and 0.2, or between 0.015 and 0.15, or between 0.015 and 0.1, or between 0.015 and 0.08, or between 0.015 and 0.05, or between 0.015 and 0.045; or between 0.02 and 0.2, or between 0.02 and 0.15, or between 0.02 and 0.1, or between 0.02 and 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 of self-healing portion.

[0224]

[0227] 2. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule further having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Includes; the self-healing component comprises, consists of, or consists essentially of a compound having at least one polymerizable group and a backbone derived from a polyether polyol, a polyester polyol, a poly(dimethylsiloxane), a disulfide polyol, or a mixture thereof; (a) the self-healing component comprises, by weight of the total composition, more than 30%, or more than 40%, or more than 50%, or more than 60%, or more than 70%, or more than 80%; or 30-80%, or 30-70%, or 40-80%, or 40-70%, or 50-80%, or 50-70%; and / or (b) The composition contains more than 0.015 equivalents, or between 0.015 and 0.5 equivalents, or between 0.015 and 0.2, or between 0.015 and 0.15, or between 0.015 and 0.1, or between 0.015 and 0.08, or between 0.015 and 0.05, or between 0.015 and 0.045; or between 0.02 and 0.2, or between 0.02 and 0.15, or between 0.02 and 0.1, or between 0.02 and 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 of self-healing portion.

[0225]

[0228] 3. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule further having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Includes; The composition comprises less than 5 wt%, or less than 3 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%, of solvent, the determination of solvent content excluding (meth)acrylate-functional compounds. (a) the self-healing component comprises, by weight of the total composition, more than 30%, or more than 40%, or more than 50%, or more than 60%, or more than 70%, or more than 80%; or 30-80%, or 30-70%, or 40-80%, or 40-70%, or 50-80%, or 50-70%; and / or (b) The composition contains more than 0.015 equivalents, or between 0.015 and 0.5 equivalents, or between 0.015 and 0.2, or between 0.015 and 0.15, or between 0.015 and 0.1, or between 0.015 and 0.08, or between 0.015 and 0.05, or between 0.015 and 0.045; or between 0.02 and 0.2, or between 0.02 and 0.15, or between 0.02 and 0.1, or between 0.02 and 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 of self-healing portion.

[0226]

[0229] 4. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule further having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Includes; (a) the self-healing component comprises, by weight of the total composition, more than 30%, or more than 40%, or more than 50%, or more than 60%, or more than 70%, or more than 80%; or 30-80%, or 30-70%, or 40-80%, or 40-70%, or 50-80%, or 50-70%; and / or (b) The composition contains more than 0.015 equivalents, or between 0.015 and 0.5 equivalents, or between 0.015 and 0.2, or between 0.015 and 0.15, or between 0.015 and 0.1, or between 0.015 and 0.08, or between 0.015 and 0.05, or between 0.015 and 0.045; or between 0.02 and 0.2, or between 0.02 and 0.15, or between 0.02 and 0.1, or between 0.02 and 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 of self-healing portion. The composition comprises one or more of the following: a. Adhesion promoter compounds as part of the additive component; b. Adhesion-promoting functional groups as part of an oligomeric, monomeric, or self-healing component; and / or c.Antioxidants as part of the additive ingredients.

[0227]

[0230] 5. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising a molecule further having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Includes; The self-healing component includes an oligomer that includes at least one disulfide group.

[0228]

[0231] 6. The composition for coating an optical fiber of embodiment 5 above, wherein the oligomer comprising at least one disulfide group further comprises at least one 2-ureido-4-pyrimidinone (UPy) group.

[0229]

[0232] 7. The self-healing component is present in an amount greater than 30% by weight, or from 30 to 80% by weight, based on the weight of the total composition; and The composition of any one of the above embodiments 1-6 of the first additional exemplary aspect, wherein the composition has greater than 0.015 equivalents, or between 0.015 and 0.10 equivalents, of the self-healing moiety per 100 g of the composition.

[0230]

[0233] 8. The composition of any one of the above embodiments 1-7 of the first additional exemplary aspect, wherein the self-healing component comprises a reactive monomer component, a reactive oligomer component, and / or a plurality of molecules configured to bind to molecules in the self-healing component.

[0231]

[0234] 9. The composition of any one of the above embodiments 1-8 of the first additional exemplary aspect, wherein the reactive monomer component, reactive oligomer component, and / or self-healing component comprises, consists essentially of, or consists of molecules comprising one or more polymerizable moieties.

[0232]

[0235] 10. The polymerizable moiety is (i) a radiation-curable moiety, or (ii) a thermoset moiety, or (iii) both radiation-curable and heat-curable moieties The composition of any one of the above embodiments 1-9 of the first additional exemplary aspect, comprising:

[0233]

[0236] 11. The composition of any one of the above embodiments 1-10 of the first additional exemplary aspect, wherein the self-healing moiety comprises, consists of, or consists essentially of multi-hydrogen bonding groups or disulfide groups, or both.

[0234]

[0237] 12. The composition of any one of the above embodiments 1-11 of the first additional exemplary aspect, wherein the self-healing moiety comprises, consists of, or consists essentially of UPy groups, or at least 50%, or at least 60%, or at least 75%, or at least 90%, or 100% of the equivalents of self-healing groups per 100 g of composition consist of UPy groups.

[0235]

[0238] 13. Self-repairing ingredients a first molecule having a first self-repairing portion; and a second molecule having a second self-repairing moiety; Including, a first self-healing portion of the first molecule configured to bind to a second self-healing portion of the second molecule; The composition of any one of the above embodiments 1-12 of the first additional exemplary aspect, wherein the bond dissociation energy between the first self-healing moiety and the second self-healing moiety is between 9 kcal / mol and 100 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 9 kcal / mol to 20 kcal / mol, wherein the bond dissociation energy is calculated according to Table 1 of The Scientific World JOURNAL (2004) 4, 1074-1082, and references cited therein; and Nature 2002, Vol. 3, pp. 836-847, and references cited therein, as a direct summation of all bonds between the self-healing moieties.

[0236]

[0239] 14. The composition of any one of the above embodiments 1-13 of the first additional exemplary aspect, wherein the first self-healing portion and the second self-healing portion are the same.

[0237]

[0240] 15. The composition of any one of the above embodiments 1-14 of the first additional exemplary aspect, wherein the first self-healing portion and the second self-healing portion are different.

[0238]

[0241] 16. The composition of any one of the above embodiments 1-15 of the first additional exemplary aspect, wherein the first self-healing portion and the second self-healing portion comprise, consist of, or consist essentially of multi-hydrogen bonding groups.

[0239]

[0242] 17. The composition of any one of the above embodiments 1-16 of the first additional exemplary aspect, wherein the first self-healing portion and the second self-healing portion are configured to form a dimer, and the dimer has three or four hydrogen bonds.

[0240]

[0243] 18. The composition of the above embodiment 17 of the first additional exemplary aspect, wherein the dimer comprises a first linear chain linked to each of the hydrogen bonds on the side of the first self-healing portion and a second linear chain linked to each of three or four hydrogen bonds on the side of the second self-healing portion, and each of the first linear chain and the second linear chain comprises fewer than seven covalent bonds.

[0241]

[0244] 19. The composition according to the above embodiment 17 of the first additional exemplary aspect, wherein the dimer comprises a ring structure or a fused ring structure.

[0242]

[0245] 20. A dimer has the following structure: TIFF0007744922000041.tif121170, wherein R is selected from organic substituents optionally having a reactive group attached thereto; The composition of any one of the above embodiments 17-19 of the first additional exemplary aspect, according to any one of: (wherein the reactive group comprises an acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydrido, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimide group.

[0243]

[0246] 21. A dimer has the following structure: TIFF0007744922000042.tif70170, wherein R is selected from organic substituents optionally having a reactive group attached thereto; The composition of any one of the above embodiments 17-20 of the first additional exemplary aspect, according to: (wherein the reactive group comprises an acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydrido, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimide group).

[0244]

[0247] 22. The composition of any one of the above embodiments 1-21 of the first additional exemplary aspect, wherein the self-healing component comprises, consists of, or consists essentially of a plurality of molecules comprising at least one 2-ureido-4-pyrimidinone (UPy) group and at least three urethane linking groups.

[0245]

[0248] 23. The composition of the above embodiment 22 of the first additional exemplary aspect, wherein the composition has more 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 of UPy groups per 100 g of composition.

[0246]

[0249] 24. The composition of any one of the above embodiments 1-22 of the first additional exemplary aspect, wherein the polymerizable portion of the reactive monomer component, reactive oligomer component, and / or self-healing component comprises, consists of, or consists essentially of (meth)acrylate groups.

[0247]

[0250] 25. The composition of any one of the above embodiments 1-24 of the first additional exemplary aspect, wherein the composition can have 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 g of the composition.

[0248]

[0251] 26. The composition of any one of embodiments 1-25 above of the first additional exemplary aspect, wherein the self-healing component has between 0.015 and 0.1 equivalents, or between 0.03 and 0.1 equivalents, or between 0.037 and 0.1 equivalents, or between 0.03 and 0.08 equivalents, or between 0.03 and 0.05 equivalents, or between 0.037 and 0.08 equivalents, or between 0.037 and 0.05 equivalents of polymerizable moieties or (meth)acrylate groups per 100 g of the composition.

[0249]

[0252] 27. The composition of any one of the above embodiments 1-26 of the first additional exemplary aspect, wherein the ratio of equivalents of (meth)acrylate groups to equivalents of UPy groups in the composition is less than 14, or less than 10, or less than 8, or less than 6, or less than 5, or 1-14, or 1-10, or 1-8, or 1-6, or 1-5, or 3-10, or 3-8, or 3-5.

[0250]

[0253] 28. A self-repairing component having the following structure (VI): [A(G) n -D m ]-[A(G) n-1 -D m ] k -Z (VI); in the formula, 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 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 bivalent spacer independently selected from: -; -C(T)=C(T)-; -C(T)=N-; -C(T)=; -N=; or combinations thereof; 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 also has a divalent D m You can choose from the same D m and forms a ring structure with another divalent T selected from: 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 selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or a maleimide group; G, for each occurrence of n, is independently selected from hydrogen, Z, or a self-healing moiety according to the following structure (VI-b): (ZD m ) j XD m ― (VI-b);(In the formula, X is a multiple hydrogen bonding group or a disulfide group; When X is divalent, j=1, and when X is monovalent, j=0; wherein for at least one occurrence of n, G is a self-repairing moiety according to structure (VI-b). The composition according to any one of the above embodiments 1-27 of the first additional exemplary aspect, comprising, consisting of, or consisting essentially of a compound according to

[0251]

[0254] 29. When X comprises, consists of, or consists essentially of disulfide groups and j=1, the compound according to structure (VI) has a theoretical molecular weight MW between 500 and 100,000 g / mol. theo 29. The composition of embodiment 28 above, having

[0252]

[0255] 30. The composition according to the above two embodiments 28 or 29 of the first additional exemplary aspect, wherein X is a 2-ureido-4-pyrimidinone (UPy) group and j=0.

[0253]

[0256] 31. The composition of any one of the above three embodiments 28-30 of the first additional exemplary aspect, wherein the UPy group is a reaction product of 2-amino-4-hydroxy-6-methyl-pyrimidine.

[0254]

[0257] 32. The composition of any one of the above four embodiments 28-31 of the first additional exemplary aspect, wherein D comprises a urethane group, and the urethane group is the reaction product of a diisocyanate compound.

[0255]

[0258] 33. Diisocyanate compounds include 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), 2, 33. The composition of embodiment 32, comprising 2,4-trimethylhexamethylene diisocyanate, 2,4,4 trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, 2,4- and / or 4,4'-methylenedicyclohexyl diisocyanate, methylene diphenyl 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, or lysine isocyanate.

[0256]

[0259] 34. The composition of the above two embodiments 32 or 33 of the first additional exemplary aspect, wherein the diisocyanate compound comprises, consists of, or consists essentially of one or more of trimethylhexamethylene diisocyanate (TMDI) and / or isophorone diisocyanate (IPDI).

[0257]

[0260] 35. The composition of any one of the above embodiments 28-34 of the first additional exemplary aspect, wherein D comprises a polyol component, the polyol component comprising a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, an acrylic polyol, and / or combinations thereof.

[0258]

[0261] 36. The composition of any one of the above embodiments 28-35 of the first additional exemplary aspect, wherein Z comprises a (meth)acrylate group.

[0259]

[0262] 37. The composition of any one of the above embodiments 1-36 of the first additional exemplary aspect, wherein the monomer component comprises methyl acrylate, ethyl acrylate, butyl acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, lauryl acrylate, ethoxylated nonyl-phenol acrylate, or diethylene-glycol-ethyl-hexyl acylate.

[0260]

[0263] 38. The self-healing component and / or molecule according to structure (VI) has a glass transition temperature (T) 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 between -30 and -20°C, or between -25 and 20°C, or between -20 and 10°C. g The composition of any one of the above embodiments 1-37 of the first additional exemplary aspect, having

[0261]

[0264] 39. The self-healing component and / or molecule according to structure (VI) has a pH 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 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) (in g / mol).

[0262]

[0265] 40. The composition of any one of the above embodiments 1-39 of the first additional exemplary aspect, wherein the initiator component comprises, consists of, or consists essentially of one or more photoinitiators, the one or more photoinitiators comprising an acylphosphine oxide photoinitiator, an α-hydroxyketone photoinitiator, and / or a Norrish Type II photoinitiator.

[0263]

[0266] 41. The composition of any one of the above embodiments 1-40 of the first additional exemplary aspect, wherein the additive comprises one or more adhesion promoters, antioxidants, inhibitors, photosensitizers, carrier surfactants, tackifiers, catalysts, stabilizers, surface agents, and / or optical brighteners.

[0264]

[0267] 42. The composition of any one of the above embodiments 1-41 of the first additional exemplary aspect, wherein the composition has a segment modulus of 0.01 MPa to 100 MPa, or 0.05 to 50 MPa, or 0.05 to 20 MPa, or 0.05 to 10 MPa, or 0.05 to 5 MPa, or 0.1 to 3 MPa, or 2 to 20 MPa, or 2 to 10 MPa, or 2 to 5 MPa, wherein the segment modulus is measured according to the methods described elsewhere herein on a film prepared by the methods described elsewhere herein.

[0265]

[0268] 43. Composition: 50s -1 The composition of any one of the above embodiments 1-42 of the first additional exemplary aspect has 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, measured at a shear rate of 100 psi and a temperature of 25°C.

[0266]

[0269] 44. The composition of any one of the above embodiments 1-43 of the first additional exemplary aspect, wherein the monomeric and / or oligomeric components are 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 weight of the total composition; and / or

[0267]

[0270] 45. The composition of any one of the above embodiments 1-44 of the first additional exemplary aspect, wherein the self-healing component is present in an amount 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.

[0268]

[0271] 46. ​​The initiator is present in an amount of 0.01% to 10% by weight, or 0.05% to 5% by weight, or 0.1% to 3% by weight, based on the weight of the total composition; And the composition of any one of the above embodiments 1-45 of the first additional exemplary aspect, wherein the additive is present at 0% to 59.99% by weight.

[0269]

[0272] 47. The composition of any one of the above embodiments 1-46 of the first additional exemplary aspect, wherein the composition is substantially free of superacids and superbases.

[0270]

[0273] 48. The composition of any one of the above embodiments 1-47 of the first additional exemplary aspect, wherein the composition is substantially free of solvents including 2-propanol, acetone, acetonitrile, chloroform (CHCl3), dichloromethane, dimethyl sulfoxide ((CH3)2SO), ethyl acetate, hexane, methanol, tetrahydrofuran, toluene, propylene glycol, methyl ethyl ketone, and water, and the solvent content is determined.

[0271]

[0274] 49. The composition of any one of the above embodiments 1-48 of the first additional exemplary aspect, wherein the composition is substantially free of solvent.

[0272]

[0275] 50. The composition is exposed to 1 J / cm 2 radiation from a radiation source emitting a peak spectral output between 360 nm and 400 nm. 2 49. The composition of any one of the above embodiments 1-49 of a first additional exemplary aspect, wherein upon curing into a 3 mil film by exposure to a dose of energy of 55°C, preferably 23°C, at least one cut flaw is formed in the film, and the film heals to a visually detectable extent 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 the film is maintained at a temperature of 55°C, preferably 23°C, wherein the healing of the film is visually determined by microscopic imaging at 40x or 100x magnification.

[0273]

[0276] 51. when the composition is cured into a first film and a second film according to the sample preparation method described elsewhere herein, the composition having a pre-cut tensile strength of the first film and a post-cut tensile strength of the second film, the pre-cut tensile strength and post-cut tensile strength being determined after the second film is subjected to the cutting procedure described elsewhere herein, and then maintained at a temperature of about 25°C or about 55°C for 12 to 14 hours; The composition of any one of the above embodiments 1-50 of the first additional exemplary aspect, wherein the tensile strength after cutting is greater than 50%, or greater than 60%, or greater than 85%, or greater than 90%, or greater than 95% of the tensile strength before cutting, wherein the pre-cut tensile strength and post-cut tensile strength are each measured according to ASTM D638 and further described elsewhere herein.

[0274]

[0277] 52. 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. 2The composition of any one of the above embodiments 1-51 of first additional exemplary aspect, when cured to a 3 mil film by exposure to a dose of energy of from 0.05 to 0.50, has a stress relaxation of from 1 second to 10 seconds, and has a modulus of elongation of greater than 20%, or greater than 30%, or greater than 50%, or 30-90%, or 30-65%, or 45-90%, or 45-75%, or 45-65%, as measured according to the methods described herein.

[0275]

[0278] 53. The composition of any one of the above embodiments 1-52 of the first additional exemplary aspect, wherein the composition, when cured into a film, has a segment modulus of 0.01 MPa to 100 MPa, or 0.05 to 50 MPa, or 0.05 to 20 MPa, or 0.05 to 10 MPa, or 0.05 to 5 MPa, or 0.1 to 3 MPa, or 2 to 20 MPa, or 2 to 10 MPa, or 2 to 5 MPa, wherein the segment modulus is measured according to the methods described elsewhere herein on a film prepared by the methods described elsewhere herein.

[0276]

[0279] A second additional exemplary aspect includes the following embodiment.

[0277]

[0280] 54. An oligomer for use in an optical fiber coating according to structure (VII) below: [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; 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 a combination thereof; 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 also has a divalent D m You can choose from the same D m and forms a ring structure with another divalent T selected from: i is an integer from 1 to 40, Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or a maleimide group; and G, for each occurrence of n, is independently selected from hydrogen, -Dm-Z, or a self-healing moiety according to the following structure (VII-b): (ZD m ) j XD m - (VII-b);(in the formula, X is a multiple hydrogen bonding group or a disulfide group; (When X is divalent, j=1, and when X is monovalent, j=0).

[0278]

[0281] 55. The composition of any one of embodiments 1-53 of the first additional exemplary aspect, further comprising an oligomer according to embodiment 54 of the second additional exemplary aspect.

[0279]

[0282] A third additional exemplary aspect includes the following embodiment.

[0280]

[0283] 56. A composition for coating an optical fiber, a glass fiber optionally comprising a core layer and a cladding layer; a first coating layer disposed around and in contact with the glass fibers; Optionally, an ink layer disposed around and in contact with the first coating layer or the second coating layer; Including, A composition for coating an optical fiber, wherein the first coating layer comprises (a) any one of embodiments 1 to 50 of the first additional exemplary aspect, and / or (b) an oligomer according to embodiment 51 of the second additional exemplary aspect.

[0281]

[0284] 57. A self-healing coated optical fiber according to the above embodiment 56 of the third additional exemplary aspect, wherein the self-healing coated optical fiber is configured to repair cavitations formed in more than 20%, or more than 50%, or more than 75%, or more than 90% of the coating layer within 48 hours, or preferably within 8 hours, or preferably within 1 hour, or preferably within 5 minutes, or preferably within 1 minute, as visually determined via microscopic imaging at 40x or 100x magnification, while the self-healing coated optical fiber is maintained at a temperature below 80°C, or preferably below 60°C, or preferably below 50°C, or preferably below 25°C.

[0282]

[0285] 58. A first coating layer is disposed around and in contact with the glass fiber, the first coating layer being a primary coating layer; A self-healing coated optical fiber according to any one of the above embodiments 56-57 of the third additional exemplary aspect, wherein the self-healing coated optical fiber further comprises a secondary coating layer disposed around and in contact with the primary coating layer.

[0283]

[0286] 59. The self-healing coated optical fiber according to any one of embodiments 56-57, wherein the first coating layer is the only coating layer on the self-healing coated optical fiber.

[0284]

[0287] 60. A self-healing coated optical fiber according to any one of the above embodiments 56-59 of the third additional exemplary aspect, wherein the glass transition temperature of the first coating layer 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.

[0285]

[0288] Unless otherwise specified, weight percent refers to the amount by weight of a particular component relative to the total liquid radiation curable composition in which it is incorporated.

[0286]

[0289] The use of the terms "a," "an," and "the" and similar referents in the context of describing the present invention (particularly in the context of the claims that follow) 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.

[0287]

[0290] 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. Furthermore, this invention encompasses any combination of the above-described elements in all possible variations thereof unless otherwise indicated herein or clearly contradicted by context.

[0288] 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 thereto without departing from the spirit and scope of the invention as claimed.

Claims

1. 1. A composition for coating an optical fiber, comprising: Optionally, reactive monomeric and / or oligomeric components; a self-healing component comprising, consisting of, or consisting essentially of a molecule having one or more self-healing moieties and optionally one or more polymerizable moieties; an initiator component; Optionally, an additive component and Including; (a) the self-healing component is present in an amount greater than 30 wt. %, based on the weight of the total composition; or (b) the composition has greater than 0.015 equivalents of self-healing moiety per 100 grams of the composition; the self-healing moiety comprises, consists of, or consists essentially of a 2-ureido-4-pyrimidinone (UPy) group or a disulfide group, or both; composition.

2. The self-healing component is present in an amount of 30 to 80 wt. % based on the weight of the total composition; and the composition has 0.015 to 0.10 equivalents of the self-healing moiety per 100 g of the composition; The composition of claim 1.

3. 3. The composition of claim 1 or 2, wherein the composition comprises less than 5 wt. % solvent, or less than 1 wt. % solvent, or less than 0.1 wt. % solvent, wherein the solvent weight content can be determined by size exclusion chromatography (SEC) method.

4. 4. The composition of claim 1, wherein the self-healing component comprises one or more compounds having a backbone derived from a polyether polyol, a polyester polyol, a poly(dimethylsiloxane), a disulfide polyol, or a combination thereof.

5. (1) an adhesion promoter compound as part of the additive component; (2) adhesion-promoting functional groups as part of an oligomeric, monomeric, or self-healing component; and / or (3) Antioxidants as part of additive components 5. The composition of claim 1, wherein the composition comprises one or more of:

6. The reactive monomer component, the reactive oligomer component, and the self-healing component each comprise one or more polymerizable moieties, the polymerizable moieties comprising: (i) radiation curable portion; (ii) a thermoset moiety; or (iii) Both radiation-curable and heat-curable moieties 6. The composition of claim 1, comprising:

7. 7. The composition of claim 6, wherein at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 99%, or 100% of the equivalent weight of the self-healing moieties in the composition consist of UPy groups.

8. Self-repairing ingredients a first molecule having a first self-repairing portion; and a second molecule having a second self-repairing moiety; Including, a first self-healing portion of the first molecule configured to bind to a second self-healing portion of the second molecule; 8. The composition of claim 1, wherein the first self-healing moiety and the second self-healing moiety are independently multiple hydrogen bonding groups.

9. 9. The composition of any one of claims 1 to 8, wherein the bond dissociation energy between the first self-healing moiety and the second self-healing moiety is between 9 and 100 kcal / mol, or between 30 and 60 kcal / mol.

10. 10. The composition of claim 1, wherein the first self-healing portion and the second self-healing portion are configured to form a dimer, the dimer having three or four hydrogen bonds, the dimer comprising a first linear chain connected to each of the three or four hydrogen bonds on the first self-healing portion and a second linear chain connected to each of the three or four hydrogen bonds on the second self-healing portion, and each of the first linear chain and the second linear chain comprising fewer than seven covalent bonds.

11. The dimer has the following structures (I) to (V): wherein R is selected from organic substituents optionally having a reactive group attached thereto; 11. The composition of claim 1, wherein the reactive group comprises an acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydrido, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimide group.

12. 12. The composition of any one of claims 1 to 11, wherein the self-healing component comprises, consists of, or consists essentially of a plurality of molecules comprising at least one UPy group and at least three urethane linking groups.

13. 13. The composition of claim 12 having greater than 0.015 equivalents of UPy groups per 100 g of composition, or from 0.015 to 0.10 UPy groups, or from 0.015 to 0.05 UPy groups.

14. the polymerizable portion of the reactive monomer component, reactive oligomer component, and / or self-healing component comprises, consists of, or consists essentially of (meth)acrylate groups; the composition has 0.1 to 0.4 equivalents of (meth)acrylate groups per 100 g of composition; and / or The composition of any one of claims 1 to 13, wherein the ratio of equivalents of (meth)acrylate groups to equivalents of UPy groups in the composition is less than 14, or from 3 to 10.

15. the self-healing component comprises a compound having a urethane group, the urethane group being a reaction product of a diisocyanate compound; The monomer component comprises methyl acrylate, ethyl acrylate, butyl acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, lauryl acrylate, ethoxylated nonylphenol acrylate, or diethylene glycol ethylhexyl acylate; the initiator component comprises, consists of, or consists essentially of one or more photoinitiators, the one or more photoinitiators comprising an acylphosphine oxide photoinitiator, an α-hydroxyketone photoinitiator, and / or a Norrish Type II photoinitiator; 15. The composition of any one of claims 1 to 14.

16. 16. The composition of any one of claims 1 to 15, wherein the self-healing component has a glass transition temperature (Tg) of from -30 to 20°C.

17. The self-healing component has a theoretical molecular weight (MW) between 500 and 8000, or between 1000 and 4000. ｔｈｅｏ 17. The composition of any one of claims 1 to 16, comprising a compound having (in g / mol):

18. 18. The composition of any one of claims 1 to 17, wherein the composition has a viscosity of less than 15 Pascal seconds (Pa·s), or from 0.05 Pa·s to 5 Pa·s, measured at a shear rate of 50 s −1 and a temperature of 25°C.

19. Based on the weight of the entire composition, the monomeric and / or oligomeric components are present at 10% to 65% by weight; the self-healing component is present at greater than 30% to 80% by weight; the initiator is present at 0.01% to 10% by weight; and the additive is present in an amount of from 0% to 59.99% by weight; 19. The composition of any one of claims 1 to 18, wherein each of the components is added to 100% by weight.

20. Providing a glass optical fiber; applying a primary coating composition onto a surface of a glass optical fiber; Optionally, applying a dose of radiation energy, including UV, sufficient to at least partially cure said primary coating composition; applying a secondary coating composition to a primary coating composition; exposing the primary coating composition and the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to affect curing of the primary coating composition and the secondary coating composition to form a cured primary coating on the surface of the optical fiber, and forming a cured secondary coating on the surface of the cured primary coating; Including, 20. A method of making a coated optical fiber, wherein the primary coating composition is any of the compositions of any one of claims 1 to 19.

21. 21. A coated optical fiber made by the method of claim 20 and / or comprising a coating that is the cured product of the composition of any one of claims 1 to 19.

22. 22. A fiber optic cable comprising a plurality of optical fibers disposed therein, at least one of the optical fibers being the optical fiber of claim 21.

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