Self-healing optical fiber and the composition used to manufacture it.

Abstract

This document discloses compositions for coating optical fibers, the compositions comprising optional reactive monomers and / or oligomers, a self-healing component having self-healing fragments, an initiator component, and optional additive components. The self-healing component preferably comprises polymerizable fragments. Such compositions contain greater than 30% by weight of the self-healing component per 100g of the composition, and / or greater than 0.015 equivalents of the self-healing fragments. This document also discloses coated optical fibers having glass fibers, at least one coating, and an optional ink layer, the coated optical fibers being configured to have self-healing properties and / or stress relaxation behavior. Further disclosed are methods for coating self-healing optical fibers, and optical fiber cables comprising one or more coated self-healing optical fibers.

Description

Technical Field

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

[0002] Cross-reference to related applications

[0003] This application claims priority to U.S. Provisional Application No. 63 / 004553, filed April 3, 2020, which is incorporated herein by reference in its entirety as if it were fully set forth herein. Background Technology

[0004] Optical fiber provides a reliable and efficient means of facilitating telecommunications and computer networking. Using light-based technology, fiber optic cables can transmit large amounts of broadband data over long distances with minimal signal loss. In this respect, it has become the preferred communication medium over other means, such as wires or coaxial cables.

[0005] Optical fibers consist of glass fibers obtained through glass melt spinning and one or more coatings disposed on the glass fibers for protective reinforcement. Optical fibers can be produced, for example, by first forming a flexible primary coating on the surface of the glass fibers, and then forming a more rigid secondary coating, known as a secondary coating, on top of the primary coating. Ribbon optical fibers or optical fiber cables having multiple fibers with coatings bonded together using an adhesive or "matrix" material are also known.

[0006] A relatively soft primary coating provides resistance to microbending. Microbending is an undesirable phenomenon that leads to a reduction or loss in fiber optic signal transmission, also known as attenuation. Microbending is a microscopic curvature in an optical fiber, involving local axial displacement of a few micrometers and spatial wavelengths of a few millimeters. Microbending can be induced by thermal stress and / or mechanical lateral forces. Coatings can provide protection against the lateral forces of microbending, but the amount of protection provided tends to decrease as the coating thickness decreases.

[0007] The primary coating preferably has a higher refractive index than the cladding of the associated optical fiber to allow it to strip erroneous optical signals from the fiber core. The primary coating should maintain sufficient adhesion to the glass fiber during thermal and hydrolytic aging and still be peelable for splicing purposes. Primary coatings typically have a thickness in the range of 20 μm to 50 μm (e.g., about 25 μm or 32.5 μm), or 15 μm to 25 μm for 200 μm fibers.

[0008] The harder secondary coating provides resistance to handling forces, such as those encountered when the coated optical fiber is ribbonized and / or cabled. Both the primary and secondary coatings are primarily formed from radiation-curable compositions. Such compositions typically contain a mixture of olefinically unsaturated compounds, including one or more acrylate-functionalized oligomers dissolved or dispersed in a liquid olefinically unsaturated diluent and a photoinitiator. The coating composition is typically applied to the optical fiber in liquid form and then exposed to photochemical radiation for curing.

[0009] For a long time, there has been a desire to provide coatings, particularly primary coatings, with the ability to minimize attenuation induced by microbending in optical fibers to which such coatings are applied. Historically, it has been recognized that there is room for improvement in the design of primary fiber coatings because they often fail to adequately limit signal loss, as they are in fact too stiff to dissipate most of the stress reaching the associated glass fibers. Furthermore, in terms of the extent to which they do absorb some stress, such primary coatings do not possess any perceptible ability to participate in stress relaxation to balance local stresses over time.

[0010] To appropriately minimize microbending-induced attenuation, primary coatings are initially engineered to have lower modulus values. In this way, it is known that softer primary coatings can absorb microstress and better buffer the fiber. However, softer coatings also tend to have lower structural integrity, making them more susceptible to damage during processing and / or handling. This tends to lead to an increase in the development of undesirable voids or defects (known as cavitation), which can also degrade fiber performance. The risk of introducing cavitation into soft primary coatings is particularly severe during fiber coating, winding, or cabling processes, but this risk can also occur during fiber installation or even naturally through thermal stress induced by post-installation temperature cycling.

[0011] Efforts have been made to mitigate the tendency for cavitation to form in soft optical fiber coatings. Such methods have historically focused on increasing toughness, structural stiffness, or minimizing the coefficient of thermal expansion of the soft primary coating.

[0012] However, to date, no known solution is believed to exist that enables the coating to adequately rearrange its internal polymer structure in situ after application and curing on the optical fiber. Therefore, it is desirable to provide compositions that impart self-healing properties to coated optical fibers produced therefrom, allowing for the minimization or even reversal of certain defect formation under various environmental conditions. Alternatively or additionally, it is desirable to provide compositions that impart excellent stress relaxation behavior to coated optical fibers produced therefrom, as this alleviates the need for reliance on overly soft, easily cavitating coatings to improve microbending properties. Summary of the Invention

[0013] This document describes several aspects and embodiments of the invention. A first aspect is a composition for coating optical fibers, the composition comprising, optionally, a reactive monomer and / or optional reactive oligomer component; a self-healing component consisting of molecules having one or more self-healing portions and optionally one or more polymerizable segments; an initiator component; and optional additive component; wherein (a) the self-healing component is present in an amount greater than 30% by weight relative to the total composition, and / or (b) the composition has a self-healing segment amount greater than 0.015 equivalents per 100g of the composition.

[0014] According to other embodiments of the first aspect, the composition has polymerizable segments, such as (meth)acrylate segments, and / or the self-healing segments may include polyhydrogen-bonded groups or disulfide groups. In some embodiments, the self-healing segments have certain specific bond energies between two bonded self-healing segments. In yet another embodiment of the first aspect, the self-healing segment includes a 2-ureido-4-pyrimidinone (UPy) group and / or at least three urethane linking groups. In further embodiments, the entire composition and / or the self-healing component specifically has UPy groups or (meth)acrylate groups in a specified equivalent value per 100g of the composition.

[0015] In another embodiment of the first aspect, the self-healing component comprises molecules according to certain specific structures, such as structure (VI) mentioned elsewhere herein. In an alternative embodiment of the first aspect, the self-healing component and / or molecules according to certain specific structures—such as structure (VI) mentioned elsewhere herein—have specified glass transition temperatures, molecular weight values, and / or specific reactants. In other embodiments, the composition has specified viscosity values, and / or amounts of monomers, oligomers, self-healing components, (photo)initiators, and / or additives.

[0016] In another embodiment of the first aspect, the composition is configured to have certain self-healing properties when present as a cured product, such as a film, as demonstrated by comparison of certain measured mechanical properties before and after a cut or tear has been applied to the cured product.

[0017] The second aspect of the present invention is a self-healing oligomer according to the following structure (VII):

[0018] [UPy-(D m -UD m ) (2+q) ]-[A(G) (n-1) -D m ] k -Z (VII);

[0019] in

[0020] UPy represents the UPy group, where the UPy group is 2-ureido-4-pyrimidinone;

[0021] U represents -NHC(O)E- or -EC(O)NH-, where E is O, NH, N (alkyl) or S;

[0022] q is a number greater than or equal to 0 and less than or equal to 10;

[0023] k is a number from 0 to 20;

[0024] A is selected from carbon and nitrogen;

[0025] n is 2 or 3, where n = 3 when A is sp3 carbon and n = 2 when A is sp2 carbon or nitrogen;

[0026] m is an integer from 0 to 500;

[0027] For each occurrence of m, D is independently selected from the following divalent spacer groups: -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)-, -C(T)=N-, -C(T)=, -N=, or combinations thereof;

[0028] in

[0029] For each instance of a single-bond D, the single-bond is concatenated with it, and for each instance of a double-bond D, the double-bond is concatenated with it.

[0030] in

[0031] For each occurrence, each T is selected from a monovalent unit, including hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl;

[0032] Each T can also be selected from divalent D. m And connected to another one also selected from D m The divalent T forms a ring structure; and

[0033] And i is an integer from 1 to 40;

[0034] Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridino, carboxylate, F, Cl, Br, I, or maleimide; and

[0035] For each occurrence of n, G is independently selected from hydrogen, -D m -Z, or a self-repairing fragment based on the following structure (VII-b):

[0036] (ZD m ) j XD m - (VII-b);

[0037] in

[0038] X is a polyhydrogen-bonded group or a disulfide group;

[0039] j = 1 when X is divalent, and j = 0 when X is monovalent.

[0040] According to other embodiments of the second aspect, the oligomer according to structure (VII) is present in the composition for coating optical fibers, preferably in a liquid radiation curable composition, such as a primary coating composition.

[0041] A third aspect of the invention is a self-healing coated optical fiber comprising a coating that is a cured product of any of the compositions described in the first aspect of the invention and / or the oligomers described in the second aspect.

[0042] According to various possible implementations of the third aspect, the coating is a primary coating, and the self-healing coated optical fiber also has a secondary coating disposed around and in contact with the primary coating.

[0043] A fourth aspect of the invention is a method for coating optical fibers, the method comprising coating glass fibers with a primary coating composition, said primary coating composition being a cured product of any composition described in any embodiment of the first aspect and / or containing any self-healing oligomer according to any embodiment of the second aspect.

[0044] The fifth aspect of the invention is an optical fiber cable having more than one optical fiber disposed therein, wherein at least one optical fiber is a self-healing optical fiber according to any embodiment of the third aspect, the self-healing optical fiber being optionally processed by any embodiment of the fourth aspect, being a cured product of a composition according to any embodiment of the first aspect, and / or containing any self-healing oligomer described in the second aspect. Attached Figure Description

[0045] Figure 1 The layout of the cutting process used to determine the self-healing efficacy of the cured film as described elsewhere in this document is schematically depicted.

[0046] Figure 2A , Figure 2B , Figure 2C , Figure 2D and Figure 2E The progress of cavitation elimination over time in a self-healing primary coating according to the invention, applied in the geometry of the optical fiber, is depicted under various ambient temperatures.

[0047] Figure 3A and Figure 3B The stress relaxation test curves for two different formulations, as described elsewhere in this article, are plotted. Detailed Implementation

[0048] A first aspect of the present invention is a composition for coating optical fibers, the composition comprising:

[0049] Optionally, reactive monomer and / or oligomer components;

[0050] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally one or more polymerizable segments;

[0051] Initiator components; and

[0052] Optionally, additive components;

[0053] Wherein (a) the self-healing component is present in an amount greater than 30% by weight, or greater than 40% by weight, or greater than 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight relative to the total composition; and / or

[0054] (b) The composition has a self-repairing fragment of greater than 0.015 equivalent per 100g of the composition.

[0055] The compositions according to the first aspect are curable, that is, they are capable of undergoing a chemical reaction, preferably a polymerization reaction, to achieve hardening or curing of the composition upon sufficient exposure to a adequate stimulus. Such a stimulus can be achieved by applying heat (thus making the composition thermally curable) or by photochemical radiation of a sufficient dose and appropriate wavelength (thus making the composition radiatively curable). According to various embodiments, such compositions may comprise optional reactive monomer components, optional oligomer components, self-healing components, initiator components, and optional additive components. Such components, described in more detail below, can be equally and suitably used in other aspects of the invention, such as compositions for coating optical fibers according to the second aspect, self-healing coated optical fibers according to the third aspect, methods for coating optical fibers according to the fourth aspect, or optical fiber cables according to the fifth aspect.

[0056] Monomer components

[0057] The composition according to a first aspect of the invention optionally comprises a monomer component; that is, a collection of one or more individual monomers having one or more specified structures or types. Monomers are molecules with low relative molecular mass whose structures can be polymerized, thereby contributing structural units to the basic structure of a macromolecule. In one embodiment, the monomer component comprises a theoretical molecular weight (MW) having a molecular weight of about 86 g / mol to about 800 g / mol, or 100 g / mol to 350 g / mol. 理论 The monomer composition of ) is MW 理论 It is determined by calculating the theoretical molecular weight of the ideal structure of the monomer used (usually indicated by the corresponding CAS number). For the purposes of this document, a single monomer should be interpreted as part of the monomeric component unless it has a self-healing fragment as described elsewhere in this document; in that case, it should be interpreted as part of the self-healing component.

[0058] Monomers are commonly used as diluents in optical fiber coating compositions. That is, they can be used to alter—and more specifically, typically reduce—the viscosity of the larger composition to which they are added. Multiple diluents are used to maximize the flowability of the associated optical fiber coating composition and, consequently, its processability.

[0059] Besides merely altering the viscosity of the liquid composition, such monomers are also preferably used to accelerate the curing speed and / or physical properties of coatings produced therefrom. Therefore, monomers are typically reactive monomers. As used herein, "reactive" refers to the ability to chemically react with another molecule, preferably to polymerize. Thus, a reactive compound will be referred to as having at least one reactive group or functional group. When used for such purposes, the monomer will be considered to have at least one reactive group or functional group. Preferably, such reactive group or functional group is a polymerizable group. If used, the monomer component preferably comprises, is composed of, or is substantially composed of reactive monomers or reactive diluent monomers.

[0060] In one embodiment, the monomer component according to the invention comprises, is substantially composed of, or is composed of a reactive monomer having at least one polymerizable group. In a preferred embodiment, the monomer component comprises reactive monomers having an average of one polymerizable group. The polymerizable group of the reactive monomer is preferably capable of co-polymerization with other polymerizable groups present in the composition (e.g., those present in self-healing components and / or optional oligomer components).

[0061] The polymerizable group of a reactive diluent can be of any known type. However, in one embodiment, the polymerizable group may comprise, consist essentially of, or be composed of, for example, acrylate, methacrylate, acrylamide, or N-vinylamide groups or any combination thereof. The reactive diluent is preferably an olefinically unsaturated polymerizable compound containing at least one reactive olefinic double bond.

[0062] Polymerizable groups can appear at any feasible point along the length of the monomer. However, in a preferred embodiment, the polymerizable group comprises, is substantially composed of, or is composed of polymerizable end groups.

[0063] The monomeric components according to the invention may include any known type of compound or substance consistent with the definitions specified elsewhere herein. However, in a preferred embodiment, the monomer comprises, is substantially composed of, or consists of one or more reactive diluent monomers containing a double bond.

[0064] Typical examples of monomers containing a single double bond are alkyl acrylates or hydroxyalkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA) and 2-hydroxyethyl acrylate, isobornyl acrylate, methyl acrylate and ethyl acrylate, lauryl acrylate, ethoxylated nonylphenol acrylate and diethylene glycol ethylhexyl acrylate (DEGEHA). Methacrylated forms of such monomers can also be suitably obtained. Other examples of monomers are acrylonitrile, acrylamide, N-substituted acrylamide, vinyl esters such as vinyl acetate, styrene, alkylstyrene, halostyrene, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl chloride and vinylidene chloride.

[0065] Examples of monomers containing more than one double bond 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 pentaerythritol tetraacrylate, and vinyl acrylate.

[0066] In one embodiment, the monomer component comprises, is substantially composed of, or is composed 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, is composed of, or is substantially composed of functional monomers (e.g., (meth)acrylic acid monomers).

[0067] One or more of the monomers described above may be used in the compositions according to the invention in any suitable amount as needed, to tune the curing rate or viscosity of the formulation associated with them to a fiber coating process suitable for use in a manner well-known in the field to which the invention applies, and may be selected individually or in combination with one or more of the types listed herein. 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 amounts of 10 wt% to 65 wt%, 10 wt% to 55 wt%, 10 wt% to 50 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%; or 20 wt% to 65 wt%, 20 wt% to 55 wt%, 20 wt% to 50 wt%, 20 wt% to 40 wt% relative to the total weight of the radiation-curable composition.

[0068] oligomer components

[0069] The compositions according to the invention optionally further comprise an oligomer component; that is, a collection of one or more individual oligomers having one or more specified structures or types. Oligomers are used herein to refer to molecules having an intermediate relative molecular mass whose structure comprises, in fact or conceptually, multiple units derived from molecules having a lower relative molecular mass. As used herein, if the component further has a molecular weight mass (MW) of about 1000 g / mol to about 100,000 g / mol... 理论 If the value is specified, the component is considered to be an oligomer, where MW... 理论 It was determined by calculating the theoretical molecular weight of the ideally structured oligomer used. For the purposes of this document, an oligomer alone should be interpreted as part of the oligomer component unless it possesses a self-healing fragment as described elsewhere in this document; in that case, it should be interpreted as part of the self-healing component.

[0070] In one embodiment, if used, the oligomer component comprises, is composed of, or is substantially composed of one or more of the following: a theoretical molecular weight of at least 2000 g / mol, or at least 3000 g / mol, or at least 4000 g / mol, or 2000 g / mol to 15000 g / mol, or 2000 g / mol to 13000 g / mol, or 2000 g / mol to 10000 g / mol, or 3000 g / mol to 8000 g / mol, or 3500 g / mol to 5500 g / mol; or in another embodiment, a theoretical molecular weight of at least 1000 g / mol, more. The oligomer composition preferably has a concentration greater than 1200 g / mol, more preferably greater than 1500 g / mol, more preferably greater 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 1500 g / mol to 12000 g / mol, or 2000 g / mol to 12000 g / mol, or 2500 g / mol to 12000 g / mol, or 2500 g / mol to 11000 g / mol, or 2500 g / mol to 10000 g / mol.

[0071] If used, the oligomer component preferably comprises, is composed of, or is substantially composed of one or more reactive oligomers having at least one reactive group or functional group. Preferably, such reactive group or functional group is a polymerizable group. Although the use of some non-reactive oligomers may be considered in the present invention, a large percentage of reactive oligomers is preferred. In one embodiment, the oligomer component consists of or is substantially composed of reactive oligomers.

[0072] In one embodiment, the reactive oligomer component according to the invention comprises, is substantially composed of, or is composed of a reactive oligomer having at least one polymerizable group. In a preferred embodiment, the reactive oligomer component comprises a reactive oligomer having at least one polymerizable group. The polymerizable group can be of any known type. In one embodiment, the polymerizable group may comprise, is substantially composed of, or is composed of acrylate or methacrylate groups, or any combination thereof. The reactive oligomer is preferably an olefinically unsaturated polymerizable compound containing one or more reactive olefinic double bonds.

[0073] Polymerizable groups can appear at any feasible point along the length of the reactive oligomer, including as polymerizable backbone groups or polymerizable end groups. Polymerizable backbone groups are present as a straight chain along the length of the oligomer or branched from a straight chain, while polymerizable end groups are polymerizable groups present at the ends of the oligomer. For example, polymerizable groups can exist separately from or directly or indirectly adjacent to other polymerizable groups, such as in a branched or forked form at the ends of the oligomer (e.g., referred to herein as "terminal points"). In a preferred embodiment, the polymerizable group comprises, is substantially composed of, or is composed of polymerizable end groups.

[0074] The reactive oligomers according to the invention can be any known type consistent with the definition specified elsewhere herein. Fiber optic coating compositions typically utilize reactive urethane oligomers because they can impart desired properties to the associated articles cured therefrom. In one embodiment, the oligomer component comprises, is composed of, or is substantially composed of one or more urethane oligomers, preferably reactive urethane oligomers. The reactive urethane oligomer comprises at least one urethane group or segment, and preferably comprises at least one backbone, a polymerizable group, and urethane groups linking said backbone to said polymerizable group. According to a first aspect, the reactive urethane oligomer comprises a reaction product of a polyol, a polyisocyanate, and an isocyanate reactive (meth)acrylate.

[0075] Examples of suitable polyol compounds preferred for forming 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 the reaction product of a polyether polyol. In one embodiment, the backbone comprises the reaction product of polypropylene glycol (PPG). As used herein, compounds derived from polypropylene glycol include end-capped PPGs, such as EO-end-capped PPGs. There are no particular limitations on the polymerization method of the structural units in these polyols. Random polymerization, block polymerization, or graft polymerization are all acceptable. As used herein, polyols are intended to include organic compounds containing two or more hydroxyl functional groups per molecule.

[0076] As used herein, a block copolymer refers to an oligomer or a portion of a polymer comprising a plurality of structural units, wherein at least one structural unit contains a feature not present in adjacent portions. As used herein, monoblock, diblock, and triblock copolymers refer to the average amount of a particular block present in an oligomer. In a preferred embodiment, a particular block refers to a polyether block derived from one or more polyols, preferably polyether polyols, as described elsewhere herein. In one embodiment, the blocks referred to in monoblock, diblock, and / or triblock copolymers are polyether blocks derived from one or more polyols described elsewhere herein. In one embodiment, a monoblock copolymer may be described as a copolymer having only about 1, or about 0.9 to less than 1.5 units of a particular block (e.g., a polyether block) on average. In one embodiment, a diblock copolymer may be described as a copolymer having about 2, or at least 1.5 to less than 2.5 units of a particular block (e.g., a polyether block) on average. In one embodiment, a triblock copolymer can be described as a copolymer having an average of about 3, or at least 2.5 to less than 3.5 units of a specific block (e.g., a polyether block). The number of polyether units in a given oligomer can be determined by the number of polyether polyol molecules utilized in the synthesis of a single oligomer.

[0077] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether glycols obtained by ring-opening copolymerization of two or more ionically polymerizable cyclic compounds. Here, examples of ionically polymerizable cyclic compounds are cyclic ethers, such as ethylene oxide, propylene oxide, isobutane oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monooxide, vinyloxetane, vinyltetrahydrofuran, vinylcyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ionicly polymerizable cyclic compounds include combinations for producing binary copolymers, such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, and tetrahydrofuran and ethylene oxide; and combinations for producing ternary copolymers, such as combinations of tetrahydrofuran, 2-methyltetrahydrofuran and ethylene oxide, combinations of tetrahydrofuran, 1-butene-1-oxide and ethylene oxide, and so on. These ring-opening copolymers of ionicly polymerizable cyclic compounds can be random copolymers or block copolymers.

[0078] These polyether polyols include, for example, the following commercially available products: PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), PEG#1000 (manufactured by Nippon Oil and Fats Co., Ltd.), PTG650(SN), PTG1000(SN), PTG2000(SN), PTG3000, PTGL 1000, and PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), PEG400, PEG600, PEG1000, PEG1500, PEG2000, PEG4000, and PEG6000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), P710R, P1010, P2010, and 1044. P series (provided by BASF) and The series (including PPG725, PPG1000, PPG2000, PPG3000, PPG4000 and PPG8000), and The series includes PO / EO polyether diols with molecular weights (Mw) of 2800 or 40000 (supplied by Covestro). Additionally, AGC Chemicals offers products under the trade name... Diols, such as Preminol S 4013F (Mw 12,000), Preminol 4318F (Mw 18,000) and Preminol 5001F (Mw 4,000).

[0079] Polyester diols obtained by reacting polyols with polyacids are given as examples of polyols. Examples of polyols include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. Examples of polyacids include phthalic acid, dimer fatty acids, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid / anhydride, etc. Preferably, the polyacid is selected such that the resulting polyester polyol is unsaturated.

[0080] These polyester polyol compounds are commercially available under trade names such as: MPD / IPA500, MPD / IPA1000, MPD / IPA2000, MPD / TPA500, MPD / TPA1000, MPD / TPA2000. A-1010, A-2010, PNA-2000, PNOA-1010 and PNOA-2010 (manufactured by Kuraray Co., Ltd.).

[0081] Triols, such as polyester or polyether triols, are also known. Particularly preferred are oligomeric triols having the general formula: A(-----OH)3; where A is a chemical organic structure, such as aliphatic, alicyclic, aromatic, or heterocyclic structure, "-----" is an oligomer chain, such as, to name just a few, a polyether chain, polyester chain, polyhydrocarbon chain, or polysiloxane chain, and "OH" is a terminal hydroxyl group. In one embodiment, the triol comprises, is composed of, or is substantially composed of polyether triols, PO homopolymers, PE homopolymers, PO-EO block copolymers, random copolymers, or hybrid block-random copolymers. In practice, polyether triols may be based on glycerol or trimethylolpropane, PO, EO, or PO and EO copolymers, wherein EO is on a terminal block or an internal block and MW 理论 The molecular weight is approximately 500 g / mol to 15,000 g / mol. Another type of polyether triol is a copolymer based on glycerol or trimethylolpropane, such as THF-PO, THF-EO, THF-PO-EO, or THF-EO-PO, and has a molecular weight between approximately 500 and 15,000. In a preferred embodiment, the triol is derived from bio-based or natural reactants, such as certain vegetable oils and fats.

[0082] Suitable commercial examples of triols include those available from Carpenter. Related propylene oxide-based polyether triols obtained under the GP name include, for example, 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. Other triols are commercially available from Covestro under the following trade names: Brands such as Arcol LHT-240 (molecular weight “Mw” of approximately 700 as stated by the manufacturer), Arcol LHT-112 (Mw 1500), Arcol LHT LG-56 (Mw 3000), and Arcol LHT-42 (Mw 4200); Product names, such as Multranol 9199 (Mw 4525), Multranol 3900 (Mw 4800), Multranol 3901 (Mw 6000), and Multranol 9139 (Mw 6000); and product names... Those include, for example, Acclaim 703 (Mw 700), Acclaim 3300N (Mw 3000), Acclaim 6300 (Mw 6000), and Acclaim 6320 (Mw 6000). Additionally, AGC Chemicals offers products under the trade name... Triols, such as Preminol S3011 (Mw 10,000), Preminol 7001K (Mw 7,000) and Preminol 7012 (Mw 10,000).

[0083] The theoretical molecular weights derived from the number of hydroxyl groups in these polyols are typically from about 50 to about 15,000, preferably from about 500 to 12,000, or from about 1,000 to about 8,000.

[0084] The reaction products of (multi) isocyanate compounds, preferably diisocyanate compounds, can be used to generate urethane groups or segments in reactive urethane oligomers according to a first aspect of the 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 include diisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, (hydrogenated)benzene dimethyl diisocyanate, 1,3-benzene dimethyl diisocyanate, 1,4-benzene dimethyl 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, methylene bis(4-cyclohexyl)isocyanate, etc. (Cyanide esters), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, 2,4-methylene dicyclohexyl diisocyanate and / or 4,4′-methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, tetramethylxylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanate-ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated phenyl dimethyl diisocyanate, tetramethylphenyl dimethyl diisocyanate, lysine isocyanate, etc.

[0085] These diisocyanate compounds can be used alone or in combination of two or more. In various embodiments, the diisocyanates include isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, 2,4-toluene diisocyanate, and / or 2,6-toluene diisocyanate (mixtures of the above two diisocyanates are commercially available under the common name "TDI"). Particularly preferred diisocyanates include trimethylhexamethylene diisocyanate (TMDI) compounds and isophorone diisocyanate (IPDI) compounds.

[0086] As used herein, “polyisocyanate” refers to an isocyanate compound having two or more isocyanate segments per molecule. In one embodiment, the oligomer component comprises, is substantially composed of, or is composed of urethane oligomers as reaction products of one or more polyisocyanates. In addition to the diisocyanates described above, polyisocyanates having three isocyanate groups per molecule, i.e., triisocyanates, may also be used. Known triisocyanates include biuret made from hexamethylene diisocyanate (HDI) or HDI trimer, which is available from Covestro under the trade name Commercially acquired, 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 XP2599, Desmodur XP2675, Desmodur XP2731, Desmodur XP 2714 and Desmodur XP 2803.

[0087] Other commercially available triisocyanates include those from Evonik for the 2k system. T (IPDI-trimer) and HT (HDI-trimer) series of polyisocyanate crosslinking agents.

[0088] In one embodiment, the reactive urethane oligomer further comprises the reaction product of an isocyanate-reactive (meth)acrylate. Any suitable (meth)acrylate, including monomers and oligomers, can be used, but (meth)acrylate monomers are preferred. Such isocyanate-reactive (meth)acrylates preferably comprise hydroxyl-containing (meth)acrylate compounds, as such compounds are known to react with isocyanates, including polyisocyanates. Examples of hydroxyl-containing (meth)acrylates include (meth)acrylates derived from (meth)acrylic acid and epoxy groups and (meth)acrylates containing epoxides, more specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and hydroxyethylcaprolactone acrylate, ethoxylated trimethylolpropane diacrylate, glycerol di(meth)acrylate and glycerol acrylate methacrylate (i.e., 3-(acryloyloxy)-2-hydroxypropyl methacrylate).

[0089] In one embodiment, the urethane oligomer further comprises the reaction product of a nonfunctional end-capping agent. Such compounds, when reacted into oligomers via (poly)isocyanate compounds and / or isocyanate-reactive (meth)acrylates, form distal termination points along at least one arm or chain of the urethane oligomer, where otherwise no polymerizable groups appear along that arm or chain. The nonfunctional end-capping agent may comprise non-UV-curable compounds having active hydrogen groups, such as compounds containing thiol groups (-SH), amino groups (-NH2), and hydroxyl groups (-OH).

[0090] In a preferred embodiment, the urethane oligomer comprises the reaction product of a monohydric alcohol that does not have a (meth)acrylic acid segment. Such compounds preferably react with the aforementioned (poly)isocyanate. The monohydric alcohol that does not have a (meth)acrylic acid segment can be used to end-cap the oligomer with a hydroxyl group, thereby making the arm or chain non-polymerizable.

[0091] In one embodiment, the monohydric alcohol compound lacking the (meth)acrylic acid segment is an aliphatic compound, such as a C1-C1 compound lacking the (meth)acrylic acid segment. 18 or C2-C 12 or C4-C 10 Straight-chain or branched monohydric alcohols.

[0092] Any suitable monohydric alcohol that does not contain a (meth)acrylic acid fragment can be used, but in a preferred embodiment, the monohydric alcohol that does not contain a (meth)acrylic acid fragment comprises, is composed of or is substantially composed of methanol, ethanol, isopropanol, butanol, pentanol, 2-ethylhexanol, cetyl alcohol, allyl alcohol, geraniol, propargyl alcohol, inositol, menthol, or any combination thereof.

[0093] In the reaction of the components used to generate urethane oligomers, one or more urethane esterification catalysts are also preferably used. For example, such catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, and triethylenediamine-2-methyltriethyleneamine. The catalyst can be used in any suitable amount, or for example, from about 0.01% to about 1% by weight of the total reactants. The reaction can be carried out at any suitable temperature, for example, between 10°C and 150°C, or from about 10°C to about 90°C, or from about 30°C to about 80°C.

[0094] In one embodiment, the urethane oligomer includes a bifunctional reactive urethane oligomer. As used herein, bifunctional means having an average of 1.5 to 2.5 polymerizable groups per molecule, as determined by nuclear magnetic resonance spectroscopy (NMR). However, in other embodiments, the oligomer component comprises, is substantially composed of, or is composed of a trifunctional reactive urethane oligomer, or an oligomer having an average of more than 2.5 to 3.5 polymerizable groups per molecule. In another embodiment, the oligomer component comprises a tetrafunctional oligomer, or those oligomers having an average of more than 3.5 to 4.5 polymerizable groups per molecule. In a preferred embodiment, the oligomer component comprises, is substantially composed of, or is composed of one or more reactive urethane oligomers with 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 oligomer component is between 1.5 and 4.2, or between 1.8 and 3.8, or between 1.8 and 3.2, or between 1.8 and 2.8.

[0095] One or more of the above-described reactive polyurethane oligomers may be used in any suitable amount in the compositions according to the invention, and may be selected individually or in combination of one or more types listed herein. Therefore, in one embodiment, the oligomer component or reactive urethane oligomer is present in an amount of less than 65% by weight, or 10-65% by weight, or 10-55% by weight, or 10-50% by weight, or 10-40% by weight; or 15-65% by weight, or 15-55% by weight, or 15-50% by weight, or 15-40% by weight; or 20-65% by weight, or 20-55% by weight, or 20-50% by weight, or 20-40% by weight; or 25-65% by weight, or 25-55% by weight, or 25-50% by weight, or 25-40% by weight; or 30-65% by weight, or 30-55% by weight, or 30-50% by weight, or 30-40% by weight, relative to the total weight of the composition.

[0096] In one embodiment, at least one of the monomeric component and the oligomeric component is present in the composition. In another embodiment, both the monomeric component and the oligomeric component are present. However, in yet another embodiment, neither the monomeric component nor the oligomeric component is present. In this case, it is preferable that the desired properties and functionality of the optical fiber coating, typically imparted by the monomers and oligomers as described herein, are otherwise primarily satisfied by the self-healing components further described below.

[0097] Self-repairing components

[0098] According to a first aspect, the composition comprises a self-healing component; that is, a collection of one or more individual components having a self-healing fragment. The self-healing component may comprise, consist of, or substantially consist of monomers and / or oligomers having at least one self-healing fragment or group. As used herein, "fragment" and "group" are used interchangeably. A self-healing fragment is a collection of atoms that together promote reversible interactions or covalent reactions with other self-healing fragments in a given composition without explicitly requiring external stimuli, such as the application of radiation energy including UV or heat. Of course, it should be understood that it is still possible for such reversible interactions or covalent reactions to be achieved or even accelerated by external stimuli. Through this process, also known as self-assembly, the self-healing fragment helps enable polymeric materials to self-heal and / or exhibit improved stress relaxation properties. Cured products of compositions containing the self-healing fragments of the present invention need not exhibit a specific minimum degree of self-healing and / or stress relaxation, as it should be understood that the degree of self-healing and / or stress relaxation will vary depending on the specific relevant formulation and the requirements and environmental conditions of the end application.

[0099] However, in a preferred embodiment, in order to generate the required amount of stress relaxation or self-healing at the temperature and timescales required for fiber optic applications, a sufficient amount of self-healing material should be present in the composition from which the fiber coating is derived or cured. The inventors have discovered that self-healing and / or stress relaxation can be optimized when the composition has a sufficient amount of self-healing component and / or when the composition has a self-healing fragment greater than a suitable minimum amount.

[0100] Therefore, according to a first aspect of the invention, the self-healing component is present in an amount greater than 30% by weight relative to the total weight of the composition, and / or the composition has a self-healing fragment of greater than 0.015 equivalents per 100g of the composition. As used herein, the “equivalent” of the self-healing fragment in a given composition is determined by adding the molar amounts of the self-healing fragments in the self-healing component (Z) according to the following expression:

[0101]

[0102] Where Wt = the amount of the corresponding component Z relative to 100g of the total relevant composition by weight; N = the number of self-repairing fragments present in one molecule of component Z; and MM is the theoretical molecular weight of component Z.

[0103] If the complete formulation of the composition is unknown, the equivalent amount of the self-repairing fragment can be determined analytically by any suitable method that should be understood by a person skilled in the art to which this invention is applied, such as size exclusion chromatography (SEC) or nuclear magnetic resonance (NMR).

[0104] In other embodiments, depending on the nature and type of the self-repairing fragment used, the composition contains 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 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents, or 0.02 to 0.1 equivalents. The equivalent amounts may be 0.02 to 0.08 equivalents, or 0.02 to 0.05 equivalents; or 0.022 to 0.15 equivalents, or 0.022 to 0.1 equivalents, or 0.022 to 0.08 equivalents, or 0.022 to 0.05 equivalents, or 0.022 to 0.045 equivalents; or 0.025 to 0.20 equivalents; or 0.037 to 0.15 equivalents, or 0.037 to 0.1 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents. For the avoidance of doubt, unless otherwise stated, all “equivalent” values ​​expressed herein refer to the equivalent amount of the desired fragment (UPy, self-healing, (meth)acrylate, etc.) per 100g of the entire composition.

[0105] Various types of self-healing fragments are known. One class of self-healing fragments contains hydrogen-bonded groups. Hydrogen-bonded groups are those groups that form hydrogen bonds during polymerization or while the composition remains in an uncured liquid state. In one embodiment, the hydrogen-bonded groups are multi-hydrogen-bonded groups. As used herein, a “multi-hydrogen-bonded group” is a group configured to provide at least three hydrogen bonds in a dimer formed from two molecules containing the same or different self-healing fragments. Preferred types of multi-hydrogen-bonded groups include 2-ureido-4-pyrimidinone (UPy) groups. UPy groups or fragments (such terms are used interchangeably herein) are desirable because they are known to be self-complementary and produce strong multi-hydrogen-bonding effects, for example on the order of about 14 kcal / mol, as 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 individual covalent bonds (e.g., carbon-carbon bonds, which are on the order of approximately 100 kcal / mol), but it exceeds the bond dissociation energy of other hydrogen-bonded groups (e.g., NH-O and NH-N, etc.), which are estimated to be between 2 and 8 kcal / mol. Therefore, the UPy fragment can produce a so-called "super" hydrogen-bonded effect. A non-limiting example of the UPy group is 6-methyl-2-ureido-4-pyrimidinone based on the following chemical structure:

[0106]

[0107] The UPy group can form a reaction product that is a precursor of a multi-hydrogen-bonded group. A non-limiting example of such a precursor is 2-amino-4-hydroxy-6-methylpyrimidine, which has the following chemical structure:

[0108]

[0109] The UPy group can be formed as a reaction product of other multi-hydrogen-bonded 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.

[0110] In one embodiment, the self-healing fragment comprises, is composed of, or is substantially composed of polyhydrogen-bonded groups. In one embodiment, the self-healing fragment comprises, is composed of, or is substantially composed of UPy groups. In one embodiment, at least 50%, at least 60%, at least 75%, at least 90%, at least 99%, or 100% of the equivalent amount of the self-healing fragment of the composition is composed of UPy groups.

[0111] Besides the UPy group, other self-healing segments are also known. One class of self-healing segments involves the use of some kind of hydrogen bonding, but not to the extent necessary to be interpreted as “multi-hydrogen bonding” as defined and described above. One such example includes a urea group. The use of urea groups as suitable self-healing segments is known and is described in particular in Applied Materials Today 19(2020)100542. The two hydrogen bonds formed between the two urea groups are responsible for the self-healing properties. The hydrogen bonds between urea groups are weaker than the multi-hydrogen bonding of the UPy segment and are therefore undesirable for use as a self-healing segment for the purposes of this article. Furthermore, monomers and / or oligomers containing urea groups without a large UPy group are difficult to be compatible in fiber optic coating compositions, so in a preferred embodiment, the self-healing component is substantially free of any urea groups except for any urea groups that are substituents for the UPy segment.

[0112] Other self-healing fragments using reversible chemistry that does not involve hydrogen bonding are also known. Examples, such as Diels Alder chemistry, typically require high temperatures to achieve self-healing or stress relaxation behavior, making them less practical for optical coating applications. However, as described in Macromolecules 2011, 44, 2536-2541, it is believed that the weaker covalent bonds inherent in disulfide groups, in particular, promote self-healing and / or stress relaxation behavior in coatings at low temperatures. Indeed, self-healing and / or stress relaxation are the result of exchange reactions occurring in disulfide groups at even milder temperatures.

[0113] Therefore, in one embodiment, the self-healing fragment includes disulfide groups. Such groups are suitable for use in fiber optic coating applications because, if properly controlled, they should not significantly inhibit the radiation curing properties of the associated composition, or otherwise significantly and harmfully affect the physical properties of the coating produced therefrom.

[0114] In various embodiments of the first aspect, the self-repairing component will have at least a first molecule and a second molecule, the first molecule having a first self-repairing fragment and the second molecule having a second self-repairing fragment, wherein the first self-repairing fragment of the first molecule is configured to bond with the second self-repairing fragment of the second molecule. In one embodiment, the bond dissociation energy formed between the first self-repairing fragment and the second self-repairing fragment is between 9 kcal / mol and 100 kcal / mol, or 9 kcal / mol to 80 kcal / mol, or 10 kcal / mol to 50 kcal / mol, or 12 kcal / mol to 50 kcal / mol, or 12 kcal / mol to 90 kcal / mol, or 9 kcal / mol to 30 kcal / mol, or 9 kcal / mol to 20 kcal / mol. Bond dissociation energy can be determined by various suitable methods, non-limiting examples of which can be found by summarizing the direct addition of all bonds in the self-repairing fragment according to Table 1 of The Scientific World Journal (2004) 4, 1074-1082; and Nature 2002, Vol. 3, 836-847. However, in practice, due to cooperation, the bond dissociation energy may actually be higher than the value obtained due to direct addition.

[0115] The first and second self-repairing segments may be different, but in a preferred embodiment they are identical. In one embodiment, the first and second self-repairing segments are identical and configured to dimerize. Dimerization is an addition reaction in which two molecules of the same compound react with each other to form an adduct. In the formation of the dimer, the two molecules will align to preferably form multiple hydrogen bonds. In a preferred embodiment, the dimer will have at least three, or at least four, or three to four hydrogen bonds. In one embodiment, the formed dimer will also comprise a first straight chain connected to each hydrogen bond on one side of the first self-repairing segment, and a second straight chain connected to each of three or four hydrogen bonds on one side of the second self-repairing segment, wherein each of the first and second straight chains contains fewer than seven covalent bonds. Some non-limiting examples of such dimer configurations of the UPy segment having four hydrogen bonds and six adjacent covalent bonds on either side of the hydrogen bonds are depicted in the following structures (I) through (IV):

[0116]

[0117]

[0118] Similarly, a non-limiting example of such a dimer configuration of the UPy segment having 3 hydrogen bonds and 4 adjacent covalent bonds on either side of said hydrogen bonds is depicted in the following structure (V):

[0119]

[0120] As can be seen from structures (I) to (V) above, the dimer may also have a cyclic or fused-ring structure. In various embodiments, for each of structures (I) to (V), R may be selected from organic substituents that optionally contain a reactive group attached thereto. In one embodiment, the reactive group includes acryloyloxy, methacryloxy, hydroxyl, amino, vinyl, alkynyl, azide, azircyclopropyl, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, azircyclopropyl, carboxylate, hydrogen, F, Cl, Br, I, or maleimide.

[0121] In one embodiment, the self-repairing component comprises, consists of, or is substantially composed of self-repairing fragments configured to dimerize according to any of the structures (I), (II), (III), (IV) and / or (V) as described above.

[0122] The complete molecular structure incorporating the self-healing fragment can be of any suitable type. However, in one embodiment, the self-healing fragment is incorporated into a monomer or oligomer, including types listed elsewhere herein, ibid. In a preferred embodiment, the self-healing fragment is incorporated into a reactive urethane oligomer. Such oligomers (which are also specifically described elsewhere herein, ibid.) can be utilized and constructed in a manner similar to that described above, and the self-healing fragment can also be added thereto via known reaction mechanisms to obtain a structure incorporated into the self-healing component. In embodiments in which the UPy group is constructed into the urethane oligomer as described elsewhere herein, the diisocyanate used may comprise, consist of, or consist substantially 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 the precursor with the UPy group and some other diisocyanate compounds (e.g., hexamethylene diisocyanate) may produce a solid product at room temperature. This tends to make the synthesis of overall oligomers more expensive and / or difficult, especially on a commercial scale.

[0123] Due to the natural tendency of self-healing fragments to self-assemble and / or dimerize, conventional small-molecule or oligomers containing self-healing fragments exhibit poor solubility and / or miscibility, including poor solubility and / or miscibility with other monomers and / or oligomers commonly found in coatings. To increase their solubility, the molecular weight of the oligomers can be increased, as disclosed in Progress in Organic Coatings 113 (2017) 160-167. However, in this case, the concentration of the self-healing fragments will inevitably decrease to a level that adversely affects the self-healing and / or stress relaxation effects to the point that these effects may become insufficient for the requirements and conditions in various applications, including fiber optic coatings. Furthermore, conventional self-healing components typically require large amounts of solvent for synthesis and often result in crystalline or solid materials with high melting points or glass transition temperatures (Tg). Therefore, conventional selection of self-healing components has been limited to those with poor solubility, low self-healing fragment content, and / or those requiring large amounts of solvent for synthesis.

[0124] The inventors have surprisingly discovered that many of the self-healing oligomers described herein, such as those containing at least three urethane bonds, tend to produce oligomers with lower viscosity values ​​and / or greater processability in fiber optic coating applications, thereby avoiding the need for process-impeding solvents and enabling the use of increased self-healing content in associated fiber optic coating compositions. The addition of a significant amount of self-healing component is important for promoting the formation of formulations suitable for the production of self-healing and / or stress-relaxed fibers that are easily processable in the production of coated optical fibers.

[0125] As described above, in various embodiments, it is desirable to minimize the use of solvents. The inclusion of solvents is undesirable because such agents tend to introduce processing difficulties and / or safety issues into fiber optic coating applications. To name just a few, several non-limiting examples of commonly used solvents include 2-propanol, acetone, acetonitrile, chloroform (CHCl3), dichloromethane, dimethyl sulfoxide ((CH3)2SO), ethyl acetate, hexane, methanol, tetrahydrofuran, toluene, propylene glycol, methyl ethyl ketone, and water. To distinguish them from reactive diluents commonly used in UV-curable compositions, for the purposes of this document, a reagent having one or more acrylate or methacrylate functional groups is not considered a solvent. The presence of these compounds can be determined by any suitable method, such as size exclusion chromatography (SEC) and HPLC; water is also readily quantified by Karl Fischer titration. The self-healing components according to aspects of the invention promote the minimization or elimination of such agents, which are further not used to promote the curing, self-healing properties, or physical characteristics required for many optical fibers. Therefore, 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.

[0126] Regardless of the foregoing, in one embodiment, the self-healing component comprises, is composed of, or is substantially composed of one or more compounds according to the following structure (VI):

[0127] [A(G) n -D m ]-[A(G) n-1 -D m ] k -Z (VI);

[0128] in

[0129] A is either carbon or nitrogen;

[0130] Where A is sp3 carbon, n = 3, and when A is sp2 carbon or nitrogen, n = 2;

[0131] m is an integer from 0 to 500;

[0132] k is a number between 0 and 20;

[0133] For each occurrence of m, D is independently selected from the following divalent spacer groups: -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)-; -C(T)=N-; -C(T)=; -N=; or combinations thereof;

[0134] in

[0135] For each instance of a single-bond D, the single-bond is concatenated with it, and for each instance of a double-bond D, the double-bond is concatenated with it.

[0136] in

[0137] For each occurrence, each T is selected from a monovalent unit, including hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl;

[0138] Each T can also be selected from divalent D. m And connected to another one also selected from D m The divalent T forms a ring structure; and

[0139] And i is an integer from 1 to 40;

[0140] Each group in each unit of m, n, and k can be the same or different;

[0141] Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, F, Cl, Br, I, or maleimide group; and

[0142] For each occurrence of n, G is independently selected from hydrogen, -D m -Z, or a self-repairing fragment based on the following structure (VI-b):

[0143] (ZD m ) j XD m - (VI-b);

[0144] in

[0145] X is a polyhydrogen-bonded group or a disulfide group;

[0146] j = 1 when X is divalent, and j = 0 when X is monovalent;

[0147] For at least one occurrence of n, G is a self-repairing fragment based on the structure (VI-b).

[0148] In one embodiment, X comprises, is composed of, or is substantially composed of a disulfide group. In a preferred embodiment, X is a 2-ureido-4-pyrimidinone group (UPy), and j = 0. The UPy group can be a reaction of any suitable compound, but in one embodiment, it comprises the reaction product of 2-amino-4-hydroxy-6-methylpyrimidinium. In one embodiment, X comprises, is composed of, or is substantially composed of the following structure (VI-c):

[0149]

[0150] Where D, m, and Z are as defined above with respect to structure (VI), and R represents the remaining fragment of structure (VI).

[0151] In some embodiments, D comprises a urethane group, wherein the urethane group is a reaction product of a diisocyanate compound. In some embodiments, D additionally or alternatively comprises a polyol component. The polyol component can 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 have been described elsewhere above, citing the same source.

[0152] In some embodiments, Z comprises (meth)acrylate groups. Such functional groups will enable the molecules according to structure (VI) to polymerize in a manner consistent with many current conventional fiber optic coatings.

[0153] In one implementation, the self-healing component comprises, is composed of, or is substantially composed of theoretical molecular weight (MW). 理论The molecular composition is between 500 g / mol and 100,000 g / mol. In a preferred embodiment, the self-repairing component comprises, is composed of, or is substantially composed of molecules according to structure (VI), said molecules further having a molecular composition between 500 and 8000; or between 500 and 5000; or between 500 and 4000; or between 500 and 3000; or between 500 and 2000; or between 500 and 1500; or between 500 and 1000; or between 500 and 900; or between 500 and 700; or between 700 and 4000. The theoretical molecular weight (MW) is 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. 理论 (in g / mol).

[0154] Depending on the application requirements, it may be important to tune the self-healing component to maximize its effectiveness in promoting self-healing properties and / or stress relaxation behavior at a specific temperature. For compositions that most effectively impart self-healing properties and / or stress relaxation behavior at room temperature, it may be preferable, for example, to tune the composition such that the glass transition temperature (Tg) of the self-healing component is below room temperature. Indeed, although not mandatory, it is preferred that the self-healing component comprises, is composed of, or is substantially composed of molecules having a Tg value below the temperature required to achieve self-healing and / or stress relaxation capabilities. In this way, any oligomers with self-healing segments, for example, do not crystallize at the operating temperature (or have entered the glassy state for amorphous materials), thereby maximizing the ability of the self-healing segments to self-assemble, dimerize, bind together, or otherwise interact in a manner required to achieve self-healing and / or stress relief.

[0155] Therefore, in one embodiment, the self-healing components and / or molecules according to the above structure (VI) have a glass transition temperature (Tg) 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 -30°C to 20°C, or -25°C to 20°C, or -20°C to 10°C. All other things being equal, a lower glass transition temperature tends to be preferred because, theoretically, they will promote self-healing and / or stress relaxation capabilities over a wider operating temperature range.

[0156] Regardless of the nature of the self-healing fragments or their associated overall structure, the self-healing component optionally comprises, is composed of, or is substantially composed of molecules that also have polymerizable fragments. If such polymerizable fragments are present, the molecules in the self-healing component can therefore undergo polymerization and / or cross-linking reactions with other molecules in the self-healing component and with those molecules in the optional monomer and / or oligomer components. In this way, the self-healing component will enable bonding to achieve a “permanent” assembly of cross-linked polymer chains to impart the desired physical properties to the fiber coating, as well as “reversible” interactions or covalent bonds that promote its self-healing and / or stress relaxation. The polymerizable segment may contain radiation-curable, heat-curable, or radiation-curable and heat-curable segments, such as, but not limited to, acryloyloxy, methacryloxy, hydroxyl, amino, vinyl, alkynyl, azide, aziridine, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, hydrogen, F, Cl, Br, I, or maleimide groups.

[0157] Preferably, the polymerizable segment of the self-healing component contains a radiation-curable segment, such as an acrylate or methacrylate group.

[0158] The inventors have also discovered that maintaining the amount of polymerizable groups in the self-healing component within a specific range improves the effectiveness and usability of the self-healing coating for optical fibers. Therefore, in one embodiment, the self-healing component has polymerizable fragments and / or (meth)acrylate groups in amounts of 0.015 to 0.1 equivalents, or 0.03 to 0.1 equivalents, or 0.037 to 0.1 equivalents, or 0.03 to 0.08 equivalents, or 0.03 to 0.05 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents per 100g of the composition.

[0159] In a broader context, regardless of whether such polymerizable fragments are included in the self-healing component, the inventors have found that this can also help control the amount of polymerizable fragments in the entire composition. Therefore, in one embodiment, the composition has 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 polymerizable fragments and / or (meth)acrylate groups per 100g of the composition.

[0160] Furthermore, the inventors have discovered that this can also help tune the relative amounts of self-healing and polymerizable segments. Without being bound by any theory, it is believed that an excessive number of polymerizable segments relative to the self-healing segments may result in a highly cross-linked cured product that does not promote sufficient internal redirection of the relatively scarce self-healing groups for self-assembly or contact with each other to impart repair. Conversely, if an insufficient number of polymerizable groups are present, the composition will not cure sufficiently (or will not cure fast enough), making such compositions unsuitable for processing in fiber coating operations and / or increasing the likelihood that the resulting cured coating will have insufficient mechanical properties.

[0161] Therefore, in one embodiment, the composition has an equivalent ratio of polymerizable groups to self-healing groups of less than 14, or less than 10, or less than 8, or less than 6, or less than 5, or is 1 to 14, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5, or 3 to 10, or 3 to 8, or 3 to 5, wherein the self-healing groups preferably comprise, are composed of, or are substantially composed of UPy groups. In a preferred embodiment, the above ratio applies to cases where the polymerizable groups comprise, are composed of, or are substantially composed of (meth)acrylate groups and the self-healing fragment comprises, is composed of, or is substantially composed of UPy groups.

[0162] The self-healing component may be present in any suitable amount, but in various embodiments it 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 relative to the total composition.

[0163] Initiator components

[0164] According to a first aspect, the composition includes an initiator component; that is, a collection of one or more individual initiators having one or more specified structures or types. An initiator is a compound that undergoes a chemical change due to the action of some external stimulus (e.g., heat or light) to generate at least one of a free radical, an acid, or a base. Initiators can be used to promote polymerization reactions through a variety of mechanisms, including free radical polymerization and cationic polymerization. In a preferred embodiment, the initiator component comprises, is composed of, or is substantially composed of an initiator that promotes free radical polymerization; that is, it comprises, is composed of, or is substantially composed of a free radical initiator.

[0165] In one embodiment, the composition comprises, consists of, or is substantially composed of one or more photoinitiators. A photoinitiator is a compound that undergoes a chemical change due to the action of light or in synergy between the action of light and the electronic excitation of a sensitized dye, preferably to promote polymerization reactions in the associated composition. Well-known types of photoinitiators include cationic photoinitiators and free radical photoinitiators. According to one embodiment of the invention, the photoinitiator comprises, consists of, or is substantially composed of a free radical photoinitiator.

[0166] In one embodiment, the photoinitiator component comprises, is composed of, or is substantially composed of one or more acylphosphine oxide photoinitiators. Acylphosphine oxide photoinitiators are known and 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 the photoinitiator component include bisacylphosphine oxide (BAPO) or monoacylphosphine oxide (MAPO). More specifically, examples include 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (CAS No. 84434-11-7) or 2,4,6-trimethylbenzoyldiphenylphosphine oxide (CAS No. 127090-72-6).

[0167] The photoinitiator component may optionally comprise, consist of, or be substantially composed of an α-hydroxyketone photoinitiator. Suitable α-hydroxyketone photoinitiators include α-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-prop-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)phenyl]propanone.

[0168] In another embodiment, the photoinitiator component comprises, is composed of, or is substantially composed of: α-amino ketones, 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; benzophenones, such as benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2-methylbenzophenone, 2-methoxycarbonylbenzophenone, 4, 4′-bis(chloromethyl)-benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 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, such as 2,2-dimethoxy-1,2-diphenyl-ethyl ketone; and monomeric or dimer phenyl glyoxylates, such as methyl phenyl glyoxylate, 5,5′-oxo-di(ethyleneoxydicarbonylphenyl) or 1,2-(benzoylcarboxyl)ethane.

[0169] Further suitable photoinitiators for the photoinitiator component include oxime esters, such as those disclosed in U.S. Patent No. 6,596,445. Another class of suitable photoinitiators for the photoinitiator component includes, for example, phenyl glyoxylate, such as those disclosed in U.S. Patent No. 6,048,660.

[0170] In another embodiment, the photoinitiator component may comprise, consist of, or consist substantially of one or more alkyl, aryl, or acyl compounds not mentioned above herein.

[0171] According to another embodiment, the composition may comprise a photoinitiator, which is an alkyl, aryl, or acyl-substituted compound. In one embodiment, the alkyl, aryl, or acyl-substituted photoinitiator has or is centered on an atom from Group 14 (carbon group). In this case, upon excitation (by absorbed radiation), the Group 14 atom present in the photoinitiator compound forms a free radical. Thus, such a compound can generate an atom or a group centered on 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 hereby incorporated by reference. Specific known acylgermanium photoinitiators include benzoyl trimethylgermane (BTG), tetraacylgermane, or diacylgermane (available from Ivoclar Vivadent AG, 9494 Schaan / Liechtenstein as...). (Originated through commercial purchase).

[0172] The photoinitiators according to the invention can be used alone or in combination of one or more as blends. 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, for example, a photoinitiator blend of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (CAS No. 162881-26-7) and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (CAS No. 84434-11-7) in a weight ratio of about 1:11, 1:10, 1:9, 1:8, or 1:7.

[0173] Another particularly suitable photoinitiator blend is 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, for example, about 3:1:15, 3:1:16, 4:1:15, or 4:1:16. Another suitable photoinitiator blend is a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone in a weight ratio of, for example, about 1:3, 1:4, or 1:5.

[0174] In one embodiment, the composition may comprise a thermal initiator. In a preferred embodiment, the thermal initiator comprises, is composed of, or is substantially composed 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(cyclohexanonitrile), 1,1′-azobis(2,4,4-trimethylpentane), CC unstable compounds (e.g., benzopinacole), peroxides, and mixtures thereof.

[0175] In one embodiment, the thermal initiator comprises a peroxide. Suitable peroxides may include organic and inorganic peroxides. In one embodiment, the thermal initiator is soluble in the composition.

[0176] Examples of peroxides include, for example, percarbonate (formula -OC(O)O-), peroxyester (formula -C(O)OO-), diacyl peroxide (also known as peracid anhydride) (formula -C(O)OOC(O)-), dialkyl peroxide or perether (formula -OO-), hydroperoxide (formula -OOH), etc. Peroxides can also be oligomers or polymers in nature.

[0177] Thermal free radical polymerization initiators can include, for example, percarbonates, peresters, or peranhydrides. Examples of peranhydrides include benzoyl peroxide (BPO) and lauroyl peroxide (as Laurox). TM (Commercially available). Peresters include, for example, tert-butyl perbenzoate and 2-ethylhexyl perlaurate. Percarbonates include, for example, di-tert-butyl percarbonate and di-2-ethylhexyl percarbonate or monopercarbonate.

[0178] One or more of the aforementioned initiators can be used in any suitable amount in the initiator component of the composition according to the first aspect of the invention, and can be selected individually or in combination of one or more types listed herein. In a preferred embodiment, the initiator component comprises, consists of, or is substantially composed 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 about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 5 wt%, or about 1 wt% to about 5 wt%, relative to the total weight of the composition.

[0179] additive

[0180] The compositions according to the invention optionally comprise additive components; that is, a collection of one or more individual additives having one or more specified structures or types. Additives are also typically added to optical fiber coatings to achieve certain desired properties, such as improved adhesion to glass optical fibers, improved shelf life, improved coating oxidation and hydrolytic stability, etc. Many different types of desired additives exist, and the invention discussed herein is not intended to be limited to these; however, they are included in the intended embodiments because of their desired effects.

[0181] Exemplary additives used in additive components include thermal inhibitors designed to prevent premature polymerization, examples of which are hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol, or sterically hindered phenols such as 2,6-bis(tert-butyl)-p-cresol. Shelf life in the dark can be extended, for example, by using copper compounds (e.g., copper naphthenate, copper stearate, or copper octanoate), phosphorus compounds (e.g., triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite, or tribenzyl phosphite), or quaternary ammonium compounds (e.g., tetramethylammonium chloride or trimethylbenzylammonium chloride).

[0182] To prevent atmospheric oxygen from entering during polymerization, additives such as paraffin or similar waxy substances can be added; these substances migrate to the surface at the start of polymerization due to their low solubility in the polymer and form a transparent surface layer that prevents air from entering. An oxygen barrier layer can also be applied.

[0183] Other potentially suitable additives include light stabilizers. Light stabilizers include UV absorbers, such as well-known commercial UV absorbers of the hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide, or hydroxyphenyl-s-triazine type. In the case of using or not using sterically hindered relatively non-basic amine light stabilizers (HALS), such compounds alone or mixtures thereof may be used. Steric hindered amines are, for example, based on 2,2,6,6-tetramethylpiperidine. UV absorbers and sterically hindered amines include, for example, the following:

[0184] 2-(2-Hydroxyphenyl)-2H-benzotriazole, such as the known commercial hydroxyphenyl-2H-benzotriazole and benzotriazole disclosed in the following U.S. Patent Numbers: 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315 ,848;4,347,180;4,383,863;4,675,352;4,681,905;4,853,471;5,268,450;5,278,314;5,280,124;5,319,091;5,410,071;5,436,349;5,516,914;5,554,760;5,563,242;5,574,166;5,607,987;5,97 7,219; and 6,166,218, for example 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy- 5-Methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,2-(3-Dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonyl)ethylphenyl)-2H-benzotriazole, dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2 -(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazole-2-yl)phenol), 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-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-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazole- Methyl 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

[0185] Another exemplary category includes 2-hydroxybenzophenone, such as 4-hydroxy derivatives, 4-methoxy derivatives, 4-octoxy derivatives, 4-decoxy derivatives, 4-dodecoxy derivatives, 4-benzyloxy derivatives, 4,2′,4′-trihydroxy derivatives, and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0186] Another exemplary category includes esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid.

[0187] Additional additives suitable for the additive components include compounds that accelerate photopolymerization, such as so-called photosensitizers, which shift or broaden the spectral sensitivity of the compositions in which they are incorporated. Photosensitizers particularly include aromatic carbonyl compounds, such as benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, and 3-acylcoumarin derivatives, as well as 3-(aromaticylmethylene)thiazoline, and eosine, rhodamine, and erythrosine dyes. Alternatively, non-aromatic carbonyl compounds can be used. An example of a non-aromatic carbonyl compound is dimethoxyanthracene.

[0188] The curing process can be aided, in particular, by the use of additives that generate or promote the formation of the coloring composition. Such additives include pigments, such as titanium dioxide, and also include additives that form free radicals under thermal conditions, such as azo compounds like 2,2′-azobis(4-methoxy-2,4-dimethylpentanonitrile), triazene, diazosulfides, pentazadiene; or peroxides, such as hydroperoxides or percarbonates, such as tert-butyl hydroperoxide, as described in U.S. Patent No. 4,753,817. Other suitable substances for this purpose include benzylpinacol compounds.

[0189] The additive components may include photoreducible dyes, such as xaton, benzoxaton, benzothiol, thiazine, pyrrolidine, 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.

[0190] Depending on the intended application, other conventional additives may be used. Examples include optical brighteners, fillers, pigments, dyes, wetting agents, or leveling agents. Thick, colored coatings may also contain glass microspheres or powdered glass fibers, as described, for example, in U.S. Patent No. 5,013,768.

[0191] In one embodiment, the additive component includes one or more of a variety of additives for enhancing one or more properties of the primary coating. Such additives include antioxidants (e.g., Irganox 1035, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or tert-butylhydroquinone), adhesion promoters, inhibitors (e.g., acrylic acid), photosensitizers, carrier surfactants, tackifiers, catalysts, stabilizers, surface agents, and fluorescent whitening agents.

[0192] In a preferred embodiment, the additive component comprises, is composed of, or is substantially composed of one or more adhesion promoter compounds. The adhesion promoter provides bonding between the polymer primary coating and the surface of the optical glass fiber. Hydrolyzable silane coupling agents are commonly used as glass adhesion promoters. Silane coupling agents are particularly described in U.S. Patent No. 4,932,750. In one embodiment, the adhesion promoter is a hydrolyzable silane compound containing a thiol group and / or multiple alkoxy groups. Such adhesion promoters are known and described in U.S. Patent Application No. 20020013383, the relevant portion of which is incorporated herein by reference.

[0193] In one embodiment, the adhesion promoter includes one or more of γ-mercaptopropyltrimethoxysilane, trimethoxysiliylpropyl acrylate, or 3-trimethoxysiliylpropane-1-thiol.

[0194] Silane coupling groups—or any other adhesion-promoting groups—are not used as independent compounds in the additive component, but may instead react with other components (e.g., oligomers, monomers, or even self-healing components). For the purposes of understanding this document, in this case, they will not be considered as additives, but rather as part of the corresponding components with which they have reacted. Thus, in one embodiment, the composition contains adhesion-promoting functional groups as part of an oligomer component, monomer component, or self-healing component.

[0195] One or more of the above-described additives may be used in the compositions according to the invention in any suitable amount, and may be selected individually or in combination of one or more types listed herein. In a preferred embodiment, the additive components are present in amounts 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, relative to the total weight of the composition; 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, relative to the total weight of the composition.

[0196] It is desirable that the compositions according to the first aspect of the invention do not contain additives or components that tend to inhibit polymerization and / or self-assembly reactions. Specifically, it is desirable that the compositions remain substantially free of agents that tend to inhibit free radical polymerization or hydrogen bonding. Those skilled in the art will understand that such components may include so-called superacids and / or superbases.

[0197] The composition according to the first aspect of the invention can be tuned such that different amounts of the aforementioned components can be contained in different amounts relative to each other. In one embodiment, the monomeric and / or oligomeric components are present in amounts of 10 wt% to 65 wt%, or 10 wt% to 55 wt%, or 10 wt% to 50 wt%, or 10 wt% to 40 wt%, or 10 wt% to 30 wt%; or 20 wt% to 65 wt%, or 20 wt% to 55 wt%, or 20 wt% to 50 wt%, or 20 wt% to 40 wt%; the self-healing component is present in amounts greater than 30 wt% to 100 wt%, or greater than 30 wt% to 75 wt%. The components are present in amounts of 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 initiator is present in amounts of 0.01% to 10% by weight, or 0.05% to 5% by weight, or 0.1% to 3% by weight; and the additives are present in amounts of 0% to 59.99% by weight; wherein the total amount of all components in the said components is 100% by weight.

[0198] For suitability for typical fiber optic coating applications, the composition should have a specific viscosity value. This viscosity can be tuned as needed according to methods well-known in the applicable field, particularly by incorporating various types of reactive diluent monomers or oligomers. Furthermore, as explained elsewhere herein, certain self-healing components, such as those having three or more, or four or more urethane bonds, and / or those according to structure (VI), can surprisingly enhance viscosity and / or solubility properties to make the associated formulations suitable for fiber optic coating applications, while still possessing a sufficient number of self-healing segments to impart the desired self-healing properties and / or stress relaxation behavior to the thus cured coating. Therefore, in one embodiment, such as at 50s… -1 The composition has a viscosity of less than 40 Pa·s, or less than 30 Pa·s, or less than 15 Pa·s, or less than 10 Pa·s, or less than 1 Pa·s, or 1 Pa·s to 20 Pa·s, or 1 Pa·s to 15 Pa·s, or 1 Pa·s to 10 Pa·s, or 0.05 Pa·s to 5 Pa·s, or 0.05 Pa·s to 1 Pa·s, as measured at a shear rate and at a temperature of 25°C.

[0199] As discussed, compositions according to the invention can possess self-healing properties and / or stress relaxation behavior. In various embodiments, it is desirable to formulate compositions exhibiting measurable self-healing properties. It is often not feasible to directly measure the magnitude of the self-healing efficacy of any coating in its pre-cured liquid state. Therefore, it is preferable to determine the self-healing efficacy of the composition by measuring certain physical properties of the resulting cured product. Specifically, the self-healing capability can be assessed by treating a fixed amount of uncured composition according to predetermined, fixed-set curing conditions, and then by measuring certain physical properties after initial curing, and then at a subsequent time after the cured product has been damaged in a controlled manner and allowed to self-heal for a period of time.

[0200] In one implementation, self-healing can be visually observed, for example, through a qualitative assessment of the disappearance of cavitation over time. Visual detection of cavitation is described in particular in, for example, US7067564, assigned to DSM IP Assets BV, the relevant portions of which are incorporated herein by reference.

[0201] The efficacy of self-repair behavior can also be observed by subjecting any composition according to any embodiment of this first aspect to 1 J / cm² of radiation from a radiation source emitting a peak spectral output of 360 nm–400 nm. 2A dose of energy is used to cure the composition into a 3-mil film, which is then configured to repair to a visually detectable degree within a time period of no more than 8 hours, preferably no more than 1 hour, preferably no more than 5 minutes, or preferably no more than 1 minute, while the film is maintained at a temperature of 55°C, preferably 25°C, wherein the repair of the film is visually determined by microscopic imaging at 40x or 100x magnification. In other embodiments, the above test can alternatively be constructed by applying and curing a composition containing self-healing components onto fibers or wires to more closely simulate the geometry and load in which the resulting self-healing coating would operate in the coated optical fiber.

[0202] In other embodiments, the self-healing properties of the composition can be determined in other ways, for example, by comparing the physical properties of the cured product before and after the coating has undergone a controlled destructive event. The controlled destructive event can be, in particular, cavitation, tearing, or cutting into the cured product (e.g., a film) induced by a controlled specified process. In one embodiment, the controlled destructive event is a cutting process, thereby... Figure 1 The orientation shown cuts through a substantially flat film formed by the coating, having a substantially rectangular cross-section and a substantially flat surface, at a 45° angle in the direction toward the substrate. (Example) Figure 1 As shown, cut 1 is made at an angle 2 of 45°; this type of cut can be made with a sufficiently sharp razor. The cut is made by a cutting tool or similar device with 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. The substrate 5 can be made of any suitable material, but in a preferred embodiment, the material is glass. The cut 3 is made such that it is substantially perpendicular to the side surface of the cured film 4, such that the angle 6 is maintained at about 90°.

[0203] In one embodiment, when the composition is cured into a first film and a second film according to the sample preparation method described elsewhere herein, it has the pre-cut tensile strength of the first film and the post-cut tensile strength of the second film, wherein the pre-cut tensile strength and the post-cut tensile strength are measured after the second film has undergone a cutting process as described elsewhere herein and then maintained at a temperature of about 25°C or about 55°C for 12-14 hours; wherein 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.

[0204] The tensile strength before and after cutting described above are preferably measured according to ASTM D638, which, as will be understood by one of ordinary skill in the art to which this invention is applicable, can be modified where applicable to allow for the measurement of softer materials. Specifically, such modifications may include applying a 3-mil thick coating with talc before conditioning overnight at 50 ± 5% relative humidity and 23.0 ± 1.0°C, and cutting the coating into strips 0.5 inches wide. These strips can then be loaded onto a mechanical testing machine equipped with a 2-pound load cell, a crosshead speed of 25.4 mm / min, and a gauge length of 2.00 inches, which can extend the strips until they break.

[0205] The second aspect of the present invention is a self-healing oligomer according to the following structure (VII):

[0206] [UPy-(D m -UD m ) (2+q) ]-[A(G) (n-1) -D m ] k -Z (VII);

[0207] in

[0208] UPy represents the UPy group, where the UPy group is 2-ureido-4-pyrimidinone;

[0209] U represents -NHC(O)E- or -EC(O)NH-, where E is O, NH, N (alkyl) or S;

[0210] 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.

[0211] k is a number from 0 to 20;

[0212] A is selected from carbon and nitrogen;

[0213] n is 2 or 3, where n = 3 when A is sp3 carbon and n = 2 when A is sp2 carbon or nitrogen;

[0214] m is an integer from 0 to 500;

[0215] For each occurrence of m, D is independently selected from the following divalent spacer groups: -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)-, -C(T)=N-, -C(T)=, -N=, or combinations thereof;

[0216] in

[0217] For each instance of a single-bond D, the single-bond is concatenated with it, and for each instance of a double-bond D, the double-bond is concatenated with it.

[0218] in

[0219] For each occurrence, each T is selected from a monovalent unit, including hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl;

[0220] Each T can also be selected from divalent D. m And connected to another one also selected from D m The divalent T forms a ring structure; and

[0221] And i is an integer from 1 to 40;

[0222] Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, F, Cl, Br, I, or maleimide group; and

[0223] For each occurrence of n, G is independently selected from hydrogen, -D m -Z, or a self-repairing fragment based on the following structure (VII-b):

[0224] (ZD m ) j XD m - (VII-b);

[0225] in

[0226] X is a polyhydrogen-bonded group or a disulfide group;

[0227] j = 1 when X is divalent, and j = 0 when X is monovalent.

[0228] The oligomers according to structure (VII) can be used to impart self-healing properties and / or stress relaxation behavior to coatings or compositions incorporating the oligomers. The oligomers can be used in a variety of end-use applications (e.g., coatings, adhesives, build materials for 3D printing applications) or to impart such properties in multilayer optical devices. Such multilayer optical devices may include, but are not limited to, optical films, polarizers, electronic device displays, lighting devices, ophthalmic lenses, microscope lenses, laser lenses, imaging lenses, or fiber optic applications. In a preferred embodiment, the oligomers according to structure (VII) are used in compositions for coating optical fibers. In a preferred embodiment, the fiber coating composition comprises optional reactive monomer and / or oligomer components, a photoinitiator component, and a self-healing component, the self-healing component comprising, being composed of, or substantially composed of the oligomers according to structure (VII).

[0229] As mentioned above regarding the composition of the first aspect, in various embodiments of the second aspect of the invention, wherein the self-healing oligomer according to structure (VII) is accompanied by an associated composition, preferably an optical fiber coating composition, a sufficient amount of self-healing component should be present. Thus, in one embodiment, the self-healing component comprising, or substantially comprising, the self-healing oligomer according to structure (VII) is present in an amount greater than 30% by weight, or greater than 40% by weight, or greater than 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 30% to 100% by weight, or greater than 30% to 90% by weight, or greater than 30% to 80% by weight, or greater than 30% to 70% by weight, or 40% to 100% by weight, or 40% to 80% by weight, or 40% to 70% by weight, or 50% to 100% by weight, or 50% to 80% by weight, or 50% to 75% by weight, relative to the total weight of the associated composition.

[0230] In other embodiments according to the second aspect, the composition associated with the self-healing oligomer according to structure (VII) has a self-healing fragment greater than certain minimum amounts. Since the self-healing oligomer according to structure (VII) has an UPy group as a self-healing fragment, in one embodiment, the composition has an amount greater than 0.015 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 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents per 100g of the composition. Amount, or 0.02 equivalents to 0.1 equivalents, or 0.02 equivalents to 0.08 equivalents, or 0.02 equivalents to 0.05 equivalents; or 0.022 equivalents to 0.15 equivalents, or 0.022 equivalents to 0.1 equivalents, or 0.022 equivalents to 0.08 equivalents, or 0.022 equivalents to 0.05 equivalents, or 0.022 equivalents to 0.045 equivalents; or 0.025 equivalents to 0.20 equivalents; or 0.037 equivalents to 0.15 equivalents, or 0.037 equivalents to 0.1 equivalents, or 0.037 equivalents to 0.08 equivalents, or 0.037 equivalents to 0.05 equivalents of UPy groups.

[0231] The amounts of various components used in formulations associated with the self-healing oligomers according to structure (VII) can be tuned to various amounts to suit the requirements of a particular intended application. However, in one embodiment, the reactive monomer and / or oligomer components are present in amounts of 10 wt% to 65 wt%, or 10 wt% to 55 wt%, or 10 wt% to 50 wt%, or 10 wt% to 40 wt%, or 10 wt% to 30 wt%; or 20 wt% to 65 wt%, or 20 wt% to 55 wt%, or 20 wt% to 50 wt%, or 20 wt% to 40 wt%; and the self-healing component is present in amounts of 30 wt% to 100 wt%, or 30 wt% to 80 wt%. The components are present in amounts of % by weight, or 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 in amounts of 0.01% to 5% by weight, or 0.1% to 3% by weight; and the additives are present in amounts of 0% to 59.99% by weight; wherein the total amount of all components in the components is 100% by weight.

[0232] Similarly, depending on the specific application requirements associated with the self-healing oligomer of structure (VII), the viscosity of the accompanying composition can vary significantly. However, in one embodiment, particularly in embodiments where the self-healing oligomer of structure (VII) is incorporated into the optical fiber coating composition, such as at 50s... -1 The composition, as measured at a shear rate and a temperature of 25°C, should be formulated to have a total viscosity of less than 40 Pa·s, or less than 30 Pa·s, or less than 15 Pa·s, or less than 10 Pa·s, or less than 1 Pa·s, or 1 Pa·s to 20 Pa·s, or 1 Pa·s to 15 Pa·s, or 1 Pa·s to 10 Pa·s, or 0.05 Pa·s to 5 Pa·s, or 0.05 Pa·s to 1 Pa·s. If the viscosity is too low, the fiber coating composition may not adhere properly to the glass fiber during the coating process; conversely, if the viscosity is too high, the coating composition may not be applied to the glass fiber quickly enough at the stretching speed of a conventional fiber coating process.

[0233] One way to tune the viscosity of the composition to a suitable level is to control the molecular weight of the self-healing oligomer according to structure (VII). The inventors have discovered that by formulating the self-healing oligomer according to structure (VII) with a certain number of linked urethane groups, both the viscosity and / or solubility of the self-healing oligomer according to structure (VII) can be maintained to a desired level. Therefore, 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. If the self-healing oligomer according to structure (VII) is configured to have three to four urethane linking groups, the oligomer ideally has a molecular weight (MW) of 500 g / mol to 4500 g / mol, or 1000 g / mol to 4500 g / mol. 理论 On the other hand, if the self-healing oligomer according to structure (VII) has 4 to 5 urethane linking groups, then the oligomer has a molecular weight ratio (MW) of 500 g / mol to 8000 g / mol, or 1000 g / mol to 8000 g / mol. 理论 .

[0234] Regardless of the presence or number of urethane linking groups, in various embodiments, the self-healing oligomer according to structure (VII) has a value 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 7 The theoretical molecular weight (MW) between 00 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. 理论 (in 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 solubility of the self-healing oligomer in the associated composition and / or diluting the content of the self-healing fragment to the extent that the self-healing and / or stress relaxation efficacy 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.

[0235] In a preferred embodiment, the self-healing oligomer UPy according to structure (VII) is represented by either (VIII-a) or (VIII-b):

[0236]

[0237] Where R represents the remainder of structure (VII), and D, m, and Z are as defined above with respect to structure (VII).

[0238] In addition to the specified UPy group, the self-healing oligomer according to structure (VII) may also have additional self-healing groups. These groups may include additional UPy groups, other hydrogen-bonded groups, or other self-healing fragments together, such as disulfide groups as described elsewhere in the text above, ibid. In one embodiment, X is a multi-hydrogen-bonded group or a disulfide group. The aforementioned hydrogen-bonded groups may also be UPy groups.

[0239] Several specific exemplary self-healing oligomers according to structure (VII) may be considered. These exemplary self-healing oligomers include those with linear or branched structures, those with different 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, the following:

[0240]

[0241] Where n is an integer, such that the structure MW 理论 Maintain a concentration between 500 g / mol and 8000 g / mol, preferably between 500 g / mol and 4500 g / mol.

[0242] As can be seen above, the self-healing oligomer according to structure (IX) is linear, having three linked urethane groups (for the purposes of this document, it is assumed that the urethane group adjacent to the UPy group is associated with it), and is capped with an acrylate group at the chain end opposite the UPy group. Other variations thereof may be considered by those skilled in the art to which this invention applies, based on guidelines consistent with those for the self-healing oligomer according to structure (VII).

[0243] Further examples of specific self-healing oligomers according to structure (VII) and the second aspect of the invention include:

[0244]

[0245] Where n is an integer, such that the structure MW 理论 It is maintained between 500 g / mol and 4500 g / mol.

[0246] Further specific examples of self-healing oligomers according to structure (VII) include branched structures, such as one or more of the following:

[0247]

[0248] Where n is an integer, such that the structure MW 理论 It is maintained between 500 g / mol and 18000 g / mol, or between 500 g / mol and 4500 g / mol.

[0249] The foregoing exemplary structures (IX) to (XXI) are not intended to be limiting examples. Other variations of the foregoing structures (IX) to (XXI) may be considered by those skilled in the art in light of the broader guidance on self-healing oligomers according to structure (VII) described elsewhere herein.

[0250] In various embodiments, the self-healing oligomer according to structure (VII) also includes a polymerizable segment. If present, the polymerizable segment preferably includes a radiation-curable segment, such as vinyl, acryloyloxy, methacryloxy, and maleimide groups, but other reactive groups may also be used, such as, but not limited to, hydroxyl, amino, alkynyl, azide, aziridine, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, F, Cl, Br, I, or similar groups.

[0251] In one embodiment, the self-healing oligomer according to structure (VII) comprises (meth)acrylate groups. If the self-healing oligomer according to structure (VII) is present as part of or entirely of the composition forming the self-healing component, the self-healing component may have any suitable amount of (meth)acrylate groups, for example, 0.015 to 0.1 equivalents, or 0.03 to 0.1 equivalents, or 0.037 to 0.1 equivalents, or 0.03 to 0.08 equivalents, or 0.03 to 0.05 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents of (meth)acrylate groups per 100g of the composition.

[0252] In other embodiments, the polymerizable groups may also be present, or alternatively, in other components of the entire formulation. In one embodiment, the composition incorporating the self-healing oligomer according to structure (VII) has (meth)acrylate groups, wherein such (meth)acrylate groups are 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 only in the monomer component; or only in the oligomer component. In such embodiments, the composition may have any suitable amount of (meth)acrylate functional groups, 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 100g of the composition.

[0253] The inventors have also discovered that the effectiveness and usability of coatings (e.g., fiber optic coatings) containing self-healing oligomers according to structure (VII) can be improved if the amount of polymerizable groups relative to the self-healing fragments in the composition is maintained within a certain ratio relative to each other. Therefore, in one embodiment, the composition has an equivalent ratio of polymerizable groups to self-healing groups of less than 14, or less than 10, or less than 8, or less than 6, or less than 5, or is 1 to 14, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5, or 3 to 10, or 3 to 8, or 3 to 5.

[0254] In order to effectively quantify the specific efficacy of any one or more self-healing oligomers according to structure (VII), it may be preferable to measure the self-healing and / or stress relaxation properties of the cured product of a composition incorporating one or more self-healing oligomers according to structure (VII).

[0255] Specifically, when a fixed amount of uncured composition is treated according to predetermined, fixed-set curing conditions, and then certain physical properties are measured after initial curing, and then at a subsequent time after the cured product has been damaged in a controlled manner and allowed to self-heal for a period of time, the self-healing and / or stress relaxation capabilities can be assessed, as described elsewhere above.

[0256] A third aspect of the invention is a self-healing coated optical fiber comprising glass fibers, the glass fibers optionally containing a core and a cladding; a first coating disposed around and in contact with the glass fibers; optionally, an ink layer disposed around and in contact with the first or second coating; wherein the first coating is a cured product of a composition, the composition being: (a) according to any embodiment of the first aspect, and / or (b) comprising an oligomer according to any embodiment of the second aspect.

[0257] In one embodiment, the self-healing fiber is configured to repair more than 20%, or more than 50%, or more than 75%, or more than 90% of the voids formed in the coating within a time period of no more than 48 hours, or more than 8 hours, or more than 1 hour, or more than 5 minutes, or more than 1 minute, while the self-healing coated fiber is maintained at a temperature below 80°C, or preferably below 60°C, or preferably below 50°C, or preferably above 25°C, as determined visually by microscopic imaging at 40x or 100x magnification.

[0258] The self-healing coated optical fiber may contain any number of coatings surrounding the glass fiber; however, in a preferred embodiment, the self-healing coated optical fiber contains at least two layers. In such embodiments, the layer disposed around and in contact with the fiber is a primary coating, while the layer disposed around and in contact with the primary coating is referred to as a secondary coating. Additional outer layers may be referred to as a third layer, etc., or, if they contain pigments or inks to enable fiber identification, such layers may be simply referred to as ink layers. If an ink layer is present, it is preferably the outermost layer of the self-healing coated optical fiber. Other multilayer coating systems are known and disclosed, for example, in WO2017173296, which is incorporated herein by reference.

[0259] According to this third aspect, the coating or primary coating is preferably a cured product of a radiation-curable composition incorporating a self-healing oligomer according to the second aspect of the invention, in any embodiment of the first aspect of the invention and / or a product of a radiation-curable composition incorporating a self-healing oligomer according to the second aspect of the invention.

[0260] In embodiments of the third aspect of the invention, any type of optical fiber can be used. However, in a preferred embodiment, the coated optical fiber has a mode field diameter of 8 μm to 10 μm at a wavelength of 1310 nm, or a mode field diameter of 9 μm to 13 μm at a wavelength of 1550 nm, and / or an effective area between 20 μm². 2 With 200μm 2 Between these two types of fibers, considering the anticipated demand for coating processes utilizing higher linear or processing speeds, such fibers can be single-mode and / or fibers with large effective area. However, other fiber types, such as multimode fibers, can also be used.

[0261] In field applications, self-healing optical fibers according to the third aspect of the invention can exhibit less cavitation than conventional optical fibers during initial fiber processing. Furthermore, they also exhibit a reduction in cavitation over time after cable installation and field use. This is because the self-healing properties and / or stress relaxation behavior of the coating according to the invention allow for structural rearrangement, which reduces and / or balances the internal stresses on the coating, due to the additional physical and / or thermal stresses or cavitation applied to the coated fiber. Over time, and depending in part on the temperature of the environment where the self-healing coated fiber is placed, at least some or even all of the associated cavitation can be reduced or even eliminated. In one embodiment, cavitation in the primary coating of the self-healing coated optical fiber according to the third aspect of the invention is visually reduced and / or eliminated within days, a day, 10 minutes, 5 minutes, or 1 minute while the fiber is maintained at 50°C or 25°C. In a preferred embodiment, while the fiber is maintained at 30°C or 25°C, the cavities in the primary coating decrease and / or disappear within 1 hour, or several days, or one day, or 30 minutes, or 10 minutes, or 5 minutes, or 1 minute.

[0262] The elimination of simulated optical fiber cavitation by coating with the self-healing primary coating composition according to the invention is achieved by... Figures 2A to 2E The photograph depicted (taken at 100x magnification) illustrates this. In such figures, the wires appear as an opaque, dark layer. The coating composition according to the invention has been applied to and cured onto the stainless steel wires to produce a primary coating. Such a primary coating... Figures 2A to 2E The first translucent layer, which is visible in contact with the stainless steel wire, is then coated with a secondary coating that acts as the outermost translucent layer, thereby creating a self-healing coated wire in a manner that mimics the geometry of a coated optical fiber. Figure 2A Prior to the photograph shown, the section of the self-healing coated conductor depicted had been hammered to induce severe cavitation events in the primary coating. Such cavitation is visible as ring-shaped bubbles with a shadowed ring around the (typically) clear core. The same section of the self-healing coated conductor was left to stand at room temperature for 2 hours before being photographed. Figure 2B The photos show that, as can be seen, the amount of cavitation has significantly decreased by 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 images were taken. Figure 2C The photograph shows that the amount of cavitation present in the primary coating has been significantly reduced, by at least 50%. Next, the same section of the self-healing coated wire is heated to 60°C and held at that temperature for 60 minutes, after which a photograph is taken. Figure 2D The photos were taken. By this point, all cavitation had been eliminated upon visual inspection. Finally, to ensure that cavitation would not reform upon cooling as is known to occur in conventional coated optical fibers, the same section of the self-healing coated conductor was cooled to -30°C and held at this temperature for 10 minutes, after which photos were taken. Figure 2E The photograph shows that cavitation did not reappear, indicating that the polymer network has rearranged rather than simply expanded.

[0263] While not strictly necessary, it is generally desirable for self-healing optical fibers to be configured such that the glass transition temperature of the self-healing coating is lower than the temperature at which repair is desired. It is not desirable to be bound by any theory, as the self-healing capability of the coating is believed to be inherently related to the segmentation movement of the polymer chains. Therefore, since a crystalline or glassy structure is believed to minimize the ability of the self-healing segments present in the coating to move and / or rearrange, it is preferable to prevent the coating from reaching a crystalline or glassy state (for amorphous, non-crystalline resins). Thus, in one embodiment, the glass transition temperature of the coating and / or the primary coating 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.

[0264] A fourth aspect of the invention is a method for coating optical fibers, the method comprising coating glass fibers with a coating composition, optionally in a single application, the coating composition being a cured product of any composition according to any embodiment of the first aspect and / or a composition using any self-healing oligomer according to the second aspect.

[0265] Methods for coating optical fibers are well known. In one embodiment, the method includes the steps of: providing a glass optical fiber, preferably by drawing the glass optical fiber via a drawing tower; applying a primary coating composition to the surface of the glass optical fiber; optionally, applying a dose of radiation energy, including ultraviolet 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 and secondary coating compositions to at least one radiation source capable of emitting ultraviolet radiation to affect the curing of the primary and secondary coating compositions, 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.

[0266] The fifth aspect of the present invention is an optical fiber cable, wherein the optical fiber comprises at least one optical fiber according to any embodiment of the third aspect of the present invention, and / or wherein the optical fiber is a cured product of a composition utilizing any self-healing oligomer of the second aspect according to any embodiment of the first aspect of the present invention, and / or wherein the optical fiber is coated according to any embodiment of the fourth aspect of the present invention.

[0267] The improved self-healing coated optical fiber of the present invention can be formulated by selecting the components specified herein, and can be further easily tuned by those skilled in the art to which the invention applies by following the formulation guidelines herein and by inferring from the general methods used in the embodiments described below. Such embodiments below further illustrate the invention, but, of course, should not be construed as limiting the scope of the invention in any way.

[0268] Example

[0269] These examples illustrate implementations of the invention. Table 1 describes the various components of the compositions used in this example. Table 2 describes various other aspects of the oligomers produced by the reagents in Table 1, the synthesis of which will be further described below. Tables 3A to 3D indicate the test results of the entire formulation created from the components described in Table 1 and the oligomers characterized in Table 2.

[0270] Table 1 - Formulation Components

[0271]

[0272]

[0273] Synthesis of oligomers

[0274] The oligomers used herein were prepared to obtain mixtures with a molecular weight statistical distribution readily identifiable to those skilled in the art. Unless otherwise stated, the structures shown in this section and elsewhere herein represent only the designed average or “ideal” structures.

[0275] Specifically, to generate oligomer 1, a mixture of AHMP (2-amino-4-hydroxy-6-methylpyrimidine, 12.5 g, 0.1 mol) and TMDI (42 g, 0.2 mpl) was placed in a four-necked flask (500 ml) and purged with nitrogen. The mixture was then stirred at 145 °C for 3.5 h under nitrogen, followed by 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 h, then cooled to 80 °C. The reaction mixture was then purged with a gas 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 2-hydroxyethyl acrylate (HEA, 11.6 g, 0.1 mol) were then added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 80°C for another 2 hours to obtain a final product mixture that was a viscous liquid with the average structure (XXII) shown below. This product could then be used in subsequent formulations without further purification. The designed structure (XXII) is described below:

[0276]

[0277] To generate oligomer 2, the steps described above for the synthesis of oligomer 1 are followed, except that 2-hydroxyethyl methacrylate (HEMA) is used instead of HEA. The viscous liquid product is a mixture of oligomers having an average structure (XXIII). This product can then be used in subsequent formulations without further purification. The designed structure (XXIII) is as follows:

[0278]

[0279] To produce oligomer 3, the steps described above for the synthesis of oligomer 1 are followed, except that 2-ethyl-1-hexylamine is used instead of AHMP. The resulting viscous liquid product is provided as a mixture of oligomers without further purification and has the average structure (XXIV) shown below:

[0280]

[0281] To generate 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-necked flask (500 ml) and purged with nitrogen. The resulting mixture was then stirred at 155 °C under nitrogen for 3 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 mixture was then stirred at 115 °C for 3 hours and cooled to 90 °C. The reaction mixture was then purged with a gas mixture 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 then added sequentially. While still purged with a 1:3 air / nitrogen mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final product mixture with an average structure (XXV) that is a viscous liquid. This product can then be used in subsequent formulations without further purification. The designed structure (XXV) is as follows:

[0282]

[0283] To generate oligomer 5, the steps leading to the synthesis of oligomer 4 are followed, except that HEMA is used instead of HEA. The viscous liquid product is a mixture of oligomers with an average structure (XXVI). This product can then be used in subsequent formulations without further purification. The designed structure (XXVI) is as follows:

[0284]

[0285] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was then stirred at 155 °C under nitrogen 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 gas mixture of air and nitrogen in a volume ratio of 1:3. Subsequently, 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. While still purged with a 1:3 air / nitrogen mixture, the reaction mixture was then stirred at 90°C for another 2 hours to obtain a final oligomer mixture that was a viscous liquid with the average structure (XXVII) shown below. The product could then be used in subsequent formulations without further purification.

[0286]

[0287] To produce oligomer 7, the procedure for synthesizing oligomer 6 as described 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, having the average structure (XXVIII) shown below:

[0288]

[0289] To generate oligomer 8, the steps described above for the synthesis of oligomer 1 are followed, except that PPG-600 is used instead of PPG-1000. The viscous liquid product is a mixture of oligomers having an average structure (XXIX). This product can then be used in subsequent formulations without further purification. The designed structure (XXIX) is as follows:

[0290]

[0291] To generate oligomer 9, the steps described above for the synthesis of oligomer 1 are followed, except that PPG-2000 is used instead of PPG-1000. The viscous liquid product is a mixture of oligomers having an average structure (XXX). This product can then be used in subsequent formulations without further purification. The designed structure (XXX) is as follows:

[0292]

[0293] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was then stirred at 145 °C for 3.5 h under nitrogen, followed by the addition of disulfide (2-hydroxyethyl disulfide, 18.82 g, 0.12 mol), DBTDL (0.02 g, 0.0317 mmol), and butyl acetate (40 g). The resulting mixture was further stirred at 100 °C for 3 h, and then cooled to 90 °C. The reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (14.2 g, 0.12 mol) were then added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final product mixture that was a viscous liquid with the average structure (XXXI) shown below. This product could then be used in subsequent formulations without further purification. The designed structure (XXXI) is described below:

[0294] To generate oligomer 11, the steps described above for the synthesis of oligomer 1 are followed, except that 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AMG) is used instead of HEA. The viscous liquid product is a mixture of oligomers having the average structure (XXXII). This product can then be used in subsequent formulations without further purification. The designed structure (XXXII) is as follows:

[0295]

[0296] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was stirred at 145 °C for 3.5 h under nitrogen, and then 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 reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. Then, DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), IEA (ethyl isocyanate acrylate, 4.64 g, 0.03 mol), and glycerol (2.75 g, 0.03 mol) were added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final product mixture that was a viscous liquid with the average structure (XXXIII) shown below. This product could then be used in subsequent formulations without further purification. The designed structure (XXXIII) is described below:

[0297]

[0298] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was stirred at 145 °C for 3.5 h under nitrogen, and then 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 reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. Then, DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and ethylene glycol (3.83 g, 0.062 mol) were added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for an additional 2 hours to obtain a final product mixture that was a viscous liquid with the average structure (XXXIV) shown below. This product could then be used in subsequent formulations without further purification. The designed structure (XXXIV) is described below:

[0299]

[0300] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was stirred at 145 °C for 3.5 h under nitrogen, and then PPG-1000 (57.8 g, 0.0578 mol), PDMS-diol 550 (hydroxyl-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 reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. Then, DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (7.07 g, 0.06 mol) were added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final oligomer mixture as a viscous liquid with the average structure (XXXV) shown below. The product was then ready for use in subsequent formulations without further purification. The designed structure (XXXV) is described below:

[0301]

[0302] To generate oligomer 15, the steps described above for the synthesis of oligomer 14 are followed, except that PDMS-diol 2500 (bis(3-aminopropyl)-terminated poly(dimethylsiloxane), Mn = 2500) is used instead of PDMS-diol 550. The viscous liquid product is a mixture of oligomers having an average structure (XXXVI). This product can then be used in subsequent formulations without further purification. The designed structure (XXXVI) is as follows:

[0303]

[0304] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was stirred at 145 °C for 3.5 h under nitrogen, and then 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 reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. Then, DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (5.48 g, 0.047 mol) were added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final oligomer mixture as a viscous liquid with the average structure (XXXVII) shown below. The product can then be used in subsequent formulations without further purification. The designed structure (XXXVII) is shown in the figure below:

[0305]

[0306] To generate 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-necked flask (250 ml) and purged with nitrogen. The mixture was stirred at 125–145 °C for 3.5 h under nitrogen, and then 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 reaction mixture was then purged with a gas consisting of air and nitrogen in a volume ratio of 1:3. Then, DBTDL (0.03 g, 0.0475 mmol), BHT (0.15 g, 0.68 mmol), and HEA (14.08 g, 0.121 mol) were added sequentially. While still purged with a 1:3 air / nitrogen gas mixture, the reaction mixture was further stirred at 90°C for another 2 hours to obtain a final product mixture that was a viscous liquid with the average structure (XXXVIII) shown below. This product could then be used in subsequent formulations without further purification. The designed structure (XXXVIII) is shown in the figure below:

[0307]

[0308] The specific oligomer reactants described above are depicted in Table 2 below.

[0309]

[0310] For the purposes of this document, oligomers having self-healing groups (e.g., but not limited to oligomers 1 to 2, 4 to 6 and 8 to 17) may be considered as part of a self-healing component, while oligomers without any self-healing groups (e.g., but not limited to oligomers 3 and 7) will not be so characterized.

[0311] The synthesis of the aforementioned oligomers, which can be considered part of a self-healing component, is intended for use in compositions for coating optical fibers, such as primary coating compositions for coating optical fibers. To further demonstrate this, subsets of these oligomers are used to generate various compositions, which are formulated and evaluated as described below. The following compositions are formulated together with appropriate controls using the selected oligomers described above that do not contain self-healing groups.

[0312] Formulations 1 to 22

[0313] Each of the formulations described in Tables 3A to 3D is prepared by testing 100g of sample in a suitable container with SpeedMixer. TM The mixture was prepared by mixing in a 100ml mixing cup used together. Specifically, oligomer and monomer components were mixed in addition to the other components specified in Tables 3A to 3D below. The mixture was then manually premixed to ensure that the oligomers were fully incorporated into the monomers used, after which the cup was closed and mixed in a SpeedMixer. TM Mix at 3500 rpm for 3 minutes in a DAC150FVZ. After this, stop mixing and transfer the resulting mixture to a suitable container. Then heat in an oven to 75°C and maintain this temperature for approximately 1 hour to ensure all components are completely dissolved. Remove the sample from the oven and mix again in a SpeedMixer for another 3 minutes using the same method. After this, add silane acrylate, resulting in a total of 100 g. Finally, mix the mixture again in a SpeedMixer for another 3 minutes using the same method.

[0314] These formulations were then characterized according to the methods described below, based on the content of their respective UPy and (meth)acrylate groups. All formulations were then tested according to the methods described below to determine their tensile strength, elongation, segment modulus, toughness, viscosity, self-healing ability of the membrane at multiple temperatures, and stress relaxation percentage. Unless otherwise stated, the values ​​of UPy equivalent, (meth)acrylate equivalent, and disulfide equivalent are expressed herein as rounded to three decimal places. Meanwhile, segment modulus and toughness values ​​have been rounded to two decimal places, and tensile strength is expressed as rounded to one decimal place. Viscosity is expressed in the nearest centipoise. Membrane healing results are reported as a qualitative binary "yes" or "no" value. Finally, stress relaxation and membrane mechanical recovery values ​​are expressed as rounded to the nearest 1%. The value of each of these measured properties is reported in Tables 3A to 3D below.

[0315] UPy equivalent

[0316] The “UPy equivalent” of a given composition is determined by first calculating the molar amount of UPy groups in each UPy-containing component (Z) according to the following expression:

[0317]

[0318] Where Wt = the amount of the corresponding component Z relative to 100g of the total relevant composition by weight; N = the number of 2-ureido-4-pyrimidinone groups present in one molecule of component Z; and MM is the theoretical molecular weight of component Z (in g / mol). The theoretical molecular weight values ​​of the reactants used to generate the oligomers (including UPy-containing oligomers) of the formulations described herein are reported in Table 2.

[0319] Then, the UPy equivalent value of the entire composition is calculated by summing the molar values ​​of the UPy groups of each UPy-containing component according to the following expression:

[0320]

[0321] Where n represents the quantity of UPy-containing components present in the formulation.

[0322] The UPy equivalent value may optionally be expressed as "UPy milliequivalents" by multiplying the sum by 1000, but unless otherwise specified, the values ​​are not reported in this manner. For clarity, where "equivalent" or "milliequivalent" is specified herein, the value will be interpreted with reference to 100 g of the associated composition unless otherwise stated. The UPy equivalent values ​​for each formulation are presented in Table 3A below.

[0323] It should be noted that if the complete formulation of the composition is not known in advance, the equivalent amount of the self-healing fragment can be determined analytically by any suitable method that a person skilled in the art to which this invention is applicable will understand, such as size exclusion chromatography (SEC), infrared spectroscopy, HPLC, MALDI-TOF mass spectrometry, or nuclear magnetic resonance (NMR) methods.

[0324] (Meth)acrylate equivalents and disulfide equivalents

[0325] The values ​​for (meth)acrylate equivalents and disulfide equivalents are determined using the same method specified above for "UPy equivalents," except that instead of evaluating UPy groups or UPy-containing components, the (meth)acrylate groups (or disulfide groups, if applicable) are counted. It is contemplated that if a given composition has both acrylate and methacrylate groups, the values ​​will be added together for the purposes of this document.

[0326] Viscosity

[0327] Viscosity was measured using an Anton Paar Rheolab QC instrument. This instrument was configured for the conventional Z3 system used. For each measurement, a sample of 14.7 ± 0.2 g was loaded into a disposable aluminum cup. The sample in the cup was examined; if visual inspection revealed the presence of air bubbles, the sample and cup were centrifuged or left to stand for a sufficient time to allow the bubbles to escape from most of the liquid. Bubbles appearing at the top surface of the liquid were considered acceptable.

[0328] Next, gently load the pendulum into the liquid in the measuring cup, then install the cup and pendulum into the instrument. Allow five minutes for the sample temperature to equilibrate with the temperature of the circulating liquid (which itself is maintained at 25 degrees Celsius). Then, set the rotation speed to a specific value to produce 50 seconds. -1 The required shear rate.

[0329] After this, the measurement reading is obtained. The instrument panel displays the viscosity value, and if the viscosity value changes only slightly (less than 2% relative change) within 15 seconds, the measurement is stopped. If a relative change greater than 2% is observed, the sample is allowed to equilibrate for an additional 5 minutes, and then the test continues. If the variability of the sample still exists during the additional equilibration period, the shear rate should be modified according to methods well known in the field to which this invention applies to more accurately capture the viscous properties of the sample. The reported results represent the average viscosity values ​​of three independently tested samples. Unless otherwise stated, the values ​​are reported in millipascal-seconds (mPa·s) and the shear rate is 50 s. -1 The results for each embodiment are reported in Tables 3A to 3D below, depending on the specific circumstances.

[0330] Membrane sample preparation

[0331] To fabricate a membrane capable of testing a wide range of physical properties, each sample was subjected to a constant nitrogen flow at 1 J / cm². 2 The UV dose was delivered using a DRS-10 / 12QN fusion unit, a 600W UV lamp system. This system had a 1600M radiator (600W / inch, which equals 240W / cm, and therefore 600W in total) equipped with an R500 reflector as the lamp. One lamp used an H-bulb, and the other used a D-bulb UV lamp, with the D-bulb used for curing the sample. The UV dose was then measured using an International Light IL390 radiometer.

[0332] Then, individual test strips approximately 1.27 cm (0.5 inch ± 1 / 32”) wide and approximately 12.7 cm (5 inch ± 1 / 8”) long were cut from the membrane. The precise thickness of each sample was measured using a calibrated micrometer.

[0333] Test methods for tensile strength, elongation, segmental modulus and toughness

[0334] The method for determining the segmented modulus used herein can be found in EP2089333B1, assigned to DSM IP Assets BV, the entire contents of which are incorporated herein by reference. Using MTScriterion TM Model 43.104 is used to determine the tensile properties (tensile strength, elongation at break, and segment modulus) of a cured film with a thickness of 3 mil for each sample prepared according to the above-described "film sample preparation" procedure.

[0335] Because of these relatively soft coatings (e.g., coatings with a modulus less than about 10 MPa), the coatings were stretched downwards and cured on a glass plate, and individual specimens were cut from the glass plate with a scalpel after a thin layer of talc was applied. A 0.9 kg (2-lb) load cell was used in an Instron 4442 tensile testing instrument, and the modulus was calculated using a least-squares fit of the stress-strain curve at an elongation of 2.5%. Prior to testing, the cured film was conditioned for 16 to 24 hours at 23.0 ± 0.1 °C and 50.0 ± 0.5% relative humidity.

[0336] For the test specimens, the gauge length 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 by averaging at least six test specimens.

[0337] The tensile strength value is determined as the highest stress the sample withstands before fracture. The toughness value is determined as the total area under the stress-strain curve.

[0338] Membrane repair test

[0339] First, for each formulation shown in the table below, test strips of cured films with a thickness of 3 mils were prepared according to the "Membrane Sample Preparation" procedure described above. Then, based on... Figure 1 The schematic diagram illustrates how individual test strips were cut under a microscope objective (40x magnification) with a suitably sharp (i.e., like new) scalpel with a blade thickness of 0.018 inches or less to observe the self-healing of the incisions in real time. Repair was then visually assessed after each sample was maintained at room temperature (25°C) for 5 minutes. Qualitative assessments of repair performed in this manner are reported in lines beginning with the phrase “membrane repair at 25°C”; if any observable amount of repair occurred under these conditions, the sample was rated “Yes”; if no observable repair occurred, the sample was rated “No”, as reported in Tables 3A through 3D below.

[0340] Then, each sample not yet rated "yes" was further heated to 55°C using a Linkham LTS120 temperature stage under a microscope objective (40x magnification) for further visual evaluation. Repair was again visually qualitatively determined after maintaining each sample at 55°C for 5 minutes. In this case, the same criteria used to determine "yes" and "no" were applied to the samples as with the room temperature repair test. Results are appropriately reported under the row beginning with the phrase "film repair at 55°C" in Tables 3A, 3B, and 3D. It should be further understood that samples exhibiting self-repair at room temperature were automatically rated "yes" (without measurement) under the 55°C condition test, which should be interpreted as repair behavior at 55°C exceeding that at room temperature.

[0341] Stress relaxation test

[0342] First, for each formulation shown in the table below, test strips of cured films with a thickness of 3 mil were prepared according to the “Membrane Sample Preparation” procedure described above. The strips were then conditioned overnight at 50% relative humidity and 23°C. The precise thickness was measured using a calibrated micrometer, and the precise width was measured using an optical microscope at 4x magnification. Samples were tested in a Dynamic Mechanical Analyzer (DMA) with a “wide strip” geometry of 0.79 inches in test length, and by mounting 1 gram held by a screw and tightened to 20 cN.m with a torque drive. Samples were isothermally tested at room temperature and held at a specified strain (2% for Tables 3A and 3D; 1.5% for Tables 3B and 3C) for 100 seconds, while stress was measured at a sampling rate of 8 points / second. Samples were run in duplicate and averaged. The total percentage decrease in stress from 1 second to 100 seconds is reported in Tables 3A and 3D below. The total percentage of stress reduction from 1 second to 10 seconds is reported in Tables 3B and 3C below.

[0343] Membrane mechanical recovery test

[0344] First, for each formulation shown in Table 3D below, prepare two 3-mil thick cured films according to the “Membrane Sample Preparation” procedure described above, except that test strips are not immediately cut from the films. For the avoidance of doubt, for each test, both films are prepared not only from the same formulation but also from the same actual batch of starting materials. Then, cut one film according to the procedure outlined in the “Membrane Repair Test” above. The other film is not cut.

[0345] Both membranes were allowed to cure overnight (up to 12-14 hours) at 50% relative humidity and 23°C or in an oven at 55°C (as specified in Table 3D). The cut membranes were not subjected to any other treatment or alteration after the cuts were made.

[0346] After a 12-14 hour recovery period, the membrane is cut into test strips following the “Membrane Sample Preparation” procedure described above. The tensile strength of the resulting strip from the uncut membrane is then measured and recorded as described above (referred to herein as “pre-cut tensile strength”). The tensile strength of the cut test strips is then determined again according to the procedure outlined elsewhere above. If the sample has been recovered at 55°C, it is first equilibrated to room temperature (over approximately 30 minutes) before tensile strength measurement. The obtained value is then recorded (referred to herein as “post-cut tensile strength”).

[0347] The membrane mechanical recovery values ​​reported in Table 3D below represent the measured post-cut tensile strength value divided by the measured pre-cut tensile strength value for each composition, expressed as a percentage closest to the integer 1%. In cases where the sample shows no repair and post-cut tensile strength cannot be measured, the value is simply reported as 0%.

[0348]

[0349] Table 3B

[0350] Formulations 11 to 17. All quantities are listed in parts by weight.

[0351]

[0352] Table 3C

[0353] Formulations 18 to 22. All quantities are listed in parts by weight.

[0354] preparation 18 19 20 21 22 Oligomer 1 70 46.7 35 23.3 Oligomer 3 23.3 35 46.7 70 EOEOEA 22.2 22.2 22.2 22.2 22.2 TMPTA 0.5 0.5 0.5 0.5 0.5 VC 5 5 5 5 5 TPO 1.2 1.2 1.2 1.2 1.2 Irganox 1035 0.6 0.6 0.6 0.6 0.6 Silyl acrylate 0.5 0.5 0.5 0.5 0.5 total 100 100 100 100 100 UPy equivalent 0.042 0.027 0.021 0.014 0 (meth)acrylate equivalent 0.203 0.203 0.203 0.203 0.203 Tensile strength (MPa) 0.5 0.3 0.3 0.2 0.3 Elongation (%) 124 83 93 75 79 Piecewise modulus (MPa) 0.88 0.60 0.47 0.40 0.26 Viscosity (cPs) 10959 No data No data No data 7840 Membrane repair, 25℃ yes No data No data No data no Stress relaxation, 1.5% (1-10s, %) 39 34 29 20 4

[0355] Table 3D

[0356] Mechanical recovery of the selected formulation. All quantities are listed in parts by weight.

[0357] preparation 3 4 9 10 Oligomer 1 70 Oligomer 3 70 Oligomer 6 70 Oligomer 7 70 EOEOEA 22.2 22.2 22.2 22.2 2-HEA TMPTA 0.5 0.5 0.5 0.5 VC 5 5 5 5 TPO 1.2 1.2 1.2 1.2 Irganox 1035 0.6 0.6 0.6 0.6 Silyl acrylate 0.5 0.5 0.5 0.5 total 100 100 100 100 UPy equivalent 0.042 0 0.032 0 (meth)acrylate equivalent 0.203 0.203 0.208 0.208 Tensile strength (MPa) 0.3 0.1 0.5 0.4 Elongation (%) 128 48 75 52 Piecewise modulus (MPa) 0.77 0.27 1.34 1.13 <![CDATA[Toughness (N*mm / mm 3 )]]> 0.24 0.01 0.20 0.14 Viscosity (cPs) 11030 1298 8669 1527 Membrane repair, 25℃ yes no no no Membrane repair, 55℃ yes no yes no Stress relaxation, 2% (1-100 seconds, %) 60 4 No data No data Membrane mechanical recovery (overnight at 23°C), % 78 0 13 0 Membrane mechanical recovery (55°C overnight), % No data 0 52 0

[0358] Results Discussion

[0359] As can be seen, given their desired viscosity, tensile strength, elongation, modulus, toughness, self-healing and / or stress relaxation test results, compositions according to various aspects of the invention tend to have properties that make them particularly suitable for optical fiber coating applications, especially as a primary coating for self-healing optical fibers.

[0360] Specifically, according to Table 3A, various compositions based on various aspects of the 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 despite the wide range of physical and / or rheological properties, such as viscosity and modulus, exhibited by such compositions. Although the measured segmental modulus value was almost 4 MPa, Example 7 still exhibited self-healing behavior.

[0361] also, Figure 3A and Figure 3B The diagram provides graphs showing the stress relaxation properties of two compositions containing self-healing fragments (Examples 3 and 5) and their analogues without self-healing fragments (Examples 4 and 6). [Go to...] Figure 3ACompared to Example 4, Example 3 exhibits significant stress relaxation behavior. Similarly, turning... Figure 3B Example 5 is shown to have similar performance advantages compared to its control analog, Example 6. Although Example 5 did not exhibit significant self-healing behavior under the conditions mentioned herein and reported in Table 3A above, it still showed a significant performance advantage in stress relaxation behavior when compared to compositions without any self-healing fragments. While many viscoelastic polymer materials may exhibit some form of stress relaxation behavior, Figure 3A , Figure 3B The examples shown in Table 3C exhibit a significant stress reduction between 1 s and 100 s, attributed to self-healing fragments, particularly the UPy groups. This stress relaxation behavior suggests that anti-cavitation coatings with higher moduli can be utilized, while still tending to minimize microbending-induced attenuation in the fiber.

[0362] Tables 3B and 3C show that additional compositions containing oligomers forming another array of self-healing components still exhibit these beneficial properties. Specifically, compositions containing self-healing oligomers with disulfide groups as functional segments still exhibit a degree of beneficial stress relaxation behavior. Formulation 16 contains a self-healing oligomer (oligomer 10) containing both UPy and disulfide groups, which exhibits the best film repair and stress relaxation results in the series at 25°C. Table 3C also shows the beneficial effects of compositions containing self-healing oligomers and oligomers that are not part of the self-healing component (e.g., formulations 19 to 21).

[0363] Finally, Table 3D shows that, compared with control formulations 4 and 10, certain compositions containing self-healing oligomers (e.g., oligomers 1 and 6) also have the potential to exhibit self-healing through the membrane mechanical recovery test method.

[0364] Formulations 3 and 18 are recognized as being based on the same chemical formulation. Nevertheless, they are reported separately because they involve different batches of raw materials (although the same batch of oligomer 1 was used). Variations in measured properties are believed to be due to batch variations in the raw materials used.

[0365] Additional exemplary implementations

[0366] The first additional exemplary aspect includes the following implementation:

[0367] 1. A composition for coating optical fibers, the composition comprising:

[0368] Optionally, reactive monomer and / or oligomer components;

[0369] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally also containing one or more polymerizable segments;

[0370] Initiator components; and

[0371] Optionally, additive components;

[0372] Wherein (a) the self-healing component is present in an amount greater than 30% by weight, or greater than 40% by weight, or greater than 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or 30-80% by weight, or 30-70% by weight, or 40-80% by weight, or 40-70% by weight, or 50-80% by weight, or 50-70% by weight, relative to the total weight of the composition; and / or

[0373] (b) The composition has a concentration of greater than 0.015 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 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents, or 0.02 to 0.1 equivalents, or 0.02 equivalents per 100g of the composition. Self-repairing fragments in quantities up to 0.08 equivalent, or 0.02 equivalent to 0.05 equivalent; or 0.022 equivalent to 0.15 equivalent, or 0.022 equivalent to 0.1 equivalent, or 0.022 equivalent to 0.08 equivalent, or 0.022 equivalent to 0.05 equivalent, or 0.022 equivalent to 0.045 equivalent; or 0.025 equivalent to 0.20 equivalent; or 0.037 equivalent to 0.15 equivalent, or 0.037 equivalent to 0.1 equivalent, or 0.037 equivalent to 0.08 equivalent, or 0.037 equivalent to 0.05 equivalent.

[0374] 2. A composition for coating optical fibers, the composition comprising:

[0375] Optionally, reactive monomer and / or oligomer components;

[0376] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally also containing one or more polymerizable segments;

[0377] Initiator components; and

[0378] Optionally, additive components;

[0379] The self-healing component comprises, is composed of or is substantially composed of a compound having at least one polymerizable group and a backbone derived from polyether polyols, polyester polyols, poly(dimethylsiloxane), disulfide polyols or mixtures thereof;

[0380] Wherein (a) the self-healing component is present, relative to the weight of the entire composition, 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 30-80 wt%, or 30-70 wt%, or 40-80 wt%, or 40-70 wt%, or 50-80 wt%, or 50-70 wt%, and / or

[0381] (b) The composition has a concentration of greater than 0.015 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 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents, or 0.02 to 0.1 equivalents, or 0.02 equivalents per 100g of the composition. Self-repairing fragments in quantities up to 0.08 equivalent, or 0.02 equivalent to 0.05 equivalent; or 0.022 equivalent to 0.15 equivalent, or 0.022 equivalent to 0.1 equivalent, or 0.022 equivalent to 0.08 equivalent, or 0.022 equivalent to 0.05 equivalent, or 0.022 equivalent to 0.045 equivalent; or 0.025 equivalent to 0.20 equivalent; or 0.037 equivalent to 0.15 equivalent, or 0.037 equivalent to 0.1 equivalent, or 0.037 equivalent to 0.08 equivalent, or 0.037 equivalent to 0.05 equivalent.

[0382] 3. A composition for coating optical fibers, said composition comprising:

[0383] Optionally, reactive monomer and / or oligomer components;

[0384] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally also containing one or more polymerizable segments;

[0385] Initiator components; and

[0386] Optionally, additive components;

[0387] The composition contains less than 5% by weight, or less than 3% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight of solvent, wherein the determination of solvent content does not include any (meth)acrylate functional compounds;

[0388] Wherein (a) the self-healing component is present, relative to the weight of the entire composition, 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 30-80 wt%, or 30-70 wt%, or 40-80 wt%, or 40-70 wt%, or 50-80 wt%, or 50-70 wt%, and / or

[0389] (b) The composition has a concentration of greater than 0.015 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 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents, or 0.02 to 0.1 equivalents, or 0.02 equivalents per 100g of the composition. Self-repairing fragments in quantities up to 0.08 equivalent, or 0.02 equivalent to 0.05 equivalent; or 0.022 equivalent to 0.15 equivalent, or 0.022 equivalent to 0.1 equivalent, or 0.022 equivalent to 0.08 equivalent, or 0.022 equivalent to 0.05 equivalent, or 0.022 equivalent to 0.045 equivalent; or 0.025 equivalent to 0.20 equivalent; or 0.037 equivalent to 0.15 equivalent, or 0.037 equivalent to 0.1 equivalent, or 0.037 equivalent to 0.08 equivalent, or 0.037 equivalent to 0.05 equivalent.

[0390] 4. A composition for coating optical fibers, the composition comprising:

[0391] Optionally, reactive monomer and / or oligomer components;

[0392] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally also containing one or more polymerizable segments;

[0393] Initiator components; and

[0394] Optionally, additive components;

[0395] Wherein (a) the self-healing component is present in an amount greater than 30% by weight, or greater than 40% by weight, or greater than 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or 30-80% by weight, or 30-70% by weight, or 40-80% by weight, or 40-70% by weight, or 50-80% by weight, or 50-70% by weight, relative to the total weight of the composition; and / or

[0396] (b) The composition has a concentration of greater than 0.015 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 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents; or 0.02 to 0.2 equivalents, or 0.02 to 0.15 equivalents, or 0.02 to 0.1 equivalents, or 0.02 equivalents per 100g of the composition. Self-repairing fragments up to 0.08 equivalent, or 0.02 equivalent to 0.05 equivalent; or 0.022 equivalent to 0.15 equivalent, or 0.022 equivalent to 0.1 equivalent, or 0.022 equivalent to 0.08 equivalent, or 0.022 equivalent to 0.05 equivalent, or 0.022 equivalent to 0.045 equivalent; or 0.025 equivalent to 0.20 equivalent; or 0.037 equivalent to 0.15 equivalent, or 0.037 equivalent to 0.1 equivalent, or 0.037 equivalent to 0.08 equivalent, or 0.037 equivalent to 0.05 equivalent;

[0397] The composition said composition comprises one or more of the following:

[0398] a. An adhesion accelerator compound, wherein the adhesion accelerator compound is a part of the additive component;

[0399] b. An adhesion-promoting functional group, wherein the adhesion-promoting functional group is part of the oligomer component, the monomer component, or the self-healing component; and / or

[0400] c. Antioxidant, wherein the antioxidant is part of the additive component.

[0401] 5. A composition for coating optical fibers, said composition comprising:

[0402] Optionally, reactive monomer and / or oligomer components;

[0403] A self-healing component, said self-healing component being composed of molecules having one or more self-healing segments and optionally also containing one or more polymerizable segments;

[0404] Initiator components; and

[0405] Optionally, additive components;

[0406] The self-healing component comprises an oligomer containing at least one disulfide group.

[0407] 6. The composition for coating optical fibers according to embodiment 5 above, wherein the oligomer containing at least one disulfide group further comprises at least one 2-ureido-4-pyrimidinone (UPy) group.

[0408] 7. The composition according to any one of the foregoing embodiments 1-6 of the first additional illustrative aspect, wherein the self-healing component is present in an amount greater than 30% by weight or 30-80% by weight relative to the total weight of the composition; and

[0409] The composition has a self-repairing fragment of greater than 0.015 equivalents or between 0.015 and 0.10 equivalents per 100g of the composition.

[0410] 8. The composition according to any one of the foregoing embodiments 1-7 of the first additional exemplary aspect, wherein the self-healing component comprises a plurality of molecules configured to bond to molecules in the reactive monomer component, the reactive oligomer component and / or the self-healing component.

[0411] 9. The composition according to any one of the foregoing embodiments 1-8 of the first additional exemplary aspect, wherein the reactive monomer component, the reactive oligomer component and / or the self-healing component comprises, substantially consists of or is composed of molecules comprising one or more polymerizable segments.

[0412] 10. The composition according to any one of the foregoing embodiments 1-9 of the first additional exemplary aspect, wherein the polymerizable segment comprises

[0413] (i) Radiation-curable segments, or

[0414] (ii) Thermocurable segments, or

[0415] (iii) Radiation-curable segments and heat-curable segments.

[0416] 11. The composition according to any one of the foregoing embodiments 1-10 of the first additional illustrative aspect, wherein the self-healing fragment comprises, is composed of or substantially comprises a multihydrogen-bonded group or a disulfide group, or both.

[0417] 12. The composition according to any one of the foregoing embodiments 1-11 of the first additional illustrative aspect, wherein the self-healing fragment comprises, is composed of, or is substantially composed of UPy groups, or wherein at least 50%, or at least 60%, or at least 75%, or at least 90%, or 100% equivalent of the self-healing groups per 100g of the composition are composed of UPy groups.

[0418] 13. The composition according to any one of the foregoing embodiments 1-12 of the first additional exemplary aspect, wherein the self-healing component comprises

[0419] The first molecule possessing the first self-repairing fragment; and

[0420] A second molecule possessing a second self-repairing fragment;

[0421] The first self-repairing fragment of the first molecule is configured to bond with the second self-repairing fragment of the second molecule;

[0422] The bond dissociation energy between the first self-repairing fragment and the second self-repairing fragment 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 between 9 kcal / mol and 20 kcal / mol, wherein the bond dissociation energy is calculated as the direct summation of all bonds between the self-repairing fragments according to Table 1 of The Scientific World Journal (2004) 4, 1074-1082, and the references cited therein; and Nature 2002, Vol. 3, 836-847, and the references cited therein.

[0423] 14. The composition according to any one of the foregoing embodiments 1-13 of the first additional illustrative aspect, wherein the first self-repairing segment and the second self-repairing segment are identical.

[0424] 15. The composition according to any one of the foregoing embodiments 1-14 of the first additional illustrative aspect, wherein the first self-repairing segment and the second self-repairing segment are different.

[0425] 16. The composition according to any one of the foregoing embodiments 1-15 of the first additional illustrative aspect, wherein the first self-healing fragment and the second self-healing fragment comprise, are composed of, or are substantially composed of multihydrogen-bonded groups.

[0426] 17. The composition according to any one of the foregoing embodiments 1-16 of the first additional exemplary aspect, wherein the first self-healing fragment and the second self-healing fragment are configured to form a dimer, wherein the dimer has 3 or 4 hydrogen bonds.

[0427] 18. The composition according to embodiment 17 of the first additional exemplary aspect, wherein the dimer comprises a first straight chain connected to each of three or four hydrogen bonds on one side of the first self-repairing segment; and a second straight chain connected to each of three or four hydrogen bonds on one side of the second self-repairing segment, wherein each of the first straight chain and the second straight chain comprises fewer than seven covalent bonds.

[0428] 19. The composition according to any one of the foregoing two embodiments 17 or 18 of the first additional exemplary aspect, wherein the dimer comprises a cyclic structure or a fused cyclic structure.

[0429] 20. The composition according to any one of the three embodiments 17-19 of the first additional exemplary aspect, wherein the dimer is based on one of the following structures: (I)-

[0430]

[0431] R is selected from an organic substituent, which optionally has a reactive group attached to the substituent;

[0432] The reactive groups mentioned therein include acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, azircyclopropyl, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, azircyclopropyl, carboxylate, hydrogen, F, Cl, Br, I, or maleimide groups.

[0433] 21. The composition according to any one of the four embodiments 17-20 of the first additional exemplary aspect, wherein the dimer is based on the following structure (I):

[0434]

[0435] R is selected from an organic substituent, which optionally has a reactive group attached to the substituent;

[0436] The reactive groups mentioned therein include acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, azircyclopropyl, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, azircyclopropyl, carboxylate, hydrogen, F, Cl, Br, I, or maleimide groups.

[0437] 22. The composition according to any one of the foregoing embodiments 1-21 of the first additional illustrative aspect, wherein the self-healing component comprises, is composed of, or is substantially composed of a plurality of molecules comprising at least one 2-ureido-4-pyrimidinone (UPy) group and at least three carbamate linking groups.

[0438] 23. The composition according to embodiment 22 of the first additional illustrative aspect, wherein the composition has a content greater than 0.015 equivalents, or 0.015 to 0.2 equivalents, or 0.015 to 0.1 equivalents, or 0.015 to 0.08 equivalents, or 0.015 to 0.05 equivalents, or 0.015 to 0.045 equivalents per 100g of the composition; or 0 UPy groups in amounts of 0.02 to 0.2 equivalents, or 0.02 to 0.1 equivalents, or 0.02 to 0.08 equivalents, or 0.02 to 0.05 equivalents; or 0.025 to 0.20 equivalents; or 0.037 to 0.2 equivalents, or 0.037 to 0.1 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents.

[0439] 24. The composition according to any one of the foregoing embodiments 1-23 of the first additional exemplary aspect, wherein the polymerizable segment of the reactive monomer component, the reactive oligomer component and / or the self-healing component comprises, is composed of or is substantially composed of (meth)acrylate groups.

[0440] 25. The composition according to any one of the foregoing embodiments 1-24 of the first additional exemplary aspect, wherein the composition has 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 100g of the composition.

[0441] 26. The composition according to the foregoing embodiment 25 of the first additional exemplary aspect, wherein the self-healing component has a polymerizable fragment or (meth)acrylate group in an amount of 0.015 to 0.1 equivalents, or 0.03 to 0.1 equivalents, or 0.037 to 0.1 equivalents, or 0.03 to 0.08 equivalents, or 0.03 to 0.05 equivalents, or 0.037 to 0.08 equivalents, or 0.037 to 0.05 equivalents per 100g of the composition.

[0442] 27. The composition according to any one of the foregoing embodiments 1-26 of the first additional exemplary aspect, wherein the equivalent of (meth)acrylate groups to the equivalent 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 is 1 to 14, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5, or 3 to 10, or 3 to 8, or 3 to 5.

[0443] 28. The composition according to any one of the foregoing embodiments 1-27 of the first additional illustrative aspect, wherein the self-healing component comprises, is composed of, or is substantially composed of a compound according to the following structure (VI):

[0444] [A(G) n -D m ]-[A(G) n-1 -D m ] k -Z (VI); where

[0445] A is either carbon or nitrogen;

[0446] Where A is sp3 carbon, n = 3, and when A is sp2 carbon or nitrogen, n = 2;

[0447] m is an integer from 0 to 500;

[0448] k is a number between 0 and 20;

[0449] For each occurrence of m, D is independently selected from the following divalent spacer groups: -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)-; -C(T)=N-; -C(T)=; -N=; or combinations thereof;

[0450] For each instance of a single-bond D, the single-bond is concatenated with it, and for each instance of a double-bond D, the double-bond is concatenated with it.

[0451] For each occurrence, each T is selected from a monovalent unit, including hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl;

[0452] Each T can also be selected from divalent D. m And connected to another one also selected from D m The divalent T forms a ring structure; and

[0453] And i is an integer from 1 to 40;

[0454] Each group in each unit of m, n, and k can be the same or different;

[0455] Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, F, Cl, Br, I, or maleimide group; and

[0456] For each occurrence of n, G is independently selected from hydrogen, Z, or a self-repairing fragment according to the following structure (VI-b):

[0457] (ZD m ) j XD m - (VI-b); where

[0458] X is a polyhydrogen-bonded group or a disulfide group;

[0459] j = 1 when X is divalent, and j = 0 when X is monovalent;

[0460] For at least one occurrence of n, G is a self-repairing fragment based on the structure (VI-b).

[0461] 29. The composition according to embodiment 28 above, wherein X comprises, is composed of, or is substantially composed of disulfide groups, and j = 1, and wherein the compound according to structure (VI) has a theoretical molecular weight MW between 500 g / mol and 100,000 g / mol. 理论 .

[0462] 30. The composition according to any one of the two preceding embodiments 28-29 of the first additional exemplary aspect, wherein X is a 2-ureido-4-pyrimidinone (UPy) group and j = 0.

[0463] 31. The composition according to any one of the 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.

[0464] 32. The composition according to any one of the four embodiments 28-31 of the first additional exemplary aspect, wherein D comprises a carbamate group, wherein the carbamate group is a reaction product of a diisocyanate compound.

[0465] 33. The composition according to embodiment 32 above, wherein the diisocyanate compound comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, (hydrogenated)benzene diisocyanate, 1,3-benzene diisocyanate, 1,4-benzene 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, methylene diisocyanate, etc. (4-Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, 2,4-methylene dicyclohexyl diisocyanate and / or 4,4′-methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, tetramethylxylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanate-ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated phenyl dimethyl diisocyanate, tetramethylphenyl dimethyl diisocyanate, or lysine isocyanate.

[0466] 34. The composition according to any one of the foregoing two embodiments 32-33 of the first additional exemplary aspect, wherein the diisocyanate compound comprises, is composed of, or is substantially composed of one or more trimethylhexamethylene diisocyanate (TMDI) and / or isophorone diisocyanate (IPDI).

[0467] 35. The composition according to any one of the foregoing embodiments 28-34 of the first additional exemplary aspect, wherein D comprises a polyol component, wherein the polyol component comprises polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, acrylic polyol and / or combinations thereof.

[0468] 36. The composition according to any one of the foregoing embodiments 28-35 of the first additional exemplary aspect, wherein Z comprises (meth)acrylate groups.

[0469] 37. The composition according to any one of the foregoing 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 nonylphenol acrylate, or diethylene glycol ethylhexyl acrylate.

[0470] 38. The composition according to any one of the foregoing embodiments 1-37 of the first additional exemplary aspect, wherein the self-healing component and / or molecule according to structure (VI) has a glass transition temperature (Tg) 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 -30°C to 20°C, or -25°C to 20°C, or -20°C to 10°C.

[0471] 39. The composition according to any one of the foregoing embodiments 1-38 of the first additional illustrative aspect, wherein the self-healing component and / or molecule according to structure (VI) has a value between 500 and 8000; or between 500 and 5000; 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 7 The theoretical molecular weight (MW) between 00 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. 理论 (in g / mol).

[0472] 40. The composition according to any one of the foregoing embodiments 1-39 of the first additional exemplary aspect, wherein the initiator component comprises, is composed of, or is substantially composed of one or more photoinitiators, wherein the one or more photoinitiators include acylphosphine oxide photoinitiators, α-hydroxy ketone photoinitiators, and / or Norrish type II photoinitiators.

[0473] 41. The composition according to any one of the foregoing 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 fluorescent whitening agents.

[0474] 42. The composition according to any one of the foregoing embodiments 1-41 of the first additional exemplary aspect, wherein the composition has a segmental modulus of 0.01 MPa to 100 MPa, or 0.05 MPa to 50 MPa, or 0.05 MPa to 20 MPa, or 0.05 MPa to 10 MPa, or 0.05 MPa to 5 MPa, or 0.1-3 MPa, or 2-20 MPa, or 2-10 MPa, or 2-5 MPa, wherein the segmental modulus is measured on a membrane prepared by means of means as described elsewhere herein.

[0475] 43. The composition according to any one of the foregoing embodiments 1-42 of the first additional illustrative aspect, wherein, as in 50s -1 The composition has a viscosity of less than 40 Pa·s, or less than 30 Pa·s, or less than 15 Pa·s, or less than 10 Pa·s, or less than 1 Pa·s, or 1 Pa·s to 20 Pa·s, or 1 Pa·s to 15 Pa·s, or 1 Pa·s to 10 Pa·s, or 0.05 Pa·s to 5 Pa·s, or 0.05 Pa·s to 1 Pa·s, as measured at a shear rate and at a temperature of 25°C.

[0476] 44. The composition according to any one of the foregoing embodiments 1-43 of the first additional illustrative aspect, wherein the monomer and / or oligomer components are present in amounts 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, relative to the total weight of the composition; and / or

[0477] 45. The composition according to any one of the foregoing 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, relative to the total weight of the composition.

[0478] 46. ​​The composition according to any one of the foregoing embodiments 1-45 of the first additional exemplary aspect, wherein 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 relative to the total weight of the composition; and the additive is present in an amount of 0% to 59.99% by weight;

[0479] 47. The composition according to any one of the foregoing embodiments 1-46 of the first additional illustrative aspect, wherein the composition is substantially free of superacids and superalkalis.

[0480] 48. The composition according to any one of the foregoing embodiments 1-47 of the first additional exemplary aspect, wherein the composition is substantially free of solvents comprising 2-propanol, acetone, acetonitrile, chloroform (CHCl3), dichloromethane, dimethyl sulfoxide ((CH3)2SO), ethyl acetate, hexane, methanol, tetrahydrofuran, toluene, propylene glycol, methyl ethyl ketone and water, wherein the content of said solvent is determined by any suitable method, such as size exclusion chromatography (SEC).

[0481] 49. The composition according to any one of the foregoing embodiments 1-48 of the first additional illustrative aspect, wherein the composition is substantially free of any solvent.

[0482] 50. The composition according to any one of the foregoing embodiments 1-49 of the first additional exemplary aspect, wherein when the composition is subjected to 1 J / cm² of radiation from a radiation source emitting a peak spectral output of 360 nm-400 nm... 2 When a dose of energy is used to solidify a 3-mil membrane, and at least one cut damage is subsequently formed in the membrane, the membrane is configured to repair >80% of the area of ​​the cut damage formed therein within a period of no more than 8 hours, or preferably no more than 1 hour, or preferably no more than 5 minutes, or preferably no more than 1 minute, while the membrane is maintained at a temperature of no more than 55°C, preferably no more than 23°C, wherein the repair of the cut damage is visually determined by microscopic imaging at 40x or 100x magnification.

[0483] 51. The composition according to any one of the foregoing embodiments 1-50 of the first additional exemplary aspect, wherein the composition, when cured into a first film and a second film according to the sample preparation method described elsewhere herein, has the pre-cut tensile strength of the first film and the post-cut tensile strength of the second film, wherein the pre-cut tensile strength and the post-cut tensile strength are measured after the second film has undergone the cutting process described elsewhere herein and then maintained at a temperature of about 25°C or about 55°C for 12-14 hours;

[0484] 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 tensile strength before cutting and the tensile strength after cutting are each measured according to ASTM D638 and further described elsewhere herein.

[0485] 52. The composition according to any one of the foregoing embodiments 1-51 of the first additional exemplary aspect, wherein when the composition is subjected to 1 J / cm² of radiation from a radiation source emitting a peak spectral output of 360 nm-400 nm... 2 When the energy dose is used to solidify the film into a 3-mil membrane, the composition, when measured according to the method described herein, has a stress relaxation of 1 to 10 seconds 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%.

[0486] 53. The composition according to any one of the foregoing embodiments 1-52 of the first additional exemplary aspect, wherein the composition, when cured into a film, has a segmental modulus of 0.01 MPa to 100 MPa, or 0.05 MPa to 50 MPa, or 0.05 MPa to 20 MPa, or 0.05 MPa to 10 MPa, or 0.05 MPa to 5 MPa, or 0.1-3 MPa, or 2-20 MPa, or 2-10 MPa, or 2-5 MPa, wherein the segmental modulus is measured on a film prepared by the method described elsewhere herein.

[0487] The second additional exemplary aspect includes the following implementation:

[0488] 54. An oligomer according to structure (VII), said oligomer for use in optical fiber coatings:

[0489] [UPy-(D m -UD m ) (2+q) ]-[A(G) (n-1) -D m ]k -Z (VII); where

[0490] UPy represents the UPy group, where the UPy group is 2-ureido-4-pyrimidinone;

[0491] U represents -NHC(O)E- or -EC(O)NH-, where E is O, NH, N (alkyl) or S;

[0492] q is a number greater than or equal to 0 and less than or equal to 10;

[0493] k is a number from 0 to 20;

[0494] A is selected from carbon and nitrogen;

[0495] n is 2 or 3, where n = 3 when A is sp3 carbon and n = 2 when A is sp2 carbon or nitrogen;

[0496] m is an integer from 0 to 500;

[0497] For each occurrence of m, D is independently selected from the following divalent spacer groups: -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)-, -C(T)=N-, -C(T)=, -N=, or combinations thereof;

[0498] in

[0499] For each instance of a single-bond D, the single-bond is concatenated with it, and for each instance of a double-bond D, the double-bond is concatenated with it.

[0500] in

[0501] For each occurrence, each T is selected from a monovalent unit, including hydrogen, F, Cl, Br, I, C1-C8 alkyl, C1-C8 alkoxy, substituted amino, or substituted aryl;

[0502] Each T can also be selected from divalent D. m And connected to another one also selected from D m The divalent T forms a ring structure; and

[0503] And i is an integer from 1 to 40;

[0504] Z is selected from hydrogen, acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, aziridine, carboxylate, F, Cl, Br, I, or maleimide group; and

[0505] For each occurrence of n, G is independently selected from hydrogen, -D m -Z, or a self-repairing fragment based on the following structure (VII-b):

[0506] (ZD m ) j XD m - (VII-b); where

[0507] X is a polyhydrogen-bonded group or a disulfide group;

[0508] j = 1 when X is divalent, and j = 0 when X is monovalent.

[0509] 55. The composition according to any one of aspects 1-53 of the first additional exemplary aspect, wherein the composition further comprises the oligomer according to embodiment 54 of the second additional exemplary aspect.

[0510] The third additional exemplary aspect includes the following implementation:

[0511] 56. A self-healing coated optical fiber, said self-healing coated optical fiber comprising:

[0512] Glass fiber, wherein the glass fiber optionally comprises a core layer and a cladding layer;

[0513] A first coating is disposed around and in contact with the glass fiber;

[0514] Optionally, an ink layer is disposed around and in contact with the first or second coating;

[0515] The first coating is a cured product of the composition, wherein the composition: (a) is as described in any one of embodiments 1-50 of the first additional illustrative aspect, and / or (b) comprises an oligomer as described in embodiment 51 of the second additional illustrative aspect.

[0516] 57. A self-healing coated optical fiber according to embodiment 56 of the third additional illustrative aspect, wherein the self-healing optical fiber is configured to repair more than 20%, more than 50%, more than 75%, or more than 90% of the voids formed in the coating within a time period of no more than 48 hours, or more than 8 hours, or more than 1 hour, or more than 5 minutes, or more than 1 minute, while the self-healing coated optical fiber is maintained at a temperature below 80°C, or preferably below 60°C, or preferably 50°C, or preferably 25°C, as determined visually by microscopic imaging at 40x or 100x magnification.

[0517] 58. A self-healing coated optical fiber according to any one of the foregoing embodiments 56-57 of the third additional illustrative aspect, wherein the first coating disposed around and in contact with the glass fiber is a primary coating;

[0518] The self-healing coated optical fiber further includes a secondary coating disposed around and in contact with the primary coating.

[0519] 59. A self-healing coated optical fiber according to any one of embodiments 56-57, wherein the first coating is the only coating on the self-healing coated optical fiber.

[0520] 60. The self-healing coated optical fiber according to any one of the foregoing embodiments 56-59 of the third additional illustrative aspect, wherein the glass transition temperature of the first coating or the primary coating 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.

[0521] Unless otherwise specified, the term % by weight refers to the amount of a particular component by mass relative to the entire liquid radiation-curable composition in which it is incorporated.

[0522] Unless otherwise specified herein or obviously contradicted by the context, the use of the terms “a,” “an,” and “the,” and similar indicative words, in the context of describing the invention (especially in the context of the following claims), should be interpreted as encompassing both the singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise indicated herein, the description of value ranges herein is intended only as a shorthand method of referring to each individual value falling within that range, and each individual value is incorporated into this specification as if it were individually referenced herein. Unless otherwise stated herein or obviously contradicted by the context, all methods described herein may be performed in any suitable order. Unless otherwise claimed, the use of any and all examples or illustrative language (e.g., “for example”) provided herein is intended only to better illustrate the invention and not to limit the scope of the invention. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0523] This document describes preferred embodiments of the invention, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments will be apparent to those skilled in the art after reading the foregoing description. The inventors encourage those skilled in the art to appropriately employ such variations, and the inventors desire to practice the invention in ways different from those specifically described herein. Therefore, the invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the invention covers any combination of all possible variations of the foregoing elements.

[0524] 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 to the present invention without departing from the spirit and scope of the claimed invention.

Claims

1. A composition for coating optical fibers, the composition comprising: Reactive monomer components and / or reactive oligomer components; A self-healing component comprising a molecule having one or more self-healing segments, at least three urethane linking groups and one or more polymerizable segments, wherein the self-healing segments include 2-ureido-4-pyrimidinone (UPy) groups; Initiator components; as well as Additive components; in (a) The self-healing component is present in an amount greater than 30% by weight relative to the weight of the composition; and (b) The composition has a self-repairing fragment of greater than 0.015 equivalent per 100g of the composition. The self-repairing component described herein has a theoretical molecular weight (MW) between 500 and 2000 in g / mol. 理论 ).

2. The composition according to claim 1, wherein the self-healing component is present in an amount of 30-80% by weight relative to the weight of the composition; and The composition contains 0.015 to 0.10 equivalents of self-repairing fragments per 100g of the composition.

3. The composition according to any one of claims 1-2, wherein 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, wherein the weight content of the solvent can be determined by size exclusion chromatography (SEC).

4. The composition according to any one of claims 1-2, wherein the self-healing component comprises a compound having a backbone derived from polyether polyols, polyester polyols, poly(dimethylsiloxane), disulfide polyols, or combinations thereof.

5. The composition according to any one of claims 1-2, wherein the composition comprises one or more of the following: (1) An adhesion accelerator compound, wherein the adhesion accelerator compound is a part of the additive component; (2) Adhesion-promoting functional group, wherein the adhesion-promoting functional group is part of the oligomer component, the monomer component, or the self-healing component; and / or (3) Antioxidant, wherein the antioxidant is part of the additive component.

6. The composition according to any one of claims 1-2, wherein the reactive monomer component, the reactive oligomer component, and the self-healing component each comprise one or more polymerizable segments, wherein the polymerizable segments include: (i) Radiation-curable segments; (ii) Thermocurable segments; or (iii) Both radiation-curable segments and heat-curable segments.

7. The composition of claim 1, wherein at least 50%, at least 60%, at least 75%, at least 90%, at least 99%, or 100% of the equivalent of the self-repairing fragment in the composition is composed of a 2-ureido-4-pyrimidinone (UPy) group.

8. The composition according to any one of claims 1-2, wherein the self-repairing component comprises The first molecule possessing the first self-repairing fragment; and A second molecule possessing a second self-repairing fragment; The first self-repairing fragment of the first molecule is configured to bond with the second self-repairing fragment of the second molecule; The first self-repairing fragment and the second self-repairing fragment are independently multi-hydrogen-bonded groups.

9. The composition according to claim 8, wherein the bond dissociation energy between the first self-repairing fragment and the second self-repairing fragment is between 9-100 kcal / mol or between 30-60 kcal / mol.

10. The composition of claim 9, wherein the first self-healing fragment and the second self-healing fragment are configured to form a dimer, wherein the dimer has three or four hydrogen bonds, wherein the dimer comprises a first straight chain and a second straight chain, the first straight chain being connected to each of the three or four hydrogen bonds on one side of the first self-healing fragment, the second straight chain being connected to each of the three or four hydrogen bonds on one side of the second self-healing fragment, wherein each of the first straight chain and the second straight chain comprises fewer than seven covalent bonds.

11. The composition according to claim 10, wherein the dimer is based on one of the following structures (I)-(V): Wherein R is selected from an organic substituent, and the organic substituent has a reactive group attached to the substituent; The reactive groups mentioned therein include acryloyloxy, methacryloyloxy, hydroxyl, amino, vinyl, alkynyl, azide, aziridine, silyl, siloxy, silyl hydride, thio, isocyanate, protected isocyanate, epoxy, carboxylate, hydrogen, F, Cl, Br, I, or maleimide groups.

12. The composition according to claim 1, wherein the composition has 0.015 to 0.05 equivalents of 2-ureido-4-pyrimidinone (UPy) groups per 100g of the composition.

13. The composition of claim 6, wherein the polymerizable segment of the reactive monomer component, the reactive oligomer component, and the self-healing component comprises (meth)acrylate groups; The composition wherein the composition has 0.1 to 0.4 equivalents of (meth)acrylate groups per 100g of the composition; and / or The ratio of the equivalent of (meth)acrylate groups to the equivalent of 2-ureido-4-pyrimidinone (UPy) groups in the composition is less than 14, or from 3 to 10.

14. The composition according to any one of claims 1-2, wherein the self-healing component comprises a compound having a carbamate group, wherein the carbamate group is a reaction product of a diisocyanate compound; The monomer components mentioned above include 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 acrylate; and The initiator component comprises one or more photoinitiators, including acylphosphine oxide photoinitiators, α-hydroxy ketone photoinitiators, and / or Norrish type II photoinitiators.

15. The composition according to any one of claims 1-2, wherein the self-healing component has a glass transition temperature (Tg) of -30°C to 20°C.

16. The composition according to any one of claims 1-2, wherein the composition has a segmental modulus of 0.1 MPa to 5 MPa or 0.1 MPa to 0.8 MPa, wherein the segmental modulus is determined using MTS Criterion. TM Model 43.104 is defined for membranes prepared from the composition; and / or In the 50s -1 The shear rate and viscosity less than 15 Pascals per second (Pa·s), or 0.05 Pascals per second to 5 Pascals per second, measured at 25°C.

17. The composition according to any one of claims 1-2, wherein, relative to the weight of the composition, The monomer and / or oligomer components are present in an amount of 10% to 65% by weight; The self-healing component is present in an amount greater than 30% to 80% by weight; The initiator is present in the form of 0.01% to 10% by weight; The additive is present in quantities ranging from 0% to 59.99% by weight; The total weight of all of the components mentioned herein is 100%.

18. A method for manufacturing coated optical fibers, the method comprising the steps of: Glass optical fibers are provided by drawing the glass optical fibers via a stretching tower; A primary coating composition is applied to the surface of the glass optical fiber; Apply a dose of radiation energy, including ultraviolet light, sufficient to at least partially cure the primary coating composition; The secondary coating composition is applied onto the primary coating composition; the primary coating composition and the secondary coating composition are exposed to at least one radiation source capable of emitting ultraviolet radiation to affect the curing of the primary coating composition and the secondary coating composition, so as 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. The primary coating composition is the composition according to any one of claims 1-17.

19. A coated optical fiber, said coated optical fiber being manufactured by the method according to claim 18 and comprising a coating, said coating being a cured product of the composition according to any one of claims 1-17.

20. An optical fiber cable comprising a plurality of optical fibers disposed therein, wherein at least one optical fiber is the optical fiber according to claim 19.

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