WO2021141719A1

WO2021141719A1 - Curable black ink compositions

Info

Publication number: WO2021141719A1
Application number: PCT/US2020/064406
Authority: WO
Inventors: John William BOTELHO; Elvis Alberto ZAMBRANO
Original assignee: Corning Incorporated
Priority date: 2020-01-06
Filing date: 2020-12-11
Publication date: 2021-07-15

Abstract

Described herein are black ink compositions. In one embodiment, the ink composition comprises: (a) a radiation-curable carrier system, the radiation-curable carrier system comprising a photoinitiator and a radiation-curable component; and (b) a blackening agent comprising two or more colored pigments, wherein the ink is black as determined by Munsell scale TIA-598-D. Also described herein are methods for making the black ink compositions as well as articles including the ink compositions such as, for example, an optical fiber coated with the composition.

Description

CURABLE BLACK INK COMPOSITIONS

[0001] This Application claims priority under 35 USC §119(e) from U.S. Provisional Patent Application Serial Number 62/957,374 filed on January 6, 2020, and which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

[0002] The present disclosure generally relates to the preparation of curable black ink compositions and articles such as optical fibers coated with such compositions.

BACKGROUND

[0003] Optical fibers products have a variety of applications and end-uses. Depending upon the application of the fiber, it is desirable for the fiber to have a colored coating. Colored coatings are needed to distinguish individual optical fibers in ribbons and cables, and the optical communications industry has established color standards for coated fibers. The addition of a colored coating on the fiber generally involves applying a coating composition containing a pigment to the fiber and subsequently curing the coating composition with UV light to form a colored coating. It is desirable to use a common manufacturing platform to produce fibers with coatings having a variety of colors. The color selected, however, can have an impact on the properties of the coating. For example, black coatings typically have a lower degree of cure than coatings of other colors when cured at a common UV dose in a particular manufacturing platform. Undercuring of colored coating compositions is undesirable because it leads to poor ribbon breakout performance. Typically, the reduced degree of cure associated with conventional black coatings has been addressed by modifying the manufacturing platform to increase the UV dose applied during the curing of black coatings. UV dose can be increased either by increasing the number of UV lamps used for curing or by using UV lamps with higher irradiance. This approach not only has cost implications but also might not be platform backward compatible if space is not available for additional UV lamps on the coloring equipment. As demand for faster coloring speeds grows, the process time for curing will decrease and the UV dose available for curing will decrease. As a result, the problem of undercuring will become more severe as coloring speed increases. There is thus a need for colored coating compositions that can be cured with lower doses of UV radiation. In particular, there is a need for new black coating compositions that can be cured to a high degree of cure with low doses of UV radiation.

SUMMARY

[0004] According to one embodiment, black ink compositions are provided herein. In one embodiment, the ink composition comprises:

(a) a radiation-curable carrier system, the radiation-curable carrier system comprising a photoinitiator and a radiation-curable component; and

(b) a blackening agent comprising two or more colored pigments, wherein the ink is black as determined by Munsell scale TIA-598-D.

[0005] Also described herein are methods for making the black ink compositions as well as articles including the ink compositions such as, for example, an optical fiber coated with the composition.

[0006] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description serve to explain principles and operation of the various embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description serve to explain principles and operation of the various embodiments.

[0008] FIG. 1 shows the change in ink degree of cure of a series of curable compositions as a function of carbon black loading.

[0009] FIG. 2 shows the % absorption in the wavelength range between 360 nm to 400 nm of selected black ink compositions. DETAILED DESCRIPTION

[0010] Additional features and advantages will be set forth in the detailed description which follows and will be apparent to those skilled in the art from the description or recognized by practicing as described in the following description together with the claims and appended drawings.

[0011] As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

[0012] “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. For example, the ink compositions described herein may optionally contain a photoinitiator, where the photoinitiator may or may not be present.

[0013] As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given numerical value may be “a little above” or “a little below” the endpoint without affecting the desired result. For purposes of the present disclosure, “about” refers to a range extending from 10% below the numerical value to 10% above the numerical value. For example, if the numerical value is 10, “about 10” means between 9 and 11 inclusive of the endpoints 9 and 11. [0014] As used herein, the term “admixing” is defined as mixing two or more components together so that there is no chemical reaction or physical interaction. The term “admixing” also includes the chemical reaction or physical interaction between the two or more components.

[0015] Throughout this specification, unless the context dictates otherwise, the word “comprise,” or variations such as “comprises” or “comprising,” will be understood to imply the inclusion of a stated element, integer, step, or group of elements, integers, or steps, but not the exclusion of any other element, integer, step, or group of elements, integers, or steps. [0016] References in the specification and claims to weight percentages of a particular component in a composition or article denote the weight relationship between the element or component and any other elements or components in the composition or article for which a weight percentage is expressed. Thus, in a composition containing 2 weight percent of component X and 5 weight percent of component Y, X and Y are present at a weight ratio of 2:5, and are present in such a ratio regardless of whether additional components are used in the composition.

[0017] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of any such list should be construed as a de facto equivalent of any other member of the same list based solely on its presentation in a common group, without indications to the contrary.

[0018] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range was explicitly recited. As an example, a numerical range of “about 1” to “about 5” should be interpreted to include not only the explicitly recited values of about 1 to about 5, but also to include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3, and 4, the sub-ranges such as from 1 -3, from 2-4, from 3-5, from about 1 - about 3, from 1 to about 3, from about 1 to 3, etc., as well as 1, 2, 3, 4, and 5, individually. The same principle applies to ranges reciting only one numerical value as a minimum or maximum. The ranges should be interpreted as including endpoints (e.g., when a range of “from about 1 to 3” is recited, the range includes both of the endpoints 1 and 3 as well as the values in between). Furthermore, such an interpretation should apply regardless of the breadth or range of the characters being described.

[0019] Disclosed are materials and components that can be used for, can be used in conjunction with, can be used in preparation for, or are products of the disclosed compositions and methods. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, that while specific reference to each various individual combination and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a blackening agent is disclosed and discussed, and a number of different radiation-curable carriers are discussed, each and every combination of blackening agent and radiation-curable carrier that is possible is specifically contemplated unless specifically indicated to the contrary. For example, if a class of radiation-curable systems A, B, and C is disclosed, as well as a class of blackening agents D, E, and F, and an example combination of A + D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A + E, A + F, B + D, B + E, B + F, C + D, C + E, and C + F is specifically contemplated and should be considered from disclosure of A, B, ad C; D, E, and F; and the example combination A + D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A + E, B + F, and C + E is specifically contemplated and should be considered from disclosure of A, B, and C; D, E, and F; and the example combination of A + D. This concept applies to all aspects of the disclosure including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed with any specific embodiment or combination of embodiments of the disclosed methods, each such composition is specifically contemplated and should be considered disclosed.

[0020] The color of an ink composition or the cured product of an ink composition is the color as determined by Munsell color system under the standard TIA-598-D. In brief, the Munsell color system consists of three independent properties of color that can be represented cylindrically in three dimensions as an irregular color solid: (1) hue, which is measured by degrees around horizontal circles; (2) chroma, which is measured radially outward from the neutral (gray) vertical axis; and (3) value, which is measured vertically on the core cylinder from 0 (black) to 10 (white). In one embodiment, the ink composition or a cured product of an ink composition has a value number in the range of 0 to 2.3, or 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0. 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1 , 2.2, or 2.3, where any number can be a lower or upper end-point of a range (e.g., 0.5 to 1.5). In another embodiment, an ink composition or a cured product of an ink composition has chroma number in the range of 0 to 0.5, or 0, 0.1, 0.2, 0.3, 0.4, or 0.5, where any number can be a lower or upper end-point of a range (e.g., 0.1 to 0.3). For example, the color black refers to black as defined by the Munsell color system under the standard TIA-598-D, the color red refers to red as defined by the Munsell color system under the standard TIA-598-D, etc.

[0021] Degree of cure (DOC) is a measure of the extent to which the curing reaction has progressed. Before initiation of the curing reaction, the concentration of acrylate functional groups is high. As the curing reaction proceeds upon initiation, the concentration of acrylate functional groups decreases. A determination of the concentration of acrylate functional groups provides a measure of the extent of the curing reaction. The concentration of acrylate functional groups can be monitored before, after or at any time during the curing reaction.

[0022] The degree of cure was measured using the reacted Acrylate Unsaturation (%RAU) method and corresponds to the %RAU value determined from the method. In the %RAU method, the concentration of acrylate functional groups is assessed by FTIR. Acrylate functional groups include a carbon-carbon double bond with a characteristic absorption frequency in the infrared centered near 810 cm ¹. The intensity of this characteristic acrylate band is proportional to the concentration of acrylate functional groups. As the curing reaction proceeds, the intensity of the characteristic acrylate band decreases and the magnitude of the decrease is a measure of the degree of cure at any point during the curing reaction.

[0023] %RAU was determined by measuring the area of the characteristic acrylate band having a peak at or near 810 cm ¹. The baseline for the measurement was taken as the tangent line through the absorption minima immediately adjacent (one on the high frequency side and the other on the low frequency side) of the characteristic acrylate band with a peak maximum at or near 810 cm ¹. The area of the characteristic acrylate band was taken as the area of the band above the baseline. To account for background intensity and instrumental effects on the area measurement, the area of a reference band in the 750-780 cm ¹ region using the baseline of the characteristic acrylate band was measured. The spectral region of the reference band is outside of the absorption range of acrylate functional groups. The ratio R of the area of the characteristic acrylate band to the area of the reference band was determined. This ratio is proportional to the concentration of unreacted acrylate functional groups in the ink composition. The ratio is greatest for the ink composition before initiation of the curing reaction and decreases as the curing reaction proceeds.

[0024] %RAU is defined in the equation below:

(R_L - R_F)X 100

%RAU =

RL where RL is the ratio R for the uncured black ink composition and RF is the ratio R for the cured blank ink composition. Non-limiting methods for determining the degree of cure are provided in the Examples.

[0025] The term “cured product” refers to a product formed by curing an ink composition described herein to a degree of cure of 85% or more. In some embodiments, a cured product has a degree of cure of at least 90%, or at least 92%, or at least 95%, or at least 98%, or at least 99%.

[0026] The term “surfactant” refers to an organic compound that may be derived from a natural product, or may result from chemical modification of a natural product, or may be completely chemically synthesized. Surfactants typically contain hydrophilic head groups and hydrophobic tails. In one aspect, the head group is anionic, cationic, non-ionic, or zwitterionic. In another aspect, the tail is composed of a hydrocarbon or a glucoside. Surfactants alter the surface tension of liquids and may form micelles or bilayers in aqueous solution. Many applications of surfactants are known in the art. Surfactants are, for example, commonly employed as emulsifiers, detergents, wetting agents, and in other related uses.

[0027] The term “dispersant” refers to a chemical compound that assists in keeping the particles of a material separated from one another when they are distributed in a medium in which they would otherwise agglomerate. Dispersants are also believed to act as wetting agents. Dispersants may be ionic (anionic or cationic), non-ionic, or amphoteric. Without wishing to be bound by theory, the charged groups within the ionic dispersant coats a particle, and imparts a net charge to the particle surface. Here, the net charges on all like particles are all positive or all negative, the particles will therefore repel one another. Meanwhile, also not wishing to be bound by theory, a non-ionic dispersant can include a high molecular weight polymer with a polar group. The polar group interacts with the particle to be dispersed through hydrogen bonding, dipole-dipole interactions, London dispersion forces, and/or van der Waals interactions, while the high molecular weight component possesses sufficient bulk to achieve separation of dispersed particles due to steric effects.

[0028] The black ink compositions described herein include a photoinitiator, one or more curable components, and a blackening agent. A blackening agent is a component that imparts a black color to the black ink composition, where black is as defined by the Munsell color system under the standard TIA-598-D. The blackening agent preferably includes two or more pigments, neither of which is carbon black and neither of which individually is a black pigment. The black ink composition is a viscous liquid. In the curing process, UV light excites the photoinitiator, which in turn excites one or more of the curable components to initiate a polymerization reaction that cures the composition to form a rigid coating. Black ink compositions typically include conventional carbon black as a pigment. The conventional carbon black is present as spherical or approximately spherical particles having a mean diameter of about 1 micron. The conventional carbon black pigment used in current black ink compositions, however, is believed to reduce the degree of cure due to absorption of UV photons by the pigment when curing ink compositions used for optical fibers. Absorption of UV photons by the carbon black pigment is undesirable in optical fiber and cable applications because it prevents them from exciting the photoinitiator, which ultimately results in a reduced rate and extent of the curing reaction. As a result, black coatings prepared from black ink compositions that include conventional carbon black as a pigment tend to form slowly and to a low degree of cure under the curing conditions used to cure ink coatings in the manufacture of optical fibers.

[0029] Described herein are black ink compositions that overcome deficiencies associated with conventional black ink compositions. The black ink compositions disclosed herein exclude conventional carbon black and other black pigments and use instead blackening agents that include two or more colored pigments, where none of the two or more colored pigments individually is a black pigment. The two or more colored pigments in combination, however, impart a black color to the black ink composition. The black ink compositions described herein exhibit high degrees of cure while meeting colorimetry specifications required by the industry for black coatings. The use of the black ink compositions described herein can prevent the need to modify existing manufacturing platforms by increasing the number of UV lamps or replacing the current UV lamps with higher intensity versions, even when the speed of coloring is increased. The black ink compositions described herein lack carbon black and other black pigments.

[0030] In one embodiment, the blackening agent present in the black ink compositions described herein includes two or more colored pigments, wherein none of the two or more colored pigments is carbon black or other black pigment. Each of the two or more colored pigments can be an inorganic or organic compound. Although none of the two or more pigments individually is black, the combination of the two or more pigments is black or functions as a blackening agent in an ink composition or cured product of an ink composition. The selection and amount of each of the two or more colored pigments can be varied to produce the black ink compositions described herein. For example, combinations of two or more colored pigments can be combined in various amounts and included as a combination as the blackening agent in a colored coating composition and the color of the coating composition can be tested by colorimetric methods known in the art to confirm that the coating composition is black. In one embodiment, a blackening agent comprising two or more colored pigments includes a red, blue, yellow, brown, purple, orange, or green pigment, or a combination thereof. In another embodiment, a blackening agent comprising two or more colored pigments incudes (1) a red pigment, a blue pigment, and a yellow pigment; or (2) a red pigment and a green pigment; or (3) a purple pigment and a yellow pigment; or (4) a blue pigment and an orange pigment; or (5) a blue pigment and a brown pigment. In another embodiment, a blackening agent consists essentially of (1) a red pigment, a blue pigment, and a yellow pigment; or (2) a red pigment and a green pigment; or (3) a purple pigment and a yellow pigment; or (4) a blue pigment and an orange pigment; or (5) a blue pigment and a brown pigment.

[0031] In one aspect, the pigments used as blackening agents to produce the black inks can be dried particles prior to mixing with the radiation-curable carrier system. Depending upon the section of the pigment and radiation-curable carrier system, the pigments and radiation-curable carrier system can be admixed so that the pigment is evenly dispersed throughout the radiation-curable carrier system prior to curing. In one aspect, the black ink described herein has a pigment solids content of from about 0.5 weight percent to about 10 weight percent, or about 0.5 weight percent, about 1.0 weight percent, about 1.5 weight percent, about 2.0 weight percent, about 2.5 weight percent, about 3.0 weight percent, about 3.5 weight percent, about 4.0 weight percent, about 4.5 weight percent, about 5.0 weight percent, about 5.5 weight percent, about 6.0 weight percent, about 6.5 weight percent, about 7.0 weight percent, about 7.5 weight percent, about 8.0 weight percent, about 8.5 weight percent, about 9.0 weight percent, about 9.5 weight percent, or about 10 weight percent, where any value can be a lower or upper end-point of a range (e.g., about 2 wt% to about 8 wt%).

[0032] In another aspect, the pigments used as blackening agents to produce the black inks can be in the form of a dispersion prior to mixing with the radiation-curable carrier system. In one aspect, the dispersion can include one or more surfactants, dispersants, suspension medium, or combinations thereof. One or more colored pigments is present as a solid in the dispersion and the weight percent of the one or more colored pigments in the dispersion is referred to as the “solids content” of the dispersion. In some embodiments, blackening agents include two or more dispersions, where each dispersion includes at least one colored pigment dispersed as a solid.

[0033] In one embodiment, a blackening agent comprising two or more colored pigments includes a dispersion of a red pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent.

[0034] In another embodiment, a blackening agent comprising two or more colored pigments includes a dispersion of a red pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent.

[0035] The amount of blackening agent comprising two or more colored pigments present in the black ink composition can vary depending upon the application of the ink composition. In one embodiment, a blackening agent comprising two or more colored pigments is present in the black ink composition in an amount from about 5 wt% to about 50 wt%, or about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt%, where any value can be a lower or upper end-point of a range (e.g., about 10 wt% to about 40 wt%).

[0036] The black ink composition includes a base ink composition and a blackening agent. The base ink composition is radiation curable and is also referred to herein as a carrier or a radiation-curable carrier for the blackening agent. Radiation-curable carriers which are suitable for producing the black ink compositions contain one or more radiation-curable components. A radiation curable component has at least one functional group capable of polymerization when exposed to light such as, for example, actinic radiation. In one embodiment, the radiation-curable component is ethylenically unsaturated and can be polymerized through radical polymerization or cationic polymerization. Examples of suitable ethylenically unsaturated groups include acrylate, methacrylate, styrene, vinyl ether, vinyl ester, N-substituted acrylamide, vinyl amide, maleate esters, and fumarate esters. Radiation-curable components include oligomers and monomers. As used herein, oligomer refers to a radiation-curable compound having a repeat unit, at least two radiation-curable functional groups, and a molecular weight greater than 500 g/mol. As used herein, monomer refers to a radiation-curable compound, with or without a repeat unit, that has only one radiation-curable functional group. The molecular weight of a monomer is typically less than 500 g/mol, but may be greater than 500 g/mol.

[0037] In another embodiment, the radiation-curable oligomers or monomers include epoxy groups, thiol-ene, or amine-ene systems. Epoxy groups can be polymerized through cationic polymerization, whereas the thiol-ene and amine-ene systems can be polymerized through radical polymerization. [0038] In another embodiment, a mixture of radiation-curable monomers and/or radiation-curable oligomers can be used to achieve the desired balance of viscoelastic properties of the radiation-curable carrier. The oligomers can include a carbon-containing backbone structure where the radiation-curable functional group(s) are bound. Examples of suitable carbon-containing backbones include polyethers, polyolefins, polyesters, polyamides, and polycarbonates. The size of the carbon-containing backbone can be selected to provide the desired molecular weight. In one embodiment, the number average molecular weight of the oligomer is between about 500 g/mol to about 10,000 g/mol.

[0039] The amount of oligomer in the black ink composition is less than 20 wt%, or less than 10 wt%, or less than 5 wt%, or in the range from 0.1 wt% to 20 wt%, or in the range from 1.0 wt% to 10 wt%. In one embodiment, the black ink composition is free of oligomers.

[0040] In other embodiments, the radiation-curable carrier system can include a reactive diluent, which is used to adjust the viscosity. In one embodiment, the reactive diluent can be a low viscosity monomer having at least one curable functional group capable of polymerization when exposed to actinic radiation. This curable functional group may be of the same nature as that used in radiation-curable monomer or oligomer as described above. In one embodiment, the reactive diluent can be a monomer or mixture of monomers having an acrylate or vinyl ether functionality and a C4-C20 alkyl or polyether moiety, hexylacrylate, 2- ethylhexylacrylate, isobornylacrylate, decyl-acrylate, laurylacrylate, stearylacrylate, 2-ethoxyethoxy-ethylacrylate, lauryl vinylether, 2-ethylhexylvinyl ether, N-vinyl formamide, isodecyl acrylate, isooctyl acrylate, vinyl-caprolactam, or N- vinylpyrrolidone,

[0041] In another embodiment, the radiation-curable carrier system can include other additives such as photoinitiators, catalysts, lubricants, wetting agents, antioxidants and stabilizers.

[0042] Photoinitiators include ketonic photoinitiators and/or phosphine oxide photoinitiators. Representative photoinitiators include 1 -hydroxycyclohexylphenyl ketone (e.g., IRGACURE 184 available from BASF)); bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide (e.g., commercial blends IRGACURE 1800, 1850, and 1700 available from BASF); 2,2-dimethoxy-2-phenylacetophenone (e.g., IRGACURE 651, available from BASF); bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE 819); (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide (LUCIRIN TPO, available from BASF (Munich, Germany)); ethoxy(2,4,6-trimethylbenzoyl)- phenylphosphine oxide (LUCIRIN TPO-L from BASF); and combinations thereof. Preferred photoinitiators have an absorption band with a maximum wavelength of absorption that closely matches the output wavelength of common UV light sources (lamps, lasers, LEDs etc.). In various embodiments, the photoinitiator has an absorption band with a maximum wavelength of absorption in the range from 325 nm to 400 nm, or in the range from 335 nm to 395 nm, or in the range from 345 nm to 390 nm, or in the range from 355 nm to 385 nm, or in the range from 350 nm to 395 nm, or in the range from 370 nm to 395 nm.

[0043] It is further preferred that the absorption of the blackening agent at the wavelength of excitation of the photoinitiator is low so that the excitation efficiency of the photoinitiator is high. In one aspect, the black ink composition has an absorption of less than 90%, or less than 85%, or less than 80%, or less than 70%, or less than 60%, or less than 50% at each wavelength in the wavelength range of from about 360 nm to 400 nm. Absorption is expressed herein as a percent and refers to the fraction of the intensity of light incident to a sample that is absorbed by a sample with thickness of 25.4 microns (0.001 inch). Absorption is determined by measuring the transmission through and reflection from a sample of thickness 25.4 microns and is computed as a percent from the formula %A = 100% - %R - %T, where A refers to absorption, R refers to reflection and T refers to transmission. Unless otherwise specified, absorption or % absorption for a black ink composition refers to absorption or % absorption of the black ink composition in an uncured state.

[0044] It is also preferred that the black ink composition has a high tinting strength as noted above. One factor contributing to tinting strength is scattering of visible radiation. High scattering of visible radiation reduces tinting strength of black color and leads to non-black coloration of the black ink composition and/or coatings formed by curing the black ink composition.

[0045] The production of the black ink compositions can be performed using a number of different techniques. In one embodiment, the blackening agent can be dispersed in one or more of the components of the radiation-curable carrier system and then processed. For example, the blackening agent can be dispersed in a low viscosity diluent and then subjected to processing. After which, the remaining components, such as oligomers or monomers, can be combined with the processed blackening agent to form the ink composition. In another embodiment, the blackening agent and the radiation-curable carrier system can be admixed with one another using techniques known in the art including, but not limited to, ultrasonication, high shear mixing, milling, and compounding.

[0046] The black ink compositions described herein can be applied to the surface of an article using techniques known in the art. In one embodiment, the black ink composition can be applied directly to the surface of the article. In other embodiments, one or more additional polymeric layers can be applied to the surface of the article, where the black ink composition is subsequently applied to the outermost polymeric layer to provide black coloration. For example, when the article is an optical fiber, primary and secondary layers can be applied to the fiber, where the black ink composition is applied to the secondary (outer) layer. In another example, the article is an optical fiber, a primary layer is applied to the optical fiber and a secondary layer comprising a blackening agent as described herein is applied to the primary layer. In one embodiment, described herein is an optical fiber comprising: an optical waveguide; a cured primary coating layer surrounding the optical waveguide; a cured secondary coating layer surrounding the cured primary coating layer; and a cured black ink coating layer surrounding the cured secondary coating layer.

[0047] The components and methods for producing the cured primary and secondary layers as described in US publication no. 2019/0177216, which is incorporated by reference in its entirety, can be used herein.

[0048] The thickness of the black ink composition applied to the article can vary. In one embodiment, the thickness of the cured black ink layer is from about 1 micron to about 50 microns.

[0049] After the black ink composition has been applied to the surface of the article, the black ink composition is cured to form a black coating. In one embodiment, one or more curing lamps (e.g. UV curing lamps) or LEDs (e.g. UV LEDs) that are adapted to effect the curing of the black ink composition can be used. The degree and kinetics of the cure is at least partially controlled by the power irradiated with the one or more curing lamps or LEDs as well as the duration of exposure to the light source as well as the temperature at which curing occurs.

[0050] The wavelength of curing radiation of the black ink composition can be infrared, visible, or ultraviolet. Representative wavelengths include wavelengths in the range from 250 nm - 1000 nm, or in the range from 250 nm - 700 nm, or in the range from 250 nm - 450 nm, or in the range from 275 nm - 425 nm, or in the range from 300 nm - 400 nm, or in the range from 320 nm - 390 nm, or in the range from 330 nm - 380 nm, or in the range from 340 nm - 370 nm. Curing can be accomplished with light sources that include a lamp source (e.g. Hg lamp), an LED source (e.g. a UVLED, visible LED, or infrared LED), or a laser source.

[0051] In one embodiment, the black ink composition is characterized by a cure speed of at least about 50 percent acrylate conversion/second, more preferably between about 80 and about 500 percent acrylate conversion/second, or between about 100 and about 400 percent acrylate conversion/second. Cure speed is a measure of the percent of acrylate conversion per second (percent/s). The percentage of cure can be evaluated in accordance with the Fourier Transform Infrared Spectroscopy analyses. Basically, an uncured film is applied to an ASI DuraSamplir® ATR crystal (or equivalent) at ~1 mm thickness, the film is purged with nitrogen for 30 sec, and then irradiated to induce polymerization with, e.g., Lesco Mark II Spot cure unit and UniBlitz® VS25 Shutter Assembly with model T132 driver. The shutter is opened for a 1 sec exposure, and spectra are collected at 6 ms intervals for 0.9 sec. Following the 0.1 sec pause, spectra are again collected for 5 sec following initial exposure. The shutter again opens for a 10 sec exposure, which allows for calculation of the 100% cure band ratio. Both uncured and fully cured band ratio are calculated for each, and a cure vs. time plot is constructed using conventional software, e.g., OPUS v3.04 in OS/2 (Spectrometer operation and data manipulation), Galactic Grams32 v5.02, and MicroCal Origin v6.0. The polymerization rate, Rp, can be calculated at any point in the curve from the slope of the curve, and the maximum polymerization rate is preferably estimated as the slope of the curve from 10% conversion to 40% conversion. The reported cure speed number is the slope of the line within this range. In one embodiment, the black ink composition cures to a degree of at least 80%, at least 85%, or at least 90%. In another embodiment, the ink composition cures to a degree of from 98% to 100%. [0052] In one embodiment, the black ink composition absorbs less of the curing radiation during the curing process than carbon black, which ultimately increases the efficiency of the curing process and the degree of cure of the ink because a greater fraction of the curing radiation excites the photoinitiator. As demonstrated in the Examples, by reducing or eliminating the amount of carbon black in the black ink composition , the UV absorption of the blackening agent is reduced and a greater fraction of UV curing radiation is absorbed by the photoinitiator. In one embodiment, the black ink composition has less than or equal to 85% absorption at each wavelength in the wavelength range between 360 nm to 400 nm, which is the wavelength region generally used in UV LED cure technology. In another embodiment, the black ink composition has from about 50% to about 85% absorption at each wavelength in the wavelength range between 360 nm to 400 nm, or about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or about 85%, where any value can be a lower and upper end-point of a range (e.g., about 60% to about 80%).

[0053] The black ink compositions described herein can be applied and cured in a common continuous manufacturing process. Alternatively, the black ink composition can be applied in a common continuous manufacturing process and subsequently cured in a separate offline process. In one embodiment, the black ink compositions described herein can be applied to an optical fiber that can be used in a number of different applications such as, for example, loose tube optical cables. In another embodiment, the black ink compositions described herein can be applied to ribbon optical fibers.

[0054] The black coatings formed as cured products of the black ink compositions described herein are black as determined by the Munsell scale under standard TIA- 598-D. Various measurement techniques can be used to verify that the cured product of a black ink composition having a blackening agent as described herein is black. In one aspect, the color of an ink composition or cured product of an ink composition can be determined by colorimetry using instrumentation and techniques known in the art including, but not limited to, spectroradiometers, spectrophotometers, and a spectrocolorimeters. [0055] The black coatings formed as cured products of the black ink compositions disclosed herein have additional properties that are desirable in certain applications such as, for example, in the field of optical fibers. In one embodiment, the black coating formed as a cured product of a black ink composition described herein can have a high Young’s modulus so it can contribute to the abrasion and/or puncture resistance of the optical fiber. In some embodiments, the Young’s modulus of the black coating may be greater than about 500 MPa at room temperature, greater than about 750 MPa at room temperature, greater than about 1000 MPa at room temperature, greater than about 1250 MPa at room temperature, greater than about 1500 MPa at room temperature, greater than about 1750 MPa at room temperature, or greater than about 2000 MPa at room temperature. The black coating includes an ink coating glass transition temperature (T_g-mk). The ink coating glass transition temperature (T_g-mk) describes the temperature at which a reversible transition occurs in amorphous materials (or in amorphous regions within semicrystalline materials) where the material goes from a hard and relatively brittle “glassy” state to a viscous or rubbery state as the temperature is increased. In some embodiments, the cured black ink coating glass transition temperature (T_g-ink) is greater than or equal to 65 °C, is greater than or equal to 75 °C, is greater than or equal to 85 °C, is greater than or equal to 95 °C, is greater than or equal to 105 °C, is less than or equal to 120 °C, is less than or equal to 110 °C, or is less than or equal to 100 °C. In other embodiments, the cured black ink coating glass transition temperature (T_g-ink) may be greater than or equal to 65 °C but less than or equal to 120 °C, may be greater than or equal to 75 °C but less than or equal to 120 °C, may be greater than or equal to 85 °C but less than or equal to 120 °C, may be greater than or equal to 95 °C but less than or equal to 120 °C, or may be greater than or equal to 105 °C but less than or equal to 120 °C.

[0056] The black ink compositions described herein can be applied to articles such as, for example optical fibers and subsequently cured. The optical fibers can be part of a cable system typically used in cable television, telecommunications and other applications where optical fibers are used. For example, ribbon optical fiber can be coated with the black ink compositions described herein and subsequently cured.

EXAMPLES [0057] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, and methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of the discovery disclosed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. Numerous variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges and conditions) can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions. Evaluation of Degree of Cure

[0058] Experiments were conducted in order to evaluate the degree of cure of the black inks described herein. Dispersions of pigments and carbon black manufactured by Penn Color (blue: 9S959D; yellow: 9Y958D; red: 9R925; and carbon black: 9B385) were used in the experiments. A black ink mix was created by mixing the red, blue and yellow pigments in proportions of 35.5 wt%, 32.3 wt% and 32.3 wt%, respectively. After the preparation of each ink, the ink was left on a roller machine overnight at room temperature to rotate the bottles until the components were sufficiently mixed and ready for use in the coloring process.

[0059] The pigment mixture was then added to the base ink (i.e. , radiation-curable carrier system) composition described in Table 2 of U.S. Patent Application Publication No. 20180215661, the disclosure of which is incorporated by reference. The components of the base ink composition are listed below:

Base Ink Composition

where SR601 is ethoxylated (4) bisphenol A diacrylate. CD9038 is ethoxylated (30)bisphenol A diacrylate. Photomer 3016 is bisphenol A epoxy diacrylate (a monomer). Lucirin TPO is 2,4,6-trimethylbenzoyl)diphenyl phosphine oxide) (a photoinitiator). Irgacure 184 is 1-hydroxycyclohexylphenyl ketone (a photoinitiator). Irganox 1035 is thiodiethylene bis(3,5-di-tert-butyl)-4-hydroxyhydrocinnamate (an antioxidant). DC190 is silicone-ethylene oxide/propylene oxide copolymer (a slip agent). The concentrations of Irganox 1035 and DC190 are expressed in units of parts per hundred (pph) relative to the remainder of the base ink composition (which includes all components with concentrations expressed in units of weight percent (wt%). For example, 1 pph DC190 corresponds to 1 g of DC190 per 100 g combined of SR601 (72 g), CD9038 (10 g), Photomer 3016 (15 g), Lucirin TPO (1.5 g), and Irgacure 184 (1.5 g) in the proportions listed above.

[0060] Four controls were evaluated in this investigation. The first control is a black ink composition that included 1.50 wt% of conventional carbon black as the pigment in the base ink composition (98.5 wt%). The first control is typical of black ink compositions currently used in the art and serves as a reference for assessing the effect of pigment composition on degree of cure. A second control is a black ink composition that included 0.27 wt% of conventional carbon black as the pigment in the base ink composition (99.73 wt%). A third control was formulated by mixing 18 wt% of the black ink mix with red, blue, and yellow pigments as described above and 82 wt% base ink composition, . A fourth control was the base ink composition with no pigment or carbon black.

[0061] Each control was individually applied to a silica glass fiber at a thickness of about 3 pm to about 8 pm and cured by exposing the coated fibers to light in the range of 365 nm to 400 nm. Degree of cure was measured by Fourier Transform Infrared spectroscopy (FTIR) (BRUKER TENSOR 27 Bruker Optik). Samples were prepared as follows: A piece of coated fiber free of lumps, abrasions, and other irregularities was cut to about 12 cm long (approximately 4 ¾”). The coated fiber was cleaned by wiping the coated fiber sample with a methanol wipe. The cleaned, coated fiber was placed horizontally across the ATR crystal surface of the instrument. The ViewlR lens was lowered to its locked position such that it was in contact with and compressing the cleaned, coated fiber sample. A scan of the cleaned, coated fiber sample was collected and the spectrum was reviewed. The degree of cure for each control composition was measured using the same sample configuration and curing conditions. The results are shown in FIG. 1 for the control compositions.

[0062]The degree of cure (DOC) of the first control (1.50 % carbon black loading, labeled “Black”) was arbitrarily set to 0% and was used as a normalization reference to assess the improvement in degree of cure observed for the remaining three control compositions. The change in degree of cure for the second, third, and fourth controls relative to the first control is plotted in FIG. 1. To illustrate the negative effect of conventional carbon black on degree of cure, the second control (0.27 % carbon black loading) was tested. The data obtained are depicted in bar graph form with horizontal striping in FIG. 1 (labeled “black and clear mix”) and show that a decrease in the concentration of carbon black from 1.50 wt% in the first control to 0.27 wt% in the second controls led to a 1.3% increase in the degree of cure under the same curing conditions. These results demonstrate that conventional carbon black interferes with the curing process and leads to a reduction in the degree of cure.

[0063] The data for the black ink produced with the red, blue and yellow inks (third control) are shown in bar graph form with slanted stripes in FIG. 1 (labeled “Black mix with RBY”) and indicate an increase in degree of cure of 2.1 % relative to the first control. For comparison, the fourth control that included the base ink composition with no pigment or blackening agent was prepared and tested. The fourth control was clear in appearance and the data (labelled “Clear”) indicate that its degree of cure was 2.1% higher than the degree of cure for the first control. The results of FIG. 1 show that higher degree of cures are possible when using blackening agents as described herein instead of using conventional carbon black in ink compositions used to coat optical fibers.

Optical Properties Analysis

[0064] Transmission and reflection were measured at different wavelengths of light for several inks in order to determine the percent absorption of the ink. The samples included the black ink formulation with 1.5 wt% carbon black provided by Penn Color (carbon black: 9B385) used in the first control above, the black ink mix without carbon black used in the third control above , and the black and clear mix with 0.27 wt% carbon black used in the second control above. Each ink sample was individually deposited on a thin sheet of glass for absorption measurements at a thickness of 25.4 pm.

[0065] FIG. 2 shows the % absorption between 360 nm to 400 nm for the three ink samples. In the measurements, % transmission (%T) through the samples and % reflection (%R) from the samples was measured and % absorption (%A) was computed as 100% - %R - %T at each wavelength in the wavelength range from 360 nm to 400 nm, which is a preferred wavelength range for UV LED cure technology. The black ink formulation with 1.5 wt% carbon black (data with circle symbols) had the highest UV absorption over the wavelength range. The black ink formulation with 0.27 wt% carbon black (data with triangle symbols) had the lowest UV absorption and the black and clear mix formulation (data with diamond symbols) had an intermediate UV absorption. By reducing or eliminating the amount of carbon black in the formulation, the UV absorption of the ink is reduced, which ultimately increases the efficiency of the curing process and the degree of cure of the ink.

[0066] Clause 1 of the present disclosure extends to:

An ink composition comprising:

(b) a blackening agent comprising two or more colored pigments, wherein the ink composition lacks a black pigment and is black as defined by the Munsell color system under the standard TIA-598-D.

[0067] Clause 2 of the present disclosure extends to:

An ink composition produced by admixing

(b) a blackening agent comprising two or more colored pigments, wherein the ink composition lacks a black pigment and is black as defined by the Munsell color system under standard TIA-598-D [0068] Clause 3 of the present disclosure extends to: The ink composition of clause 1 or 2, wherein the two or more colored pigments comprises a red pigment, a blue pigment, a yellow pigment, a brown pigment, a purple pigment, an orange pigment, a green pigment, or any combination thereof.

[0069] Clause 4 of the present disclosure extends to:

The ink composition of clause 3, wherein the two or more colored pigments comprise a red pigment, a blue pigment, and a yellow pigment.

[0070] Clause 5 of the present disclosure extends to:

The ink composition of clause 3, wherein the two or more colored pigments comprise a red pigment and a green pigment.

[0071] Clause 6 of the present disclosure extends to:

The ink composition of clause 3, wherein the two or more colored pigments comprise a purple pigment and a yellow pigment.

[0072] Clause 7 of the present disclosure extends to:

The ink composition of clause 3, wherein the two or more colored pigments comprise a blue pigment and an orange pigment.

[0073] Clause 8 of the present disclosure extends to:

The ink composition of clause 3, wherein the two or more colored pigments comprise a blue pigment and a brown pigment.

[0074] Clause 9 of the present disclosure extends to:

The ink composition in any one of clauses 1-8, wherein a solids content of the two or more colored pigments in the ink composition is in a range from about 0.5 weight percent to about 10 weight percent.

[0075] Clause 10 of the present disclosure extends to:

The ink composition in any one of clauses 1-9, wherein the blackening agent comprises a dispersion of a red pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent. [0076] Clause 11 of the present disclosure extends to:

The ink composition in any one of clauses 1-9, wherein the blackening agent comprises a dispersion of a red pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent.

[0077] Clause 12 of the present disclosure extends to:

The ink composition in any one of clauses 1-11, wherein the radiation- curable component comprises a radiation-curable monomer or oligomer.

[0078] Clause 13 of the present disclosure extends to:

The ink composition in any one of clauses 1-11, wherein the ink composition has a % absorption at each wavelength between 360 nm and 400 nm less than or equal to 85%.

[0079] Clause 14 of the present disclosure extends to:

The ink composition in any one of clauses 1-11, wherein the ink composition has a % absorption at each wavelength between 360 nm and 400 nm in the range from about 50% to about 85%.

[0080] Clause 15 of the present disclosure extends to:

An article comprising a coating of the ink composition in any one of clauses

1-14.

[0081] Clause 16 of the present disclosure extends to:

A cured product of the ink composition in any one of clauses 1-14.

[0082] Clause 17 of the present disclosure extends to:

The cured product clause 16, wherein the cured product has a degree of cure of at least 85%.

[0083] Clause 18 of the present disclosure extends to:

The cured product clause 16, wherein the cured product has a degree of cure of at least 95%.

[0084] Clause 19 of the present disclosure extends to: An article comprising a cured product of the ink composition in any one of clauses 1-14.

[0085] Clause 20 of the present disclosure extends to:

The article of clause 19, wherein the article comprises an optical fiber.

[0086] Clause 21 of the present disclosure extends to:

The article of clause 20, wherein the article comprises a ribbon, the ribbon comprising the optical fiber.

[0087] Clause 22 of the present disclosure extends to:

The article of clause 20, wherein the article comprises a cable, the cable comprising the optical fiber.

[0088] Clause 23 of the present disclosure extends to:

A method of coating an article comprising: applying the ink composition in any one of claims 1 -14 to a surface of the article to produce a coated article; and curing the ink composition.

[0089] Clause 24 of the present disclosure extends to:

The method of clause 23, wherein the curing comprises exposing the coated article to UV light, infrared light, or visible light.

[0090] Clause 25 of the present disclosure extends to:

The method of clause 23 or 24, wherein the curing cured the ink composition to a degree of cure of at least 85%.

[0091] Clause 26 of the present disclosure extends to:

The method of clause 23 or 24, wherein the curing cures the ink composition to a degree of cure of at least 90%.

[0092] Clause 27 of the present disclosure extends to:

The method of clause 23 or 24, wherein the curing cures the ink composition to a degree of cure from 98 to 100%.

[0093] Throughout this publication, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the methods, compositions, and compounds herein.

[0094] Various modifications and variations can be made to the materials, methods, and articles described herein. Other aspects of the materials, methods, and articles described herein will be apparent from consideration of the specification and practice of the materials, methods, and articles disclosed herein. It is intended that the specification and examples be considered as exemplary.

Claims

What is claimed is:

1. An ink composition comprising: a radiation-curable carrier system, the radiation-curable carrier system comprising a photoinitiator and a radiation-curable component; and a blackening agent comprising two or more colored pigments, wherein the ink composition lacks a black pigment and is black as defined by the Munsell color system under the standard TIA-598-D.

2. The ink composition of claim 1, wherein the two or more colored pigments comprise a red pigment, a blue pigment, a yellow pigment, a brown pigment, a purple pigment, an orange pigment, a green pigment, or any combination thereof.

3. The ink composition of claim 2, wherein the two or more colored pigments comprise a red pigment, a blue pigment, and a yellow pigment.

4. The ink composition of claim 2, wherein the two or more colored pigments comprise a red pigment and a green pigment.

5. The ink composition of claim 2, wherein the two or more colored pigments comprise a purple pigment and a yellow pigment.

6. The ink composition of claim 2, wherein the two or more colored pigments comprise a blue pigment and an orange pigment.

7. The ink composition of claim 2, wherein the two or more colored pigments comprise a blue pigment and a brown pigment.

8. The ink composition in any one of claims 1-7, wherein a solids content of the two or more colored pigments in the ink composition is in a range from about 0.5 weight percent to about 10 weight percent.

9. The ink composition of claim 1, wherein the blackening agent comprises a dispersion of a red pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 10 weight percent to about 50 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent.

10. The ink composition of claim 1, wherein the blackening agent comprises a dispersion of a red pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, a dispersion of a blue pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent, and a dispersion of a yellow pigment that is from about 30 weight percent to about 40 weight percent of the blackening agent with a solids content of from about 0.1 weight percent to about 5 weight percent.

11. The ink composition in any one of claims 1-10, wherein the radiation-curable component comprises a radiation-curable monomer or oligomer.

12. The ink composition in any one of claims 1-11, wherein the ink composition has a % absorption at each wavelength between 360 nm to 400 nm less than or equal to 85%.

13. The ink composition in any one of claims 1-11, wherein the ink composition has a % absorption at each wavelength between 360 nm and 400 nm in the range from about 50% to about 85%.

14. An article comprising a coating of the ink composition in any one of claims 1-13.

15. A cured product of the ink composition in any one of claims 1 -13.

16. The cured product of claim 15, wherein the cured product has a degree of cure of at least 95%.

17. An article comprising the cured product of any one of claims 1-13.

18. The article of claim 17, wherein the article comprises an optical fiber.

19. The article of claim 18, wherein the article comprises a ribbon, the ribbon comprising the optical fiber.

20. The article of claim 18, wherein the article comprises a cable, the cable comprising the optical fiber.

21. A method of coating an article comprising: applying the ink composition in any one of claims 1-13 to a surface of the article to produce a coated article; and curing the ink composition.

22. The method of claim 21, wherein the curing comprises exposing the coated article to UV light, infrared light, or visible light.

23. The method of claim 20 or 21, wherein the curing cures the ink composition cures to a degree of cure of at least 90%.