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    • 专利摘要:
    LED CURE OF RADIATION CURABLE FIBER OPTIC COATING COMPOSITIONS.A radiation curable coating composition for an optical fiber comprising: at least one urethane (meth) acrylate oligomer, at least one reactive diluent manomer and at least one photo indicator is described and claimed. The composition is capable of photopolymerization when coated on an optical fiber and when irradiated by a crazy light emitter (LED), having a wavelength of about 100 nm to about 900 nm, to provide a cured coating on the fiber optics, with the cured coating having an upper surface, and the cured coating having a React Acrylate Unsaturation (% RAU) percentage on the upper surface of about 60% or greater. Also described and claimed are the processes for coating an optical fiber with the LED curable coating for optical fiber and a coated optical fiber where the coating has been cured by application of LED light.
    公开号:BR112012018396A2
    申请号:R112012018396-6
    申请日:2010-12-16
    公开日:2020-10-13
    发明作者:Timothy Edward Bishop；Keqi Gan
    申请人:Dsm Ip Assets B.V.；
    IPC主号:
    专利说明:

    'LED CURE OF FIBER OPTIC COATING COMPOSITIONS
    CURABLE BY RADIATION Cross Reference to Related Patent Applications This patent application claims priority for US Provisional Patent Application No. 61 / 287,567 filed on December 17, 2009, which is incorporated herein by reference in its entirety. Field of the Invention The present invention relates to radiation curable coatings for optical fiber and methods of formulating these compositions. Background of the Invention The use of ultraviolet mercury arc lamps to emit ultraviolet light suitable for curing the radiation curable coatings applied to optical fiber is well known. Ultraviolet arc lamps emit light by using an electric arc to excite mercury that resides inside an inert gas environment (eg, argon) to generate ultraviolet light that effects healing. Alternatively, microwave energy can also be used to excite mercury lamps in an inert gas medium to generate ultraviolet light. Throughout this patent application, arc-excited and microwave-excited mercury lamps, in addition to various modified additive forms (ferrous metals, gallium, etc.) of these mercury lamps are identified as mercury lamps. However, the use of ultraviolet mercury lamps as a radiation source suffers from several disadvantages, including the environmental issues of mercury
    ] 2: and ozone generation as a by-product. In addition, mercury lamps typically have a low energy conversion ratio, require heating time, generate heat during operation, and consume a large amount of energy when compared to LED. (In the production of coated optical fiber, the heat generated by the mercury UV lamps can negatively impact the liquid coating due to the fact that if the coating is not formulated to avoid the presence of volatiles, these volatiles can be excited and deposit on the quartz tube surface, blocking UV rays from irradiation of the liquid coating on the glass fiber which inhibits the curing of the liquid coating to a solid.). Consequently, alternative radiation sources are being investigated.
    Light emitting diodes (LEDs) are semiconductor devices that use the phenomenon of electroluminescence to generate light. The LEDs consist of a semiconductor material doped with impurities to create a p-n junction capable of emitting light as the positive vacancies join with negative electrons when the voltage is applied. The wavelength of light emitted is determined by the materials used in the active region of the semiconductor. Typical materials used in LED semiconductors include, for example, elements from Groups 13 (III) and 15 (V) of the periodic table. Such semiconductors are referred to as III-V semiconductors and include, for example, GaAs, GaP, GaASP, AlGaAs, InGaASP, AlGalnP, and InGaN semiconductors. Other examples of semiconductors used in LEDs include Group 14 compounds (IV-IV semiconductors) and Group
    12-16 (II-VI). The choice of materials is based on multiple factors, including desired emission wavelength, performance parameters, and cost. LEDS have recently used gallium arsenide (GaAs) to emit infrared (IR) radiation and low-intensity red light. Advances in material science have led to the development of LEDs capable of emitting light with a higher intensity and shorter wavelengths, including other colors of visible light and UV light. It is possible to create LEDs that emit light anywhere from a low wavelength of about 100 nm to a high of about 900 nm. Currently, known UV LED light sources emit light at wavelengths between about 300 and about 475 nm, with 365 nm, 390 nm and 395 nm, with peak spectral productions being common. See textbooks, "Light-Emitting Diodes", by E. Fred Schubert, 2nd Edition, No. E. Fred Schubert 2006, published by Cambridge University Press.
    LED lamps offer advantages over mercury lamps in curing applications. For example, LED lamps do not use mercury to generate UV light and are typically less bulky than mercury UV arc lamps. In addition, LED lamps are instant on / off sources that do not require heating time, which contributes to the low energy consumption of LED lamps. LED lamps also generate much less heat, with greater energy conversion efficiency, have longer lamp life and are essentially monochromatic, emitting a desired wavelength of light that is regulated by the choice of materials
    '4' semiconductors used in the LED.
    Several manufacturers offer LED lamps for commercial curing applications. For example, Phoseon Technology. Summit UV Honle UV America, Inc., 1ST Metz GmbH, Jenton International Ltd., Lumios Solutions Ltd., Solid UV Inc., Seoul Optodevice Co., Ltd, Spectronics Corporation, Luminus Devices Inc., and Clearstone Technologies, are some of the manufacturers currently offering LED lamps for curing inkjet printing compositions, PVC floor covering compositions, metal coating compositions, plastic coating composition and adhesive compositions.
    In known UV curing applications for dental work, existing LED curing devices are available. An example of a well-known curing device for dental work is the Elipar "" FreeLight 2 LED for light curing from 3M ESPE. This device emits light in the visible region with a peak irradiance at 460nm.
    LED equipment is also being tested in the inkjet printing market: IST Metz has publicly presented a demonstration of its entry into UV curing via LED. This company says it has been working on LED-based UV curing technology in recent years, mainly for the inkjet market, where this technology is currently used.
    Current radiation-curable fiber optic coating compositions are not suitable for curing with LED lamps, because until now these compositions have been formulated to be cured by mercury lights
    Ú that produce a different spectral output, namely, a spectral product over various wavelengths. Although "curing conventionally" UV curable coatings for fiber optics are currently available, they can actually initiate curing when exposed to light from an LED light source, the cure speed is so slow that the coating would not cure at speeds current "fast" line speeds of over 1500 meters / minute. Therefore, it is not practical to use LED lamps currently available to cure the radiation curable coatings currently available for optical fiber.
    US Patent 7,399,982 ("the '982" patent) provides that it provides a method of coating or UV curing prints on various objects, particularly objects such as wires, cables, tubes, pipes, hoses, pipes, CDs, DVDs, golf balls, golf tees, glasses, contact lenses, string instruments, decorative labels, detachable labels, detachable stamps, doors and counters. Although the '982 patent refers to optical fiber in the background or in the context of the mechanical configuration of the coating apparatus, it does not disclose a coating composition, or ingredients therefrom, which is successfully coated and cured on an optical fiber using UV- LED. There is thus no disclosure of enabling LED curable coatings for optical fiber in the '982 patent.
    US Patent Application Publication 2007/0112090 ("publication * '090") provides that it provides a LED radiation curable rubber composition comprising an organopolysiloxane having a plurality
    '(meth) acryloyl groups, a radiation sensitizer, and an optional organic compound containing titanium.
    The publication '090 determines that the composition is useful as a protective coating agent or a sealing agent for liquid crystal display electrodes, organic electronic displays, flat panel displays, or for other electrical and electronic components.
    The publication '090 determines, in the description of the prior art, that the UV curable composition of the prior art patent (US Patent 4,733,942) comprising organopolysiloxane having a plurality of vinyl functional groups such as acryloyloxy groups or (Met) groups. acryloyloxy is unable to meet the demand or requirement that the composition must be curable by UV-LED, due to slow cure rates.
    In addition, publication '90 states that another prior art patent (US Patent 6,069,186) proposed a radiation-curable silicone rubber composition comprising an organopolysiloxane, which contained a radiation sensitive organic group containing a plurality of groups ( met) acryloyloxy at each of the molecular chain terminals, a photosensitizer and an organosilicon compound that does not contain any alkoxy groups.
    According to publication '090, the composition of the' 186 patent does not satisfy the above demand.
    Thus, there is no disclosure of enabling LED curable coatings for optical fiber in publication '090 or in any of the documents (the' 942 patent and the '186 patent) cited therein.
    US Patent Application Publication 2003/0026919 ("publication '919") provides that it discloses an apparatus
    ] resin fiber optic coating having an ultraviolet flash lamp used for coating an optical fiber with an ultraviolet curing resin, a lamp lighting circuit to make the ultraviolet flash lamp emit light, and a circuit control panel to control this lamp lighting circuit.
    The '919 publication states that, as a source of ultraviolet light, at least one ultraviolet laser diode or ultraviolet light emitting diode may be used instead of an ultraviolet flash lamp.
    Although the '919 publication states that the epoxy acrylate resin as an example of an ultraviolet curing resin, it does not provide details about the resin or a composition comprising such resin.
    The '919 publication does not disclose an optical fiber coating composition, comprising at least one acrylate oligomer, at least one photoinitiator and at least one reactive diluent monomer that is successfully coated and cured in an LED light using optical fiber.
    Thus, there is no disclosure that makes it possible to compose an LED radiation curable coating for optical fiber in publication '919. Published PCT Patent Application WO 2005/103121, entitled "Method for the photopolymerization of resin compositions", assigned to DSM IP Assets BV, describes and claims Methods for curing by Light Emitting Diode (LED) of a curable resin composition containing a photoionization system, characterized by the fact that the longest wavelength at which the maximum absorption of the photoionization system occurs (AMax PIS) is at least 20 nm below, and not more than 100 nm below, the wavelength in which O
    'maximum LED emission occurs (ALED). The invention of the present PCT patent application relates to the use of LED curing in structural applications, in particular in applications for covering or refining objects, and for objects containing a cured resin composition obtained by curing LED. This invention provides a simple, environmentally safe and readily controllable method for coating pipes, tanks and vessels, especially for such pipes and equipment that have a large diameter, in particular more than 15 cm. Thus, there is no disclosure that makes possible a composition of an LED radiation curable coating for optical fiber in publication WO 2005/103121.
    Patent application publication US 20100242299, published on September 30, 2010, describes and claims a rotatable, stackable indexable apparatus and method for UV curing of an elongated member, or at least a UV curable ink, coating or adhesive applied to it is further described comprising at least one UV-LED mounted on one side of the elongated member, and an elliptically formed reflector positioned on the other side of the elongated member opposite to at least one LED-UV. In the same patent family as Published Patent Application US 20100242299, US Patent 7,175,712 issued, issued February 13, 2007 describes and claims a UV curing apparatus and a method is provided to improve the distribution and application of UV light for UV photoinitiators in a UV-curable paint, coating or adhesive. The UV curing apparatus and method comprises sets of UV LEDs in a first row with the
    'UV LED sets spaced from adjacent UV LED sets. At least a second row of a plurality of UV LED arrays is provided next to the first row, but with the second row UV LED arrays positioned adjacent to the spaces between the adjacent UV LED arrays in the first row to thereby scale the second row of UV LED sets from the UV LED sets in the first row. Desirably, the rows of staggered UV LED arrays are mounted on a panel. Products, articles or other UV-curable objects, containing UV photoinitiators that are on or over a web can be transported or otherwise bypassed the ranks of UV LED sets for effective UV curing. This arrangement facilitates the more uniform application of UV light on UV-curable paint, coating and / or adhesives, on UV-curable products, articles or other objects. The apparatus may include one or more of the following: rollers to move the mesh, mechanisms to cause the panel to move in an orbital or reciprocal path, and an injection tube to inject a non-oxygen gas into the curing area by UV light.
    The foregoing shows that there is an unmet need to provide radiation-curable optical fiber coating compositions that are suitable for LED light curing, to provide processes for coating optical fiber with coating compositions of this type, and to provide coated optical fibers comprising coatings prepared from such compositions.
    Summary of the Invention
    : The first aspect of the claimed invention is a radiation curable coating composition for an optical fiber, wherein the composition is capable of photopolymerization when coated on an optical fiber and when irradiated by a light-emitting diode (LED) light , having a wavelength of 100 nm to 900 nm, to provide a cured coating on the optical fiber, said cured coating having an upper surface, said cured coating having a percentage of Reacted Acrylate Unsaturation (% IAR) on the surface 60% or higher.
    The second aspect of the claimed invention is a radiation curable coating composition of the first aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength: - from 100 nm to 300 nm; - from 300 nm to 475 nm, or - from 475 nm to 900 nm.
    The third aspect of the claimed invention is a radiation-curable coating composition, according to the first aspect of the claimed invention, said composition comprising: (a) at least one urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (c) at least one photoinitiator.
    The fourth aspect of the claimed invention is a radiation-curable coating composition of the third aspect of the claimed invention, wherein
    'the photoinitiator is a type II photoinitiator.
    The fifth aspect of the claimed invention is a radiation-curable coating composition of the third aspect of the claimed invention, wherein the photoinitiator is a type II photoinitiator and the composition includes a hydrogen donor.
    The sixth aspect of the claimed invention is a radiation curable coating composition of any of the first to fifth aspects of the claimed invention, wherein the coating composition is selected from the group consisting of a primary coating composition, secondary coating composition , an ink coating composition, a buffer coating composition, a matrix coating composition and an Upjacketing coating composition.
    The seventh aspect of the claimed invention is a radiation curable coating composition of any of the first to sixth aspects of the claimed invention in which at least 1.5% of the ingredients in the coating are bio-based rather than petroleum-based. , preferably at least 20% of the ingredients, more preferably at least 25% of the ingredients.
    The eighth aspect of the claimed invention is a process for coating an optical fiber comprising: (a) providing a glass optical fiber, (b) coating said glass optical fiber with at least one radiation curable coating composition
    for an optical fiber, preferably a radiation curable coating composition according to any one of the first to seventh aspects of the claimed invention, wherein said at least one radiation curable coating composition comprises: (i) at least one urethane (meth) acrylate oligomer; (ii) at least one reactive diluent monomer; and (iii) at least one photoinitiator; to obtain a glass optical fiber coated with an uncured coating, and (c) curing said uncured coating on said glass optical fiber coated by irradiation of said uncured coating with a light emitting diode (LED) light, having a wavelength of 100 nm to 900 nm, to obtain a cured coating having an upper surface, said "cured coating having a%% reacted acrylate unsaturation (% IAR) on the upper surface of about 60% or greater.
    The ninth aspect of the claimed invention is a process according to The eighth aspect of the claimed invention, wherein said glass optical fiber is provided by operating a glass stretching tower to produce the glass optical fiber, The tenth aspect of the claimed invention is a process of the ninth aspect of the claimed invention, wherein the glass stretch tower is operated at a fiber optic line speed of 100 m / min to 2500 m / min, such as 1000 m / min at 2400 m / min, or from 1200 m / min to 2300 m / min.
    The eleventh aspect of the claimed invention is a process of any one of the eighth to eleventh aspects of the claimed invention, wherein the light emitting diode (LED) has a wavelength - from 100 nm to 300 nm; - from 300 nm to 475 nm; or - from 475 nm to 900 nm.
    The twelfth aspect of the claimed invention is a process of any one of the eighth to eleventh aspects of the claimed invention, wherein the photoinitiator is a type I photoinitiator.
    The thirteenth aspect of the claimed invention is a process of any one of the eighth to eleventh aspects of the claimed invention, wherein the photoinitiator is a Type II photoinitiator and the composition includes a hydrogen donor.
    The fourteenth aspect of the claimed invention is a coated optical fiber that is obtainable by the process of any of the eighth to thirteenth aspects of the claimed invention.
    The fifteenth aspect of the claimed invention is a coated optical fiber of the fourteenth aspect of the claimed invention, wherein the coating composition is selected from the group consisting of a primary coating composition, a secondary coating composition, a coating composition ink, a buffer coating composition, a matrix coating composition and an Upjacketing coating composition.
    the sixteenth aspect of the claimed invention is a radiation curable coating composition for an optical fiber comprising: (a) at least one Ss urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (c) at least one photoinitiator; where the composition is able to undergo light curing when coated in an optical fiber and when irradiated by a light emitting diode (LED), having a wavelength of about 100 nm to about 900nm, to provide a cured coating on the optical fiber, said cured coating having an upper surface, said cured coating having a percentage of Reacted Acrylate Unsaturation (% IAR) on the upper surface of about 60% or greater.
    the seventeenth aspect of the present claimed invention is a coated optical fiber comprising an optical fiber and at least one coating, wherein said at least one coating is produced by coating the optical fiber with at least one radiation curable coating composition for a fiber optics comprising: (a) at least one urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (c) at least one photoinitiator; to obtain an uncured coated optical fiber, and said uncured optical fiber coated by irradiation with a light emitting diode (LED) having a wavelength of about 100 to about 900nm, to obtain a cured coating
    having a top surface, said cured coating having a percentage of Reacted Acrylate Unsaturation (% IAR) on the top surface of about 60% or greater. The eighteenth aspect of the claimed invention is a process for coating an optical fiber comprising: (a) operating a glass stretching tower to produce a glass optical fiber; (b) coating said glass optical fiber, with at least one radiation curable coating composition for an optical fiber, wherein said at least one radiation curable coating composition comprises: (i) at least one oligomer of ( met) urethane acrylate; 215 (ii) at least one reactive diluent monomer; and (iii) at least one photoinitiator; to obtain a glass optical fiber coated with an uncured coating, and (ec) cure said uncured coating on said glass optical fiber coated by irradiation of said uncured coating with a light emitting diode (LED) light, having a wavelength of about 100 nm to about 900 nm, to obtain a cured coating having a top surface, said cured coating having a% React Acrylate Unsaturation (% TAR) on the top surface of about 60% or greater .
    the nineteenth aspect of the claimed invention is a radiation curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the diode light
    'light emitter (LED) has a wavelength of about 100 nm to about 300 nm.
    The twentieth aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength of about 300 nm at about 475nMm.
    The twenty-first aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength of about 475 nm at about 900nm.
    The twenty-second aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the photoinitiator is a type I photoinitiator.
    The twenty-third aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the photoinitiator is a type II photoinitiator and the composition includes a hydrogen donor.
    The twenty-fourth aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein the coating composition is selected from the group consisting of a primary coating composition, a coating composition secondary, an ink coating composition, a buffer coating composition, a matrix coating composition and an Upjacketing coating composition.
    The twenty-fifth aspect of the claimed invention is a radiation-curable fiber optic coating composition of the sixteenth aspect of the claimed invention, wherein at least about 15% of the ingredients in the coating are bio-based, rather than bio-based. Petroleum.
    The twenty-sixth aspect of the claimed invention is a radiation-curable fiber optic coating composition of the twenty-fifth aspect of the claimed invention, wherein at least about 20% of the ingredients in the composition are biobased, rather than Petroleum.
    The twenty-seventh aspect of the present claimed invention is a radiation-curable fiber optic coating composition of claim 11, wherein at least about 25% of the ingredients in the composition are bio-based rather than petroleum-based.
    The twenty-eighth aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength from about 100 nm to about 300 nm.
    The twenty-ninth aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength from about 300 nm to about 475 nm.
    The thirtieth aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the light emitting diode (LED) light has a wavelength of about 475 nm to about 900 nm.
    The thirty-first aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the photoinitiator is a type I photoinitiator.
    The thirty-second aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the photoinitiator is a type II photoinitiator and the composition includes a hydrogen donor.
    The thirty-third aspect of the claimed invention is an optical fiber coated with the seventeenth aspect of the claimed invention, wherein the coating composition is selected from the group consisting of a primary coating composition, a secondary coating composition, a coating composition ink, a buffer coating composition, a matrix coating composition, and an Upjacketing coating composition.
    The thirty-fourth aspect of the claimed invention is a process of the 18th aspect of the claimed invention, wherein the optical fiber line speed is from about 100 m / min to about 2500 m / min.
    The thirty-fifth aspect of the claimed invention is a process of the 18th aspect of the claimed invention, wherein the optical fiber line speed is from about 1000 m / min to about 2400 m / min.
    The thirty-sixth aspect of the claimed invention is a process of the 18th aspect of the claimed invention, wherein the optical fiber line speed is from about 1200 m / min to about 2300 m / min.
    Detailed Description of the Invention Throughout this patent application the following terms have the meanings indicated: Optical fiber: a glass fiber that carries light along its inner core. The light is kept in the fiber optic core by total internal reflection. This causes the fiber to act as a waveguide. The fiber consists of a core surrounded by a covering layer, both of which are made of dielectric materials. To confine the optical signal to the core, the refractive index of the core must be greater than that of the coating.
    In a typical Single Mode optical fiber (see definition below) the outer diameter of the glass core is about 8 to about 10 microns. In a typical MultiMode optical fiber (see definition below) the outer diameter of the glass core is about 50 to about 62.5 microns. In a typical optical fiber, the outer diameter of the cover is about 125 microns. (see diagram, page 98, article entitled "Optical Fiber Coatings" by Steven R. Schmid and Anthony F. Toussaint, DSM Desotech,
    'Elgin, Illinois, Chapter 4 of the Special Fiber Optics Manual, edited by Alexis Mendez and T.F. Morse, 92007 by Elsevier Inc.). Optical fibers that support many propagation paths or transverse modes are called Multi-Mode (MMF) fibers, while those that can only support a single mode are called Single-Mode (SMF) fibers.
    Primary coating: is defined as the coating in contact with the covering layer of an optical fiber. The primary coating is applied directly to the fiberglass and, when cured, forms a soft, elastic, adherent and compatible material that encapsulates the fiberglass. The primary coating serves as a buffer to cushion and protect the fiberglass core when the fiber is folded, tied, rolled up or otherwise handled. During the early years of development of optical glass fibers, the primary coating was sometimes referred to as the "internal primary coating". The outer diameter of the primary coating is about 155 to about 205 microns (see diagram, page 98, article titled "Optical Fiber Coatings", by Steven R. Schmid and Anthony F. Toussaint, DSM Desotech, Elgin, Illinois, Chapter 4, Special Fiber Optics Manual, edited by Alexis Mendez and TF Morse, 92007 by Elsevier Inc.).
    Secondary coating: The secondary coating is applied over the primary coating and functions as a protective, resistant outer layer that prevents damage to the fiberglass during processing and use. Certain characteristics are desirable for the secondary coating. Before curing, the secondary coating composition must have adequate viscosity and be able to cure quickly to enable processing of the optical fiber. After curing, the secondary coating must have the following characteristics: sufficient stiffness to protect the encapsulated glass fiber, still sufficient flexibility for handling (ie, module), low water absorption, low tackiness to enable the manipulation of the optical fiber, chemical resistance, and sufficient adhesion to the primary coating.
    To achieve the desired characteristics, conventional secondary coating compositions generally contain urethane-based oligomers in high concentration with monomers being introduced into the secondary coating composition as reactive diluents to reduce viscosity.
    During the early years of development of optical glass fibers, the secondary coating was sometimes referred to as the "external primary coating". In a typical optical glass fiber the outer diameter of the secondary coating is about 240 to about 250 microns.
    Ink or ink coating: it is a radiation-curable coating comprising pigments or dyes that make the color of the coating visible to correspond with one of the various standard colors used in the identification of optical fiber upon installation. An alternative to using an ink coating is to use a secondary coating that comprises pigments or dyes. A “secondary coating comprising pigments and / or dyes is also known as a coating
    '"secondary color". In a typical optical glass fiber the typical thickness of an ink or ink coating is about 3 microns and about 10 microns. Matrix or Matrix Coating: is used to manufacture a fiber optic tape. A fiber optic strip includes a plurality of substantially aligned, substantially planar fibers and a radiation curable matrix material encapsulating the plurality of optical fibers.
    Locose Tube Configuration: As an alternative to be manufactured on a fiber optic tape, optical fibers can be implanted in the field, which is known as a "loose tube" configuration. A loose tube configuration is when the many fibers are positioned in a hollow protective tube. The fibers can be surrounded by a protective jelly on the Loose Tube or they can be surrounded by another type of protective material or The loose tube can contain only optical fibers.
    Coating. “Upjacketing or Upjacketing: is a radiation-curable coating that is applied over a colored secondary coating or over a coating layer of paint in a relatively thick amount, which causes the outer diameter of the coated optical fiber to increase the desired thickness 400 microns, 500 microns, or 600 microns or 900 microns tight buffered fibers. These diameters are also used for the finished upjacketing coated optical fibers described as either 400 microns, 500 microns or 600 microns or 900 microns of "tight buffered" fibers.
    Primary coatings and secondary coatings and ink coatings and matrix coatings and radiation curable Upjacketing coatings for optical fiber are described and claimed in US Patents; 4,472,019, 4,496,210, 4,514,037, 4,522,465, 4,624,994,
    4,629,287, 4,682,851, 4,806,574; 4,806,694; 4,844,604;
    4,849,462; 4,932,750;
    5,093,386; 5,219,896; 5,292,459; 5,336,563; 5,416,880;
    5,456,984; 5,496,870; 5,502,145; 5,596,669; 5,664,041;
    5,696,179; 5,712,035; 5,787,218; 580,431 1; 5,812,725;
    5,837,750; 5,845,034; 5,859,087; 5,847,021; 5,891,930;
    5,907,023; 5,913,004; 5,933,559; 5958584, 5977202, 5986018, 5998497;
    6,014,488; 6,023,547; 6,040,357; 6,052,503; 6,054,217;
    6,063,888; 6,080,483; 6,085,010; 6,107,361; 61 10,593;
    6,130,980; 6,136,880; 6,169,126; 6,180,741; 6,187,835; 6,191 187; 6,197,422; 6,214,899; 6,240,230; 6,246,824; 6,298,189;
    6,301,415; 6,306,924; 6,309,747; 6,339,549; 6,323,255;
    6,339,666; 6,359,025; 6,350,790; 6,362,249; 6,376,573;
    6,391,936; 6,438,306; 6,472,450; 6,528,553; 6,534,557;
    6,538,045; 6,563,996; 6,579,618; 6,599,956; 6,630,242;
    6,638,616; 6,661,959; 6,714,712; 6,775,451; 6,797,740;
    6,852,770; 6,858,657; 6,961,508;
    7,043,712; 7,067,564; 7,076,142; 7,122,247; 7,135,229;
    7,155,100; T.171.103 ,; 7,214,431; 7,221,841; 7,226,958;
    7,276,543 and 7,493,000, all of which are incorporated by reference, in their entirety.
    UVA radiation is radiation with a wavelength between about 320 and about 400nm.
    UVB radiation is radiation with a wavelength between about 280 and about 320 nm.
    UVC radiation is radiation with a wavelength between about 100 and about 280 nm. As used here, the term "renewable resource material" is defined as a starting material that is not derived from petroleum, but as a starting material derived from a plant, including fruits, nuts and / or plant seeds. These plant-derived materials are ecological and bio-based materials. Thus, these raw materials are also often referred to as "bio-based" materials or "natural oil" materials.
    In addition to the understood definition of "bio-based", according to the FRSIA (Farm Security and Rural Investment Act), "bio-based products" are products determined by the US Secretary of Agriculture as " goods of a commercial or industrial nature "(with the exception of food or feed), composed in whole or in a significant part of biological products, forest materials or renewable domestic agricultural materials, including plant, animal or marine materials.
    The biobased content can be determined by testing with ASTM Method D6866-10, METHODS OF
    STANDARD TESTS FOR DETERMINING THE BIOLOGICAL BASED CONTENT OF SOLID, LIQUID AND GASEOUS SAMPLES USING RADIOCARBON ANALYSIS. This method, similar to radiocarbon dating, compares how much of a decomposing carbon isotope remains in a sample with how much it would be in the same sample if it were made from recently fully grown materials. The percentage is called the bio-based content of the product.
    People skilled in the radiation-curable coating technique are aware of how to select ingredients and understand whether the ingredient is bio-based or petroleum-based. What is different now is the complete abundance of bio-based raw materials suitable for use in radiation-curable coatings. For example, bio-based raw materials can be found in polyols and other ingredients.
    the sixteenth aspect of the claimed invention is a radiation curable coating composition for an optical fiber comprising: (a) at least one urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (e) at least one photoinitiator; in which the composition is capable of undergoing photopolymerization when coated in an optical fiber and when irradiated by a light emitting diode (LED), having a wavelength of about 100 to about 900 nm, to provide a cured coating on the optical fiber, said cured coating having an upper surface, Said cured coating having a percentage of Reacted Acrylate Unsaturation (% IAR) on the upper surface of about 60% or greater, Urethane (meth) acrylate oligomers are well known in the technique of radiation curable coatings for optical fiber. See pages 103-104 of the article entitled "Optical Fiber Coatings" by Steven R.
    Schmid and Anthony F. Toussaint, DSM Desotech, Elgin,
    Illinois, Chapter 4 of the Manual of Special Optical Fibers, edited by Alexis Mendez and T.F. Morse, 92007 by Elsevier Inc., for a succinct summary of these types of oligomers. For further descriptions of urethane (meth) acrylate oligomers suitable for use in the invention claimed in the present claimed invention see US patents, previously listed in this document and previously incorporated by reference.
    As indicated on pages 103-104 of the article, "Optical Fiber Coatings" as described in the previous paragraph, urethane (meth) acrylate oligomers are based on combinations — stoichiometric diisocyanates (DICsS), polyols and some types of species hydroxy-functional terminators containing a UV-reactive terminal. Depending on the desired properties, different types of polyols are chosen. These polyols include, but are not limited to, polyether polypropylene - * glycol (PPG) and polyether polytetramethylene glycol (PTMG). Polyols are typically used in the synthesis of urethane (meth) acrylate oligomers.
    The components of oil-based urethane (meth) acrylate oligomers, such as polyester and polyether polyols have several disadvantages. The use of such polyester or polyether polyols contributes to the depletion of petroleum derived oil, which is a non-renewable resource. In addition, the production of a polyol requires the investment of a large amount of energy because the oil needed to make the polyol must be drilled, extracted and transported to a refinery from where it is refined and processed to purified hydrocarbons which i are subsequently converted into. alkoxides and finally to the finished polyols. As the consumer public becomes increasingly aware of the environmental impact of this production chain, consumer demand for more environmentally friendly products will continue to grow. To help reduce depletion of petroleum-derived oil, while satisfying increased consumer demand, it would be advantageous to partially or fully replace the petroleum-derived polyester or polyether polyols used in the production of urethane (meth) acrylate oligomers by components environmentally responsible and more renewable.
    Reactive Diluent Monomers are well known in the technique of optical fiber radiation curable coatings, see pages 105 of the article entitled “Optical Fiber Coatings” by Steven R. Schmid and Anthony F. Toussaíint, DSM Desotech, Elgin, Illinois, Chapter 4 of the Manual of Special Optical Fibers, edited by Alexis Mendez and TF Morse, º2007 by Elsevier Inc., for a succinct summary of these types of reactive diluting monomers. For further descriptions of reactive diluting monomers suitable for use in the claimed invention see US patents listed earlier in this document and incorporated earlier by reference.
    In consultation with suppliers of raw materials used in the manufacture of radiation-curable coatings for optical fiber, it is possible to identify alternative bio-based raw materials for selective inclusion in the coatings. By emphasizing the importance of choosing to synthesize the oligomer and the coating made with the oligomer with bio-based raw materials, it is possible to synthesize radiation-curable coatings for optical fiber in which at least about 15% of the ingredients in the coating are bio-based instead of oil-based.
    In one embodiment, the radiation curable optical fiber coating composition of the claimed invention is such that at least about 15% of the ingredients in the coating are bio-based, rather than petroleum-based.
    In one embodiment, the radiation curable fiber optic coating composition of the claimed invention is such that at least about 20% of the ingredients in the coating are bio-based, rather than petroleum-based.
    In one embodiment, the radiation curable optical fiber coating composition of the claimed invention is such that at least about 25% of the ingredients in the coating are bio-based, rather than petroleum-based.
    The compositions of the present invention include a free radical photoinitiator since urethane (meth) acrylate oligomers require a free radical photoinitiator. In general, photoinitiators are well known in the art of coatings, curable by optical fiber radiation. See pages 105 of the article entitled “Optical Fiber Coatings” by Steven R. Schmid and Anthony F. Toussaint, DSM Desotech, Elgin, Illinois, Chapter 4 of the Manual of Special Optical Fibers, edited by Alexis Mendez and TF Morse, 92007 by Elsevier Inc., for a succinct summary of these types of photoinitiators. For further descriptions of photoinitiators suitable for use in the present claimed invention see US patents listed earlier in this document and previously incorporated by reference.
    Typically, free radical photoinitiators are divided into those that form radicals by cleavage, known as "Norrish Type I" and those that form radicals by hydrogen abstraction, known as "Norrish type II". "Norrish type II" photoinitiators require a hydrogen donor, which serves as the free radical source.
    To successfully formulate a radiation curable coating for optical fibers, it is necessary to analyze the wavelength sensitivity of the photoinitiator (s) present in the coating to determine whether they will be activated by the LED light chosen to provide the polymerization.
    For LED light sources emitting in the 300 - 4756m wavelength range, especially those emitting 365nm, 390Nm, or 395nm, examples of suitable absorbent photoinitiators in this area include: benzoylphosphine oxides, such as, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (Lucirin TPO from BASF) and 2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide (Lucirin TPO-L from BASF), bis oxide (2,4,6- trimethylbenzoyl) -phenylphosphine (Irgacure 819 or BAPO de Ciba), 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropanono-l (Irgacure 907 de Ciba), 2-benzyl-2- (dimethylamino) - l- [4- (4-
    morpholinyl) phenyl] -1-butanone (Irgacure 369 de Ciba), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) - butan-l-one (Irgacure 379 from Ciba), 4-benzoyl-4'-methyl diphenyl sulfide (Chivacure BMS from Chitec), 4.4! bis (diethylamino) benzophenone (Chivacure EMK de Chitec), and 4,4'-bis (N, N'-dimethylamino) benzophenone (Michler's ketone). Also suitable are the mixtures thereof.
    Additionally, photosensitizers are useful in conjunction with photoinitiators in curing with LED light sources that emit in this wavelength range. Examples of suitable photosensitizers include: anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone, thioxanthones and xanthones, such as isopropyl thioxanthone, 2-chlorotioxanthone, 2,4-diethyloxoxanone and 1-chloro-4-propoxyoxanthone, methyl benzoyl format (Darocur MBF de Ciba), methyl-2-benzoyl benzoate (Chivacure OMB de Chitec), 4-benzoyl-4'-methyl diphenyl sulfide (Chivacure BMS de Chitec ), 4,4'-bis (diethylamino) benzophenone (Chivacure EMK de Chitec).
    When photosensitizers are used, other absorbent photoinitiators at shorter wavelengths can be used. Examples of such photoinitiators include: benzophenones, such as benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, and dimethoxybenzophenone, and, 1-hydroxyphenyl ketones, such as 1-hydroxycyclo-phenyl ketone, phenyl (1-hydroxy -isopropyl) - ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone, and 4-isopropylphenyl (11-hydroxy) ketone, benzyl dimethyl ketal, and oligo- [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] (Esacure KIP 150 from Lamberti). It is possible that UV LED light sources are designed to emit light at shorter wavelengths.
    For LED light sources emitting at wavelengths between about 100 and about 300 nm, absorbent photoinitiators with the shortest wavelengths can be used.
    Examples of such photoinitiators include: benzophenones, such as benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, and dimethoxybenzophenone, &, 1-hydroxyphenyl ketones, such as l-hydroxycyclo-phenyl ketone, phenyl (l- hydroxy) ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone, and 4-isopropylphenyl (1-hydroxy-isopropyl) ketone, benzyl dimethyl ketal, and oligo- [ 2-hydroxy-2-methyl-l1- [4- (L-methylvinyl) phenyl] lpropanone] l (Esacure KIP
    150 from Lamberti). LED light sources can also be designed to emit visible light, which can also be used to cure fiber optic coatings, paints, buffers, and matrix materials.
    For LED light sources that emit light at wavelengths between about 475 nm to about 900 nm, examples of suitable photoinitiators include: camphorquinone, 4,4'-bis (diethylamino) benzophenone (Chivacure EMK de Chitec), 4 , 4'-bis (N, N'-dimethylamino) benzophenone (Michler's ketone), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 or BAPO de Ciba), metallocenes, such as bis (eta 5-2-4- cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl titanium (Irgacure 784 from Ciba), and photoinitiators
    visible light from Spectra Group Limited, Inc., such as H-Nu-470, H-Nu-535, H-Nu-635, H-Nu-Blue-640 and H-Nu-Blue-660. In one embodiment of the claimed invention, the light emitted by the LED is UVA radiation, which is radiation with a wavelength between about 320 and about 400 nm.
    In an embodiment of the claimed invention, the light emitted by the LED is UVB radiation, which is radiation with a wavelength between about 280 and about 320 nm.
    In an embodiment of the claimed invention, the light emitted by the LED is UVC radiation, which is radiation with a wavelength between about 100 and about 280 nm.
    In an embodiment of the claimed invention, the present composition comprises, in relation to the total weight of the composition, from about 0.5% by weight to about 7% by weight of one or more free radical photoinitiators. In one embodiment, the present composition comprises, in relation to the total weight of the composition, from about 1% by weight to about 6% by weight of one or more free radical photoinitiators, in relation to the total weight of the composition. In another embodiment, the present composition comprises, in relation to the total weight of the composition, from about 2% by weight to about 5% by weight of one or more free radical photoinitiators.
    Typically, cationic photoinitiators are not required or desired in radiation curable coatings based on urethane (meth) acrylate oligomers to function as photoinitiators. However, it is known that the use of small amounts of commercially available cationic photoinitiators in
    : radiation to function chemically as a source of photolactent acid. Photolacting acid has value in the coating since its presence is known to enhance fiber strength, See US Patent Number 5,181,269.
    The fiber optic production process offers a unique condition for the application of LED. It is well known that current LED light (360 nm, and longer) can provide a good cure through a coating layer because its longest wave of its longest wavelength is suitable for good penetration.
    Regarding surface curing, it has been observed in LED curing of other types of coatings, that the LED curing results on the coating surface are less than satisfactory due to oxygen inhibition. Oxygen inhibition of LED-induced surface curing is not emitted in fiber optic production, because fiber optic surface inertization with inert nitrogen gas during curing of coatings has been standard in the fiber optic industry for some time. In practice for optical fiber coatings with radiation-curable coatings, the curing environment of the coating is in a small, controlled quartz tube surrounding area with a nitrogen atmosphere, resulting in very low oxygen levels being present (so low as much as 20 ppm). Thus, the LED can offer good cure through and good surface cure of fiber optic coatings.
    It is anticipated that there will be a transition period for the introduction of LED lamps for the fiber industry
    Optics. During this period, they can be used in conjunction with conventional mercury lamps, instead of replacing them completely, (this paragraph has been moved to the fundamentals of the invention.) Measuring the amount of cure that a (met ) Radiation-curable urethane acrylate is generally made by conducting a "Reactive aAcCcrylate Unsaturation Percentage" (abbreviated by "% ARI"). For the coatings of the claimed invention, after curing with an LED light having a wavelength of about 100 nm to about 900 nm, the% IAR on the top surface of the coating is about 60% or greater, preferably about from 70% or greater, more preferably, about 75% or greater, more highly preferably about 80% or greater, more preferably about 85% or greater, most highly preferably about 90% or greater, and most highly preferably about 95% or more. It is possible to achieve a 100%% IAR using LEDs to cure the compositions of the claimed invention.
    It is the upper surface of the coating where the% IAR is measured, because, as previously described; LED light is expected to provide good cure through. However, the amount of cure on the upper surface is critical to reaching the indicated level in order to produce viable coated optical fiber.
    The seventeenth aspect of the present claimed invention is a coated optical fiber comprising an optical fiber and at least one coating, wherein said at least one coating is produced by coating the
    optical fiber with at least one radiation curable coating composition for an optical fiber comprising: (a) at least one urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (e) at least one photoinitiator; to obtain an uncured coated optical fiber, and cure said irradiated uncured coated optical fiber with a light emitting diode (LED) light having a wavelength of about 100 nm to about 900 nm, to obtain a cured coating having an upper surface, said cured coating having a percentage of Reacted Acrylate Unsaturation (% IAR) on the upper surface of about 60% or greater.
    The new radiation curable compositions of the present invention claimed can be applied to conventional commercially available optical fibers, fold-resistant optical fiber, photonic crystal fiber and can also be applied over airtight optical fiber. The radiation curable coatings of the claimed invention are feasible for application to both Single Mode and MultiMode optical fibers.
    In the coating of an optical fiber, the optical fiber is first stretched in a stretch tower and then the primary coating is applied, and with wet to dry processing, the next step is for an LED to be used to emit enough light to cure the primary coating, said primary coating cured having a percentage of Reacted Acrylate Unsaturation (% TIAR) on the upper surface of about 60% or greater.
    With wet-to-wet processing the next step is to apply the secondary coating.
    Either way, after the primary coating is applied, then the secondary coating is applied to the top of the primary coating, so LEDs are used to emit light to cure the radiation curable coatings on the optical fiber resulting in the secondary coating being cured. .
    LEDs are commercially available. Commercially available LED suppliers have been listed earlier in this document.
    After the secondary coating is cured, a layer of "ink coating" is optionally applied, and then the ink and coated optical fiber can be further configured in a Loose Tube configuration or placed together with other coated and ink optical fibers. in a "set of tapes" and a radiation curable matrix coating is used to keep the optical fibers in the desired location in the set of tapes, or in some other type of configuration suitable for implantation in a telecommunications network.
    It is also possible that individual coated fibers can be coated with an "upjacketing" coating that increases the outside diameter of the fiber considerably., Upjacketing coated fibers can be dyed, colored or coated with starch (clear coated). Fibers with upjacketing coating can be processed for the implantation of a telecommunications network.
    It is also possible to group the fibers together in multiple arrays that may or may not be flat, thus producing an intensified ribbon structure or blown fiber model.
    In one embodiment of the claimed invention, the radiation curable coating is being used either as a primary coating, or as a secondary coating, or as a matrix coating, or as an ink coating or as an upjacketing coating. the nineteenth aspect of the claimed invention is a process for coating an optical fiber comprising: (a) operating a glass stretching tower to produce a glass optical fiber; (b) coating said glass optical fiber with at least one radiation curable coating composition for an optical fiber, wherein said at least one radiation curable coating composition comprises: (1) at least one (met) oligomer ) urethane acrylate; (ii) at least one reactive diluent monomer; and (iii) at least one photoinitiator; to obtain a glass optical fiber coated with an uncured coating, Ee (ec) cure said uncured coating on said glass optical fiber coated by irradiation of said uncured coating with a light emitting diode (LED) light, having a wavelength of about 100 nm to about 900 nm, to obtain a cured coating having an upper surface, said cured coating having a Reactive Acrylate% Unsaturation (% IAR) on the upper surface of about 60% or bigger.
    In an embodiment of the process of the third aspect of the claimed invention, for application of an Upjacketing coating the line speed of the optical fiber is at least about 25 m / minute.
    In an embodiment of the process of the third aspect of the present invention claimed, for the application of the Upjacketing coating the line speed of the optical fiber is at least about 100 m / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the primary and secondary coatings the line speed of the optical fiber is at least about 500 m / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the primary and secondary coatings the line speed of the optical fiber is at least about 750 m / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the primary and secondary coatings the line speed of the optical fiber is at least about 1000 m / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the paint coating the line speed of the optical fiber is no more than about 3000 m / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the primary and secondary coatings the line speed of the optical fiber is no more than about 2500 m / minute.
    In an embodiment of the process of the third aspect of the claimed invention, for the application of
    'primary and secondary coatings the line speed of the optical fiber is no more than about 2400 m / minute.
    In a process embodiment of the claimed third aspect of the present invention, for the application of the primary and secondary coatings the optical fiber line speed is no more than about 2300 m / minute. In a process embodiment of the third aspect of the present invention. claimed for the application of primary and secondary coatings the line speed of the optical fiber is no more than about 2100 m / min.
    In an embodiment of the process of the third aspect of the present invention claimed, for the application of the primary and secondary coatings the line speed of the optical fiber is from about 100 m / min to about 2500 m / min for the application of the Primary and Secondary. In another embodiment of the process of the third aspect of the claimed invention, the optical fiber line speed is from about 100 m / min to about 2400 m / min. In another embodiment of the process of the third aspect of the claimed invention, the line speed of the optical fiber is from about 1000 m / min to about 2400 m / min. In another embodiment of the process of the third aspect of the claimed invention, the line speed of the optical fiber is from about 1000 m / min to about 2300 m / min. In another embodiment of the process of the third aspect of the claimed invention, the optical fiber line speed is from about 1200 m / min to about 2300 m / min. In another embodiment of the process of the third aspect of the claimed invention, the optical fiber line speed is from about 1200 m / min to about
    4th 2100 m / min.
    In an embodiment of the process of the third claimed aspect of the present invention, for application of the paint layer, the line speed of the optical fiber is between about 500 meters / minute and 3000 meters / minute. In an embodiment of the process of the third claimed aspect of the invention, for application of the paint layer, the line speed of the optical fiber is between about 750 meters / minute and about 2100 meters / minute.
    In an embodiment of the process of the third aspect of the present claimed invention, for the application of the upjacketing coating, the optical fiber is run at a line speed of between about 25 meters / minute and 100 meters / minute.
    The specific examples disclosed here are to be considered as primarily illustrative. Various changes, in addition to those described, will undoubtedly occur to those skilled in the art, and such modifications should be understood as forming a part of the present invention as they fall within the spirit and scope of the attached claims.
    EXAMPLES The present invention is further illustrated with a number of examples, which should not be considered as limiting the scope of the present invention. The components listed in these examples have the following trade names, are available from the listed source and have the indicated chemical composition .
    Table 1. Description of the components used in the examples
    Components Description Number of Provider or Registration
    CAS BHT Stabilizer 3,5- / 128-37-0 Asland di-tert-butyl Hydroxy toluene to Chivacure 2- | Photosensitized | 83846-86-0 Chitec ITX r 2-isopropyl thioxanthone Chivacure Photoinitiator of 83846-85-9 Chitec BMS Chivacure 4-benzol-4'-methyl diphenyl sulfide Photoinitiator | 75980-60-8 Chitec TPO 2,4,6-trimethylbenzoyl diphenylphosphine CN-110 Ooligomer | 55818-57-0 Sartomer bifodnol acrylate A epoxy CN120% Z Oligomer | 55818-57-0 Sartomer bifodnol acrylate A CN549 epoxy treta-acrylate | Property | Amine modified polyester sartomer
    CN971A80 80% oligomer | Property | + 42978-66- urethane acrylate sartomer in SR-306 5 Darocur 1173 | Photoinitiator of | 7473-98-5 Ciba 2-hydroxy-2-methyl-1-phenol propane Corning Corning Ebercril 350 | Silicone property [argacure 264 | [arasa ema = Irgacure 369 | Photoinitiator 1- | 119313-12-1 | Ciba hydroxy cyclohexyl phenyl ketone Irgacure 819 | 2-benzyl-2- 162881-26-7 | Ciba (dimethylamino) -1- (4- (morpholino) phenyl] - 1-butanone Irgacure 907 | Photoinitiator 2- | 71868-10-5 Ciba methyl-1- [4- (methylthio) phenyl] - 2- morpholinopropane-1 Irgacure Photoinitiator 2- | 106797-53-9 | Ciba 2959 hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-
    [Lion co |] | | Irganox Antioxidant 41484-35-9 Ciba 1035 thiodiethylene bis- (3,5-di-tert-butyl-4s-hydroxy) hydroxycinnamate Ooligomer A PPG / TDI / HEA Property | DSM Urethane acrylate Desotech oligomer, PM = 1580 Dispersion of / 20% dispersion 72102-84-2 DSM Cromophthalmic pigment | + 15625-89- | Desotech Orange orange on SR-351 5 SR-238 Monomer | 13048-33-4 Sartomer hexanediol diacrylate SR-295 Tetra- monomer | 4986-89-4 + | Sartomer acrylate | 3524-68-3 pentaerythriol SR-306 Monomer of | 42978-66-5 Tripropylene glycol diacrylate SR-349 | 64401-02-1 Ethoxylated bisphosphonol A sartomer SR-351 | 15625-89-5 Trimethylpropane triacrylate s es E | ethoxylate 87-0 SR-506 Monomer | 5888-67-1 Sartomer isobornyl acrylate Tinuvin 123 Stabilizer | 129757-67-1 | Ciba bis- light (1-
    octyloxy-2,2,6,6-
    tetramethyl-4-
    piperidinyl) sebaca to Dispersion of | 60% dispersion | / 13463-67-7 DMS dioxide pigment | + 15625-89- | Desotech white titanium on SR-351 5
    Table 2A.
    Secondary Coatings and Paints Using
    Dome Black Diamond UV LED light source at 8 m / min in the air [[less [menpro2 | mxengios - [exenpao + | Components | This is an | Example of This is an | Example of (quantity- example Invention, example Invention, des in% p) Comparativ | Om Cures | Comparative | Cures o Cures | LED light | Cures | with 365 nm light with 365 LED
    Systems Systems | Fusion 300 nm
    Fusion 300 W / in wW light / in UV lamp
    UV and D steam mercury lamp
    D steam
    'ae mercury | onsgender a | soon | aa | | [teaching ago | eos] | ema [| oo] ane [| | eme PP ans | 2236 | ses The wing | nes] the year DP | 23] | ss | so Dos DO | | A E E A] | smsos | so | if | 09 | ae | oemase | aso [| 42 | 56 | 5066 | White pigment dispersion 3.80 8.55 Chivacure orange pigment dispersion 0.50 0.47 Em
    TPO “= = | A 184 819
    E 2907
    ELAS 1173 [ensvaare | O [sw | 1 |
    | Bo PK Eos 2-ITX [ass [an] 300 1035 [mr ns | 0.46 | [eee asso [OP 500 | as [eople | bone [esto | om | os | | % ISR at 42.6 69.04 50.7 61.1 upper surface% ISR at 85.1 85.1 56.9 72.3 lower surface Table 2B.
    Secondary coatings and paints, as described in Table 2A Using Phoseon RX Fireflex LED light source at 8 m / min in air [[memos [mentos [menio7 [mention 6 | This is an Example This is an Example of the example of the example Invention, Comparati- | Invention, Comparati- | Formulation for Formulation for Example Formulation for Formulation | 4 for Cures Cures Do for Cures Invention, for example example 2 | for Example | Cures with 1 with light 3 with LED light LED systems 365 nm Fusion 365 nm Fusion 300 W / 300 W / in UV lamp D light UV lamp mercury vapor lamp D % ISR at 45.7 61; 05 44.8 65.7 upper surface% ISR at 88.3 291.0 73.8 80.6 lower surface Table 3, Secondary Coatings using UV LED Summit light source at Paint Coating Example Comparative Example - | Invention, Formulation of | Formulation of Example 1 | / Example 1, Cures with | light cures LED systems at 365 Fusion 300 W / | mm in UV light of D mercury vapor [25 nin, nierogen - | | |
    Lower RE PPP
    LU [200 nin, ierogen | % of ISR ma meetíi me | 74.0 top bottom Table 4. Paints Using the UV Summit LED light source in the Paint Coating Example Comparison Formulation - | EXAMPLE 3 of (Invention formulation, Example 3) Cures with light Cures with LED at 365 nm Systems Fusion 300 W / in UV light from mercury vapor D lamp [200 mms, aterogemto [| superior Lo [200 nin, mierogenio - | | |
    Table 5. Conventional Curable Coatings (Comparative Example) and LED Curable Primers Components (quantities | EXxXample Example of in% p) Comparative invention, Cures with | Cures with light 365 LED systems Fusion 300 W / | nm in UV light of D lamp of mercury vapor Acrylate - of - urethane polyether [only to Ds | resoxanthone and isopropiza | = | as | [target 20as | as | es | y-mercaptopropyl trimethoxy 1.0 1.0 silane Table 6. Conventional Curable Matrix Material (Comparative Example) and LED Curable
    '50 Components (quantities Example Example of in% p) Comparative invention, Cures with Cures with light 365 LED systems Fusion 300 W / nm in UV light from D lamp of urethane mercury vapor' [sas o ao | [station 268 [to | = | ensvacure 90 | as [| . | | gacure and Pa | | ensvacure ms [ao [wings à Table 7. Conventional curable coating (Comparative Example) and LED curable buffer Components (Example quantities Example in% p) Comparative invention, Cures with Cures with
    LED Fusion Light Systems 300 W / 365 nm in UV light from lamp D with urethane mercury vapor | partnerw 2213 - | o | - | [station 619 [| to | | enivacure sm a [ara ao | Table 8. Conventional Curable Coating Cures (Comparative Example) and LED curable buffer with visible light source LED Components Example Example of (quantities in% p) Comparative invention, Cures with light Cures LED systems at 455 Fusion 300 W / nm in UV light from D lamp with urethane mercury vapor | cansorguinona Po | [teaching Table 9. Conventional Curable Coating Cures (Comparative Example) and LED Curable Buffer with UVB Light Source LED Components Example Example of (quantities in% p) Comparative invention, Cures with light cures LED systems a 285 Fusion 300 W / nm in UV light from D mercury vapor lamp Acrilaco —of - urethane polyether | stopped for | rgscure for a | rgscure 29 [a | [eople | 20 |
    Table 10, Conventional Curable Coating Cures (Comparative Example) and LED Curable Buffer with UVC Light Source LED Components Example Example of (quantities in% p) Comparative invention Cures with light Cures 210 Fusion LED systems W / nm in UV light from mercury vapor D lamp 35.0 Polyether acrylate 35.0 urethane emo2-z | pairs 2195 po | enivacure mo o O -
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    NE ug —AA g o e | ooa "el e / el e) ol o & | a | e | 8/8] Se) 8) 3) 8/88 al dl eta e ee RA 3) 3 |. a als aps |« | Ss seje sl Za g | & al & E) HE | 7 to “o 2 4 o It is bad Gn | ooo A) SA = mA | Aa) oo E |) is Sl | 2a) o) o É É Ss)” 8 A ST | 4 / ul ol Aa o H DU) 1 / Aa; A el. "O = vv) O) s4 | A | no mi o E DT) Oo, & / mm H |) $ s | à Mm> bo p | the ME | als a o o O, o 41 Ao n D | Dl 84) gl 4) oO) <| 89 HA)! & ww) N | |) | 4) 4 3) 4H 0/84 | / o vv) oSO | 4/4] 4) 4 / O) 3) 6 / 5/0 Al à mo a | ca | l O) lime | o) 6) 3 | / o El E | = |) 8) 8/4) 8 | S / a 8) 5 / o & |) 6 | e) << al 8 a) 8/8
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    H er]. A n “1 2 U o As
    Reactive Acrylate Unsaturation Percentage for the primary coating abbreviated as% IAR of the Primary Test Method: The degree of cure on the top surface of a primary coating on an optical fiber or metal wire is determined by FTIR using a diamond ATR accessory . FTIR instrument parameters include: 100 co-added scans, 4 cm resolution, DTGS detector, 4000 - 650 cmº spectrum range, and approximately 25% reduction in standard mirror speed to improve signal-to-stop -noise. Two spectra are needed; one of the uncured liquid coatings that corresponds to the coating on the fiber or yarn and a primary coating on the fiber or yarn.
    The spectrum of the liquid coating is obtained after completely covering the diamond surface with the coating. The liquid should be from the same batch that is used to coat the fiber or yarn, if possible, but the minimum requirement is that it must be of the same formulation. The final shape of the spectrum should be absorbance.
    A thin film of contact cement is spread over the central area of a 1-inch square piece of 3-mil Mylar film. After the contact cement becomes sticky, a piece of wire or optical fiber is placed on it. The sample is placed under a low-power optical microscope. The coatings on the fiber or yarn are cut through the glass using a sharp scalpel. The coatings are then cut longitudinally down on the top side of the fiber or yarn approximately 1 cm, making sure that the cut is clean and that Oo
    86.
    secondary coating does not bend in the primary coating. Then, the coatings are spread open over the contact cement in such a way that the primary coating next to the glass or wire is exposed as a flat film. The fiberglass or wire is broken in the area where the primary coating is exposed.
    The primary coating exposed on the Mylar film is mounted in the center of the diamond with the axis of the fiber or wire parallel to the direction of the infrared beam. Pressure should be placed on the back of the sample to ensure good contact with the crystal. The resulting spectrum should not contain any absorbances from the contact cement. If contact cement peaks are observed, a new sample must be prepared. It is important to run the spectrum immediately after sample preparation, instead of preparing multiple samples and running spectra when all sample preparations are complete. The final shape of the spectrum should be absorbance.
    Both the liquid and the cured coating measure the peak area of both acrylate double bond peaks at 810 cmº and a reference peak in the 750 - 780 cm region. The peak area is determined using the baseline technique where a baseline is chosen to be tangent to the minimum absorbance on each side of the peak. The area under the peak and above the baseline is then determined. The integration limits for the liquid and the cured sample are not identical, but they are similar, especially for the reference peak.
    The ratio of peak acrylate area to the area of the o reeene — n O AAÚA [AÔ AAA ”AAÀ .W .." "" "nn nn 22 - 2 / A 2 7] T] wao At)“ ”. NÓ çiwuiirCôIO Sneneir- = ÉE Sn tt tttéeéP GC $) IA = tA = ** “a | VIIP ”BÚú'óoo". Ns ") ssE: ss $ .0s 0 II.
    Ú 0 "0 87 is vv 04 Rats = (Benz Re) x 100: R, reference peak is determined for both the liquid and the cured sample.
    The degree of cure, expressed as a percentage of Reacted Acrylate Unsaturation (% IAR), is calculated from the equation below: Where R, is the ratio of the net sample area and R; is due to the area of the cured primary.
    The percentage of Reacted Acrylate Unsaturation for the secondary coating is abbreviated as% IAR for The Tecundário Test Method.
    The degree of cure of the secondary coating on an optical fiber is determined by FTIR using a diamond ATR accessory.
    The FTIR instrument parameters include: 100 co-added scans, 4-in 'resolution, DTGS detector, a spectrum range of 4000 - 650 cm ”, and a reduction of approximately 25% in the standard mirror speed to improve the ratio of signal-to-noise.
    Two spectra are needed; one of the uncured liquid coatings corresponding to: coating on the fiber and one of the external coatings: on the fiber.
    The spectrum of the liquid coating is obtained after | completely cover the diamond surface with the coating.
    The liquid should be from the same batch that is used to coat the fiber if possible, but the minimum requirement is that it must be of the same formulation.
    The final shape of the spectrum should be absorbance.
    The fiber is mounted on the diamond and sufficient pressure is placed on the fiber to obtain a suitable spectrum for quantitative analysis.
    For maximum spectral intensity, the fiber must be placed in the center of the
    'diamond parallel to the direction of the infrared beam. If 7 insufficient intensity is obtained with a single fiber, 2-3 fibers can be placed on diamond parallel to each other and as close as possible. The final shape of the spectrum should be absorbance.
    For both the liquid O and the cured coating, the measurement of the area of the acrylate double bond peak at 810 cmº * and a reference peak in the region of 750 - 780 cm. The peak area is determined using the baseline technique in which a baseline is chosen to be tangent to the minimum absorbance on both sides of the peak. The area under the peak and above the baseline is then determined. The integration limits for the liquid and the cured sample are not identical, but they are similar, especially for the reference peak.
    The ratio of the acrylate peak area to the reference peak area is determined for both liquid 6% RAU = (R, - R,) x 100
    R as for the cured sample, The degree of cure, expressed as a percentage of Reacted Acrylate Unsaturation (% TAR), is calculated from the equation below: where R, is the ratio of the area of the liquid sample and Rx Is the ratio of secondary coating area cured.
    All references, including publications, patent applications and patents cited herein, are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were established in their entirety here.
    'The use of the terms "one, one" and "ones, ones" and "o, a, os,] as" and similar referents in the context of the description of the invention (especially in the context of the following claims) should be interpreted as meaning cover both the singular and the plural, unless otherwise stated in this document or in clear contradiction with the context. The terms "comprising" "having", "including" and "containing" are to be interpreted as open terms (ie, which means "including, but not limited to,"), unless otherwise stated. The recitation of the ranges of values described here is merely intended to serve as an abbreviated method of referring individually to each separate value that falls within the range, unless otherwise indicated here, and each separate value is incorporated into the report. descriptive as if it were individually recited here. All methods described here can be performed in any appropriate order, unless otherwise indicated here or otherwise clearly contradicted by the context. The use of any and all examples, or exemplary language (for example, "such as") provided here is intended only to further clarify the invention and does not represent a limitation on the scope of the invention, unless otherwise stated. No language in the specification should be interpreted as indicating any unclaimed element as essential to the practice of the invention.
    Preferred embodiments of the present invention are described here, including the best way known to the inventors for carrying out the invention. Variations in preferred modalities may become evident to
    "o. versed in the technique by reading the previous description".
    The inventors expect those skilled in the art to employ such variations as appropriate, and the inventors intend that the invention be practiced in a manner other than that specifically described herein.
    Thus, the present invention includes all modifications and equivalents of the subject matter in the appended claims here as permitted by applicable law.
    In addition, any combination of the elements described above in all possible variations thereof is encompassed by the invention, unless otherwise indicated here or clearly contradicted otherwise by the context.
    权利要求:
    Claims (15)
    [1]
    1. Composition of radiation curable coating for an optical fiber, characterized by the fact that the composition is capable of undergoing photopolymerization when coated on an optical fiber and when irradiated by a light emitting diode (LED) light, having a length of wave from 100 nm to 900 nm, to provide a cured coating on the optical fiber, said cured coating having an upper surface, said cured coating 10 having a React Acrylate Unsaturation (% IAR) percentage on the upper surface of 60 % or greater.
    [2]
    2. Composition of radiation-curable coating according to claim 1, characterized by the fact that | whereas light emitting diode (LED) light has a wavelength of - from 100 nm to 300 nm; - from 300 nm to 475 nm; OR: - from 475 nm to 900 nm. THE
    [3]
    Radiation-curable coating composition according to claim 1, characterized in that said composition comprises: (a) at least one urethane (meth) acrylate oligomer; (b) at least one reactive diluent monomer; and (c) at least one photoinitiator.
    [4]
    4. Radiation-curable coating composition according to claim 3, characterized by the fact that the photoinitiator is a type I photoinitiator.
    [5]
    5. Composition of radiation-curable coating according to claim 3, characterized by the fact that
    : 2, that the photoinitiator is a type II photoinitiator and the composition includes a hydrogen donor.
    [6]
    A radiation-curable coating composition according to any one of claims 1, 2, 3, 4 OR 5, characterized in that the coating composition is selected from the group consisting of a 'primary coating, a composition secondary coating composition, an ink coating composition, a buffer coating composition, a matrix coating composition, and an Upjacketing coating composition.
    [7]
    7. Radiation-curable coating composition according to any one of claims 1, 2, 3, 4, 5 OR 6, characterized by the fact that at least 15% of the ingredients in the coating are bio-based, rather than base oil, preferably at least 20% of the ingredients, more preferably, at least 25% of the ingredients.
    [8]
    8. Process for coating an optical fiber, À 20 characterized by the fact that it comprises: (a) providing a glass optical fiber, (b) coating said glass optical fiber, with at least one coating composition curable by radiation to an optical fiber, preferably a radiation curable coating composition according to any one of claims 1, 2, 3, 4, 5, 6 or 7, wherein said at least one radiation curable coating composition comprises: (1) at least one urethane (meth) acrylate oligomer;
    E 3 7 (ii) at least one reactive diluent monomer; and (iii) at least one photoinitiator; to obtain a glass optical fiber coated with an uncured coating, and (ce) cure said uncured coating on said glass optical fiber coated by irradiation of said uncured coating with a light emitting diode (LED) light, having a wavelength of 100 nm to 900 nm, to obtain a cured coating having a top 10 surface, said cured coating having a &% Reacted Acrylate Unsaturation (% IAR) on the top surface of about 60% or greater .
    [9]
    9. Process according to claim &, characterized by the fact that said glass optical fiber is provided by the operation of a glass stretching tower to produce the glass optical fiber.
    [10]
    10. Process according to claim 9, characterized by the fact that the glass stretch tower is operated at a fiber optic line speed and 20 from 100 m / min to 2500 m / min, such as 1000 m / min at 2400 m / min, or from 1200 m / min to 2300 m / min, q.
    [11]
    Process according to any of claims 8, 9 or 10, characterized in that the light emitting diode (LED) light has a wavelength from - from 100 nm to 300 nm; - from 300 nm to 475 nm; OR - from 475 nm to 900 nm.
    [12]
    12. Process according to any of claims 8, 9, 10 or 11, characterized by the fact that
    % that the photoinitiator is a type I photoinitiator.
    [13]
    13. Process according to any of claims 8, 9, 10 or 11, characterized in that the photoinitiator is a type II photoinitiator and the composition includes a hydrogen donor.
    [14]
    14. Coated optical fiber characterized by the fact that it is obtainable by the process according to any one of claims 8 to 13.
    [15]
    15. Optical fiber coating according to + 10 claim 14, characterized in that the coating composition is selected from the group consisting of a primary coating composition, a secondary coating composition, an ink coating composition, a composition buffer coating, a matrix coating composition, and a jacketing coating composition. O
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    IN2012DN05061A|2015-10-09|
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    EP2513002A1|2012-10-24|
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    JP2015212222A|2015-11-26|
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    JP6197197B2|2017-09-20|
    CN106082706A|2016-11-09|
    BR112012018396B1|2021-06-01|
    US20120196122A1|2012-08-02|
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    法律状态:
    2020-10-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
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    PCT/US2010/060652|WO2011075549A1|2009-12-17|2010-12-16|Led curing of radiation curable optical fiber coating compositions|
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