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    • 专利摘要:
    The present invention includes an optical fiber coating that exhibits pressure sensitive adhesive properties. The viscoelastic window for the coating includes at least one set of coordinates within the second, third, or fourth quadrant of the window viscoelasticity of the rheological standard curve or the transition flow region, or at least not one quadrant of the window viscoelasticity of the rheological standard curve. It will not contain a single coordinate set.
    公开号:KR20040035851A
    申请号:KR10-2004-7004102
    申请日:2002-08-08
    公开日:2004-04-29
    发明作者:에드워드 제이. 퓨커스；그레고리 에프. 제이콥스；인나 아이. 쿠즈미나；케빈 알. 맥카티；환-헝 성；크리스티 엘. 시몬튼
    申请人:코닝 인코포레이티드；
    IPC主号:
    专利说明:

    Optical fiber coatings with pressure sensitive adhesive characteristics
    [3] Fiber optics are increasingly important in the field of telecommunications, which can often replace copper. This trend has a significant impact on local networks (ie, fiber-to-home use), and the use of fiber is greatly increasing. With the establishment of local area networks capable of delivering vast amounts of data to residential and commercial users in the form of data, audio and video signals, there is a growing expectation for the use of subscriber line telephone and cable TV services. In addition, the use of fiber optics for internal data, voice, and video communications in the home and commercial business sector has begun and is expected to increase.
    [4] Optical fibers typically contain a glass core, glass cladding, and at least two coatings, such as a first (or inner) coating and a second (or outer) coating. The first coating is applied directly to the glass fibers and, upon curing, forms soft, stretchable, and elastic materials that can encapsulate the glass fibers. The first coating acts as a buffer to absorb and protect the impact of the glass fiber core when the fiber is bent, cabled or wound. The second coating is applied over the first coating and functions as a sturdy protective outer layer to prevent damage to the glass fibers during operation and use.
    [5] Summary of the Invention
    [6] The coating of the present invention has desirable tack and mechanical properties such as low Young's modulus, high elongation and good adhesion to the glass surface of the optical fiber. The coatings of the present invention also provide resilience in commercial supply of raw materials and inexpensive raw materials.
    [7] The first aspect of the invention comprises an optical fiber coating. The coating of the present invention comprises a radiation curable composition comprising a reactive monomer and a photoinitiator. Chang viscoelastic window upon curing of the composition exhibits at least one set of coordinates, said coordinates being logarithmic of viscous shear modulus (G ") and elastic shear modulus (G ') in Pascals, Located in at least one of the windows defined by the window set: (1) (about 3.000, about 4.480), (about 3.000, about 3.000), (6.000, about 4.480) and (about 6.000, about 3.000); (2) ( Greater than about 3.840, about 5.180), (greater than about 3.84, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180) and (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, 5.729) or window viscoelastic windows upon curing of the composition Is any window defined by a set of windows of Not located to the right, the coordinates are logarithmic of viscous shear modulus (G ") and elastic shear modulus (G ') in Pascals: (A) (about 3.000, about 5.180), (about 3.000, about 4.480), (less than about 3.850, about 5.180), and (less than about 3.85, about 4.480); (B) (about 3.000, about 6.000), (about 3.000, about 5.180), (about 4.530, about 6.000), and (about 4.530, about 5.180); And (C) (about 4.530, about 5.729), (about 4.530, about 5.604), (about 5.112, about 5.729), and (about 5.112, about 5.604).
    [8] Other features and advantages of the present invention will be described in more detail below, and the present invention has been made through the description or practice of the present invention as set forth in the following detailed description, claims, and accompanying drawings. Will be evident from. It will be apparent that the following general description and the detailed description are only exemplary embodiments of the present invention, and as claimed, the present invention provides an overview or configuration for understanding the nature and characteristics of the present invention.
    [1] The present invention relates to Edward J. Fuchs, Gregory F. Jacobs, Inna I. Kuzmina, and Kevin R. McCarty, Huan-Hung Wong, and Christie L .. Priority is claimed to US Provisional Application No. 60 / 323,622, filed Sep. 21, 2001, entitled Fiber Optic Curing with Pressure Sensitive Adhesive Properties of Simonton.
    [2] The present invention relates to optical fibers and more particularly to the field of optical fiber coatings.
    [9] 1 is a cross-sectional view of an optical fiber coated with a dual coating system according to the present invention.
    [10] 2 is a schematic view of a process for coating optical fibers with a dual coating system in accordance with the present invention.
    [11] 3 shows an example of a viscoelastic window associated with a pressure sensitive adhesive.
    [12] 4 is a graph showing window viscoelastic windows for various test coatings and controls.
    [13] 5 is a graph showing window viscoelastic windows for various test coatings.
    [14] Reference numerals are used to more specifically describe the accompanying drawings showing preferred embodiments of the present invention. Wherever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts. One embodiment of the optical fiber coating of the present invention is shown in FIG. 1, the entirety of which is indicated by reference numeral 10.
    [15] 1 is a cross-sectional view of the coated optical fiber 10. In FIG. 1, the optical fiber 10 includes a glass core 12, an adjacent cladding layer 14 surrounding the glass core 12, and an adjacent first (internal) coating material 18 surrounding the first coating material 16. It includes. The components of the optical fiber of the present invention may optionally have a colored material such as a pigment or a dye, or additionally a colored ink coating around the coating 18.
    [16] Any conventional material used to form the glass core 12, such as that disclosed in Berkeley, US Pat. No. 4,486,212, which is incorporated by reference herein, may be used. The core is typically silica glass having a cylindrical cross section and a diameter in the range of about 5-10 μm for single-mode fibers and in the range of about 20-100 μm for multi-mode fibers. The core may optionally contain various amounts of materials that modify the refractive index of the core, such as, for example, titanium, thallium, germanium and boron oxide. Other dopants known in the art can also be added to the glass core to modify the properties.
    [17] The cladding layer 14 preferably has a refractive index less than the refractive index of the core. Cladding materials are variously used in the manufacture of glass fibers, both plastic and glass (eg, silicate and borosilicate glass). Any conventional cladding material known in the art can be used to form the cladding layer 14 in the optical fiber of the present invention.
    [18] Preferred types of fibers are single mode fibers with a large effective area (with a core diameter of less than 10 μm), for example LEAF® from New York, Corning, Corning.
    [19] Definition of the fiber
    [20] The effective area is shown in Equation 1 below, the limit value is 0 to ∞, and E is an electric field associated with light propagating in the optical waveguide.
    [21]
    [22] The effective diameter, Deff, is defined as in Equation 2 below.
    [23]
    [24] With large effective area, effective area of fiber is 60㎛2More, more preferably, the effective area of the fibers is 65 μm2Excess And most preferably the effective area of the fiber is 70 mu m.2It means exceeding. About 80 to 9070 탆2It is possible to have fibers with more effective area.
    [25] Relative refractive index% is the following equation (3), in which ni is the maximum refractive index in the region i without a specific condition, nc is the average refractive index in the cladding region without a specific condition.
    [26]
    [27] The term α-profile is a refractive index profile expressed in Δ (b)%, b is a radius, as shown in Equation 4. In Equation 4, bo is the point where Δ (b)% is the maximum, b1 is the point where Δ (b)% is 0, b is the range of bi <b <bf, where delta is as described above, and bi is α. The initial point of the profile, bf is the final point of the α profile, and α is the exponent of the real number.
    [28]
    [29] The initial and final points of the α-profile are selected and entered into the computer model. As used herein, if the α-profile is advanced according to a stepped refractive profile or other profile type, the starting point of the α-profile is the intersection of the α-profile and the stepped profile or other profile.
    [30] Polarization Maintaining Fiber is a fiber that maintains the polarization of light entering the fiber. Understand Fiber Optics, published in 1993, 2nd edition of 72, 73, 252, 253, 418, and 455 additional background information on polarity or polarization retaining fibers is incorporated by reference. . An example of polarization retaining fiber is Panda fiber, Corning, NY.
    [31] Dispersion compensating fibers are optical fibers that exhibit negative dispersion and negative dispersion slopes. Dispersion compensation fibers can be associated with transmission fibers, which exhibit positive dispersion and / or positive dispersion slopes. For further background on dispersion compensation fiber see U.S. Patent No. 60/304662, filed Jul. 11, 2001. An example of a dispersion compensation fiber is PureForm ™ fiber, available from Corning, NY.
    [32] Dispersion management fibers appear in fibers in which dispersion is replaced by portions of the fiber from positive to negative or negative to positive.
    [33] Multi-mode disgust is an optical fiber that transmits or emits multi-modes of light. An example of a multi-mode fiber is InfiniCor, commercially available from Corning, NY.
    [34] Preferably coating 16 exhibits the properties of a pressure sensitive adhesive. These properties include that the coating 15 is a tacky material and exhibits adhesion to the surface under low pressure. Techniques for determining the pressure-sensitive adhesive properties of a coating include the viscous shear modulus (G "(dynamic loss modulus)) (x-axis) of the coating by the window viscoelastic window (G '(dynamic storage modulus)) of the coating. It is to make a graph of (y-axis).
    [35] The window of a particular coating can be compared to the window viscoelastic window for other regions of the rheological master curves for the pressure sensitive adhesive of FIG. 3. In 1999, D. Satas' Handbook on Pressure Sensitive Adhesive Technology, additional background on the window viscoelastic windows of pages 171-184 of the third edition, was incorporated by reference. The coordinates of the window viscoelastic window can be represented as shown in FIG. 3 or on a logarithmic scale. Coordinates as shown in FIG. 3 are expressed in Pascals. As used herein, a particular set of viscoelastic window coordinates is denoted in Pascal unless otherwise noted. The first quadrant of the window represents the coordinates for the coating that is not pressure sensitive and is known as a rubbery region. Properties of the coating include a mixture of low loss and high modulus. The second quadrant is known as the transition-plateau region. Pressure sensitive adhesive properties exhibited by the two quadrants are high loss and high modulus. The second quadrant is also known as a high shear pressure sensitive adhesive. The third quadrant is known as a removable pressure sensitive adhesive or plateau flow region. Pressure sensitive adhesive properties of the region include low loss and low modulus. Four quadrants are known as hot and cold pressure sensitive adhesives or flow-flow regions. Characteristics associated with the quadrants include low modulus and high loss. The window also includes a transition flow region associated with a general purpose pressure sensitive adhesive. Representative features include medium modulus and medium loss.
    [36] Preferably the window viscoelastic window for a particular coating has at least one set of coordinates in the 2,3, or 4 quarter or transition-flow region. More preferably, the coating has a logarithmic scale and has at least one set of coordinates in at least one window defined by the following set of coordinate windows: (1) (about 3.000, about 4.480), (about 3.000, about 3.000) , (6.000, about 4.480) and (about 6.000, about 3.000); (2) (greater than about 3.840, about 5.180), (greater than about 3.84, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); And (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, 5.729). More preferably, at least a second set of window viscoelastic windows of the coating is located in one of the window sets of coordinates described above. Most preferably, at least a third set of window coordinates is located in one of the window sets of coordinates described above.
    [37] In one embodiment of the invention, it is preferred that at least one set of coordinates of the composition 16 is located in one of the second set of windows of the following coordinates. (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (7) (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850); (8) (about 5.440, about 4.480), (about 5.440, about 3.000), (about 6.000, about 4.480), and (about 6.000, about 3.000); (9) (about 4.530, about 3.850), (about 4.530, about 3.000), (about 5.440, about 3.850), and (about 5.440, about 3.000); (10) (about 4.106, about 5.474), (about 4.106, about 5.350), (about 4.930, about 5.474), and (about 4.930, about 5.350); (11) (about 4.232, about 5.375), (about 4.232, about 5.235), (about 4.958, about 5.375), and (about 4.958, about 5.235); And (12) (about 4.139, about 5.488), (about 4.139, about 5.409), (about 4.894, about 5.488), and (about 4.894, about 5.409).
    [38] More preferably, at least a second set of window coordinates is located in one of the second set of windows of the following coordinates: (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000 ), And (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); And (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480).
    [39] Preferably, the above-described window viscoelastic window has a deformation of the linear viscoelastic region at room temperature, preferably about 2% or less, more preferably about 1% or less, and is determined at a frequency of 0.01R / S or 100R / S. Optionally, the boundaries of each window include G "and G 'defined as follows: (G" @ 0.01R / S, G' @ 0.01R / S), (G "@ 0.01R / S, G @ 100R / S), (G "@ 100R / S, G '@ 0.01R / S), and (G" @ 100R / S, G' @ 100R / S) .Riometric Scientific, Peace Cutaway, NJ A dynamic mechanical analyzer, such as DMTA-IV by Rheometric Scientific of Piscataway, NJ), can be used for the above-described measurement methods.
    [40] For fibers that are sensitive to fine microbending, the fiber has at least one set of coordinates located in the second or fourth quadrant or transition region, more preferably in the second quadrant or transition region, and most preferably in the second quadrant. It is preferable. More preferably, the coating has at least two sets of coordinates located in two quadrants, four quadrants, transition regions, or some combination thereof. More preferably, at least three sets of coordinates are located in two quadrants, four quadrants, transition regions, or some combination thereof. Most preferably all four sets of coordinates are located in two quadrants, four quadrants, transition regions or some combination thereof.
    [41] In another embodiment of the invention, at least one set of coordinates of the window viscoelastic window of the composition 16 is on a logarithmic scale and is not located in any window defined by the set of windows of the following coordinates upon curing: (A) (About 3.000, about 5.180), (about 3.000, about 4.480), (less than about 3.850, about 5.180), and (less than about 3.85, about 4.480); (B) (about 3.000, about 6.000), (about 3.000, about 5.180), (about 4.530, about 6.000), and (about 4.530, about 5.180); And (C) (about 4.530, about 5.729), (about 4.530, about 5.604), (about 5.112, about 5.729), and (about 5.112, about 5.604). Preferably at least two coordinate sets of the coating are not located anywhere in the above-mentioned windows (A)-(C), more preferably at least three coordinate sets represented by the coating, and most preferably represented by the coating All four coordinate sets are not located anywhere in the above windows (A)-(C).
    [42] Preferably the uncured composition 16 of the coating is not solid at ambient temperature, more preferably the uncured coating is actually liquid at ambient temperature. More preferably, the coating has a defined viscosity at ambient temperature.
    [43] More preferably, the composition is a photocurable composition. The photocurable coating used in the present invention may be cured through, but is not limited to, electron beams, electromagnetic radiation (eg, light), or microwave energy.
    [44] Preferred components of the first coating composition 16 of the present invention are at least one monomer component. Preferably, the monomer is an ethylenically unsaturated monomer, more preferably a (meth) acrylate monomer. In general, suitable monomers are final homopolymers having a glass transition temperature (Tg) of about 20 ° C, preferably about 10 ° C. Generally, low molecular weight (ie about 120-600) liquid (meth) acrylate-functional monomers are added to the formulation to provide the fluidity needed to apply the coating composition with conventional liquid coating equipment. Typical acrylate-functional liquid phases in such systems include monofunctional and multifunctional acrylates (ie, monomers having two or more acrylate functional groups). An example of such a multifunctional acrylate is a double functional acrylate having two functional groups; Triple functional acrylates having three functional groups; And tetrafunctional acrylates having four functional groups. Monofunctional and multifunctional methacrylates may also be used.
    [45] Suitable ethylenically unsaturated monomers include lauryl acrylate (e.g. SR335 from Sartomer, Ageflex FA12 from CPS Chemicals (Old Bridge, NJ), and Photomer 4812 from Cognis fka Henkel (Pennsylvania), Ethoxylated nonylfetol acrylate (e.g., SR504 from Sartomer, Photomer 4003 from Cognis), caprolactone acrylate (e.g., SR 495 from Sartomer, and Union Carbide (Connecticut, Danbury) Tone M100), phenoxyethyl acrylate (e.g. SR339 from Satomer, Ageflex PEA from CPS Chemical, and Photomer 4035 from Cognis), isooctyl acrylate (SR440 from Saromer, and Age of CPS Chemical) Flex FA8), tridecyl acrylate (SR489 from Sartomer), phenoxyglycidyl acrylate (e.g., CN131 from Sartomer), lauryloxyglycidyl acrylate (e.g., Sato CN130), isobonyl acrylate (e.g., SR506 from Sartomer, and Ageflex IBOA from CPS Chemical), tetrahydrofurfuryl acrylate (SR285 from Satomer), stearyl acrylate (e.g., Sato Mercer's SR257), isodecyl acrylate (e.g., SR395 from Satomer, and AgeFlex FA10 from CPS Chemical), 2- (2-ethoxyethoxy) ethyl acrylate (e.g., SR256 from Sartomer) ), And mixtures thereof.
    [46] A list of other types of suitable monomers includes the formula:
    [47] (1) R 2 -R 1 -O- (CH 2 CH 3 CH-O) n-COCH = CH 2 ;
    [48] (2) R 1 -O- (CH 2 CH 3 CH-O) n-COCH = CH 2 ;
    [49] (3) R 2 -R 1 -O- (CH 2 CH 2 CH 2 -O) n-COCH = CH 2 ;
    [50] (4) [(CH 2 CH 3 CH-O) n- (R 3 CH 2 -O) b] xH;
    [51] (5) [(CH 2 (R 3 ) CH-O) n- (CH 2 CH 2 -O) b] xH; And
    [52] (6) [(CH 2 R 4 CH-O) n- (R 3 CH 2 -O) b] xH.
    [53] R 1 and R 2 in the above formula are aliphatic or aromatic or mixtures thereof, n = 1 to 10 and R 3 and R 4 are alkylated or alkylene oxides which may be alkylated to give a single or multifunctional alkylate Group. The coefficients, "a", "b", and "x" are all positive integers. Preferably each co-monomer comprises at least one n-propyl, isopropyl, or substituted isopropyl group. Examples of monomers having substituted isopropyl groups are as follows:
    [54]
    [55] And
    [56]
    [57] Wherein R 3 and R 4 are alkyl, alkyl oxide, or alkylene oxide groups that can be alkylated to provide mono- or polyfunctional alkylates.
    [58] If it is desired to use a moisture resistant component, the monomer component is selected based on compatibility with the selected moisture resistant oligomer. For satisfactory coating compatibility and moisture resistance, preference is given to using liquid alkylate monomer components comprising mainly saturated aliphatic mono- or di-alkylate monomers or alkoxy alkylate monomers.
    [59] Thus, even if one or more monomers are mixed into the composition, the first coating composition preferably contains at least one ethylenically unsaturated monomer. Preferably, the ethylenically unsaturated monomer is present in an amount of 10 to 90% by weight, more preferably 20 to 60% by weight, and most preferably 25 to 45% by weight.
    [60] In addition, the coating composition of the present invention typically contains at least one component of higher molecular weight than the monomer. Examples of such components include polymers or oligomers.
    [61] The polymer is a block copolymer comprising at least one hard block and at least one soft block, the hard block having a Tg greater than the Tg of the soft block. For the purposes of the present invention, the hard block is greater than 20 ° C. Tg and the soft block has a Tg of less than 20 ° C. Tg is determined by DMA at 1Hz frequency. Tg is defined as the temperature at which the loss tangent (tanδ) is the maximum as a function of temperature. Preferably the backbone of the soft block is fatty. Preferred fatty cast irons include poly (butadiene), polyisoprene, polyethylene / butylene, polyethylene / propylene and diol blocks. An example of a block polymer is a di-block copolymer having the general structure of A-B. However, the present invention is not limited to di-block copolymers, and another example of a preferred copolymer is a tri-block having a general structure of A-B-A. Preferably the mid block has a molecular weight of at least 10,000, more preferably more than 20,000, more preferably more than 50,000, and most preferably more than 100,000. In the case of tri-block copolymers (A-B-A), the mid-block (B as butadiene in the SBS copolymer as defined herein) has a Tg of less than 20 ° C. Examples of multi-blocks beyond three blocks include thermoplastic polyurethanes (TPUs). The source of TPU is BASF, B.F. Callus, and Bayer. The block copolymer may have any number of multiblocks. According to one embodiment, the composition comprises at least two thermoplastic final end blocks and an elastic mid block caster between two end blocks. The composition further comprises at least one reactive monomer. Thermoplastics are softened polymers and can be fluid when heated. The thermoplastic polymer is cooled to cure and retains the imparted form at elevated temperatures.
    [62] The polymer component may or may not be chemically crosslinked upon curing. Preferably, the polymer is a thermoplastic elastomer polymer. Preferably, the component has at least two thermoplastic final end blocks and an elastic cast iron between the two end blocks. The composition comprises a polymer component in an amount of 5 to 95% by weight, preferably 10 to 30% by weight, and most preferably 12 to 20% by weight. The polymer is preferably present in an amount of at least 10% or more, more preferably greater than 10%.
    [63] Suitable thermoplastic final terminal block materials include polystyrene and polymethyl methacrylate. The thermoplastic material is preferably a high polymer that exceeds the entanglement molecular weight. The entangled molecular weight is the molecular weight when the effect of neighboring molecules on the molecular migration of the subject molecule can no longer be explained by local friction alone. Viscoelasticity revealed strong additional binding to neighboring molecules. The main molecule acts as if it is located at a rather wide separation point along the molecular chain of the main molecule. For further background on entangled molecular weight, see pages 103-107, and pages 116-120 of Hymens (1984) Polymer Chemistry: Basic Concepts, (New Jersey, New York).
    [64] According to one embodiment of the polymer, the coating 16 comprises at least two thermoplastic end terminal blocks between the two end blocks and a first component having an elastic cast iron and a second component crosslinked to the first component and For example, the second component may be a monomer which is polymerized when the coating is cured. If the first component has a reaction group, for example, butadiene is present in the mid-block, a polymerization reaction occurs in which the mid-block is involved in the polymerization reaction. Optionally, if the mid-block is non-reactive, such as hydrogenated polybutadiene, the second component is polymerized and crosslinked with its surroundings through the first component rather than the first component.
    [65] The present invention describes an optical waveguide coating formulation comprising the following chemical components. However, references to specific compositions are for illustrative purposes and are not intended to limit the invention as claimed. One embodiment includes the use of styrene block copolymers (“SBCs”) in photocurable fiber optic coating compositions that also include acrylate monomers and photoinitiators. While the concept has been described using acrylate functional monomers, other ethylenically unsaturated monomers may also be used. Preferably other acrylate monomers can dissolve the elastomer. In addition to "SBC", other thermoplastic elastomers can be used. Preferably the elastomer is suitable for dissolving in the monomer and can photocure the coating. Suitable midblocks include ethylene propylene diene monomer ("EPDM") and ethylene propylene rubber. The elastomeric mid-block may be polybutadiene of the SBS series, polyisoprene of the SIS series, polyethylene / butylene of the SEBS series, and polyethylene / propylene of the SEP series of copolymers. SBC combines the properties of thermoplastics and elastomers and is known as thermoplastic elastomers (TPE).
    [66] Preferably, the styrene block copolymer contains a main chain consisting of three parts: an elastomeric mid-block and two thermoplastic end-blocks. Commercially available block copolymer structures include polybutadiene (SBS series), polyisoprene (SIS), polyethylene / butylene (SEBS), and polyethylene / propylene (SEP).
    [67] Examples of commercially available styrene block copolymers include Kraton® (Texas, Houston, and Kryton Polymers), Calprene® (Spain, Repsol Quimicasa SA), Solprene ( Philips Petroleum Corp., Ohio, Akron's Firestone Tires and Rubber Corp.'s Stereon®, Kraton D1101 (Styrene-Butadiene Linear Block Copolymer-SBS) (Kraton Polymer, Houston, Texas), Kraton D1193 (Styrene-isoprene linear block copolymer-SIS) (Kraton Polymer, Houston, Texas), Kraton FG1901X (grafted with styrene-ethylene-butylene block polymer-S-EB-S, 2% by weight malic anhydride) (Craton Polymer, Houston, Texas), Kraton D1107 (styrene-isoprene linear block copolymer-SIS) (Craton Polymer, Houston, Texas), and isoprene 400 Hardman Isolene © (liquid) Polyisoprene) (New Jersey, Element performance performance company of Bellville) have. In short, the thermoplastic elastomer has a double-phase form with a network of physical crosslinks.
    [68] The polymer also includes homopolymers such as liquid polyisoprene. An example of a preferred homopolymer is Hardman Isolen® of Elementis Performance Polymers, Bellville, NJ.
    [69] If the coating formulation comprises an oligomer, preferably the oligomer is an ethylenically unsaturated oligomer, more preferably a (meth) acrylate oligomer. (Meth) acrylate means an acrylate or a methacrylate. The (meth) acrylate end groups in the oligomers may be prepared by conventional methods such as monohydric poly (meth) acrylate capping components, or mono (meth) acrylate capping components such as 2-hydroxyethyl acrylate. Is provided through. It is also preferred that the oligomers can be involved in further polymerization reactions.
    [70] Urethane oligomers are typically provided through reaction of aliphatic or aromatic diisocyanates with dihydric polyethers or polyethers, most commonly polyoxyalkylene glycols such as polyethylene glycol. The oligomers typically have 4 to 10 urethane groups and are, for example, high molecular weights of 2000 to 8000. However, low molecular weight oligomers in the range of 500 to 2000 can also be used. US Pat. No. 4,608,409 to Cody et al. And US Pat. No. 4,609,718 to Bishop et al., Incorporated herein by reference, describe the synthesis of the oligomers described above in more detail.
    [71] When it is desirable to use moisture resistant oligomers, polar polyethers or polyether glycols can be synthesized in a similar manner except that they are mainly avoided for saturated and nonpolar aliphatic diols. The diols include, for example, alkanes or alkylene diols of 2 to 250 carbon atoms, and are preferably substantially free of ether or ester groups. The range of oligomer viscosities and molecular weights obtained from such systems are the same as those obtained in unsaturated, polar oligomer systems, and their viscosity and coating properties can be maintained substantially unchanged. The reduced oxygen content of these coatings confirmed that the adhesion properties of the coating to the surface of the glass fibers to be coated did not degrade.
    [72] In the course of the synthesis, the polyurea component prepared by replacing diols or polyols with diamines or polyamines may be mixed in the oligomer. The small presence of the polyurea component in the coating system of the present invention is not considered detrimental to coating performance, and sufficiently dipolar or saturates the diamine or polyamine used in the synthesis so as not to affect the moisture resistance of the system.
    [73] Thus, even if one or more oligomer components are mixed into the composition, it is preferred that the first coating system of the present invention contain at least one ethylenically unsaturated oligomer. Preferably, the oligomer is present in an amount of 10 to 90% by weight, more preferably 35 to 75% by weight, and most preferably 40 to 65% by weight.
    [74] Preferred ethylenically unsaturated oligomers for the first coating include polyether urethane acrylate oligomers (e.g., CN986, from Satomer, Pennsylvania, Westchester), and BR3731 and STC3-149, tri (from Boma Specialty, Connecticut, Winstead). Hydroxyethyl) isocyanurate acrylate oligomer (Sanomer Co., Ltd.), (meth) acrylated acrylic oligomer (Cognis Co., Pennsylvania, Ambler), polyester urethane acrylate oligomer (eg Sato Merca's CN966 and CN973, and Boma Specialty's BR7432), polyurea urethane acrylate oligomers (e.g., U.S. Pat.Nos. 4,690,502 and 4,798,852 to Zimmerman et al., Incorporated herein by reference, and Bishop, US Pat. 4,609,718, and oligomers disclosed in US Pat. No. 4,629,287 to Bishop et al., Polyether acrylate oligomers (eg, Genomer3456) from Rahn AG (Zurich, Switzerland), Ecryryl 80, 584 and 657 from Polyester acrylate oligomer (UCB Radcure (Atlanta, Georgia)), Poly Urea acrylate oligomers (oligomers disclosed in US Pat. Nos. 4,690,502 and 4,798,852 to Zimmerman et al., Incorporated by reference herein, Bis. Pat. No. 4,609,718, and Bishop et al. US Pat. No. 4,629,287), epoxy acrylates Oligomers (CN120 from Sartomer, and Evercryl 3201 and 3604 from UCB Radcure), hydrogenated polybutadiene oligomers (e.g., Eco Resin MBNX from Eco resin and Laboratories, Missouri, Versailles) and Mixtures thereof.
    [75] The optical fiber coating composition also contains a polymerization initiator suitable for causing polymerization (ie, curing) of the composition after application to the glass fibers. Suitable polymerization initiators for use in the first coating compositions of the present invention include thermal initiators, chemical initiators, electron beam initiators, and photoinitiators. More preferably, it is a photoinitiator. In most acrylate-based coating formulations, conventional photoinitiators such as known ketone photoinitiators and / or phosphine oxide additives are preferred. When used in the compositions of the present invention, the photoinitiator is present in an amount sufficient to provide fast ultraviolet curing. Generally it is 0.5 to 10.0% by weight, more preferably 1.5 to 7.5% by weight.
    [76] Photoinitiators used in small amounts or in amounts that are effective to promote photocuring should provide a reasonable cure rate without causing premature gelation of the coating composition. Preferred cure rates are sufficient to cause substantial cure of the coating material. As measured in the usage vs. modulus graph, the cure rate for 25 to 35 μm coating thickness is, for example, less than 1.0 J / cm 2, preferably less than 0.5 J / cm 2.
    [77] Preferred photoinitiators are Irgacure184, (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide from 1-hydroxycyclohexylphenyl ketone (e.g., Ciba Specialty Chemicals, Hawthorne, NY). For example, Irgacure1800, 1850 and 1700 from Ciba Specialty Chemicals, 2,2-dimethoxyl-2-petyl acetophenone (eg Irgacure651 from Ciba Specialty Chemicals), bis (2,4,6-trimethyl benzoyl) phenyl- Phosphine oxide (Irgacure 819), (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (Lucerin TPO from BASF, Munich, Germany), ethoxy (2,4,6-trimethyl Benzoyl) phenyl phosphine oxide (Lucerine TPO from BASF), and mixtures thereof.
    [78] As used herein, the weight percent of certain components means the content mixed in the bulk composition excluding the adhesion promoter and other additives. The content of the adhesion promoter and the various additives mixed in the bulk composition to prepare the composition of the present invention is expressed in parts per hundred. For example, when the oligomer, monomer, and photoinitiator are mixed to form a bulk composition, the total weight percentage of the composition is equal to 100%. Addition of, for example, 1.0 part by weight of an adhesion promoter to the bulk composition exceeds 100% by weight of the bulk composition.
    [79] The coating composition may also include an adhesion promoter. Preferred adhesion promoters include compounds having at least one reactive silane, reactive titanate, reactive zirconate or mixtures thereof. Preferred examples of silane adhesion promoters are cyclic structures independently located between at least two reactive silanes of alkoxysilanes or halosilanes, for example bis (trimethoxysilylethyl) benzene or bis (triethoxysilylethyl) benzene It contains a compound containing. Bis (trimethoxysilylethyl) -benzene can be purchased from Gelist Corporation (Teletown, Pennsylvania) and United Chemical Technologies (Bristol, Pennsylvania). Bis (triethoxysilylethyl) benzene can be synthesized from bis (trimethoxysilylethyl) benzene through trans-esterification with ethanol.
    [80] Other preferred silane adhesion promoters are 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane, vinyl trimethoxysilane, allyl trimethoxysilane and the like 3-mercaptopropyltrimethoxysilane from Gelist.
    [81] In the case of an adhesion promoter consisting of a titanate containing compound, the promoter optionally consists of at least one ethylenically unsaturated titanate containing compound, and more preferably at least one neoalkoxy titanate containing compound. Most preferably, the titanate-containing compound is tetra (2,2 diallyloxymethyl) butyl, di (ditridecyl) phosphito titanate (Kenrich Petrochemical, Inc. (Kernich) (NJ, Bayon)). KR55), neopentyl (diaryl) oxy, trineodecanoyl titanate (LICA01 from Kenrich), neopentyl (diaryl) oxy, tri (dodecyl) benzene-sulfony titanate (LICA09 from Kenrich) ), Neopentyl (diaryl) oxy, tri (dioctyl) phosphato titanate (LICA12 from Kenrich), neopentyl (diaryl) oxy, tri (dioctyl) pyro-phosphato titanate (LICA38 from Kenrich) ), Neopentyl (diaryl) oxy, tri (N-ethylenediamino) ethyl titanate (LICA44 from Kenrich), neopentyl (diaryl) oxy, tri (m-amino) phenyl titanate (LICA97 from Kenrich) ), Neopentyl (diaryl) oxy, trihydroxy caproyl titanate (LICA99 from Kenrich) and mixtures thereof At least one compound group.
    [82] Preferably, the titanate containing compound contains at least one UV curing functional group. More preferably, the functional group is a (meth) acrylate or an acrylate functional group. However, it is not necessary for the titanate containing compound to contain UV curing groups.
    [83] In the case of an adhesion promoter consisting of a zirconate-containing compound, preferably the promoter consists of at least one ethylenically unsaturated zirconate-containing compound, and more preferably at least one neoalkoxy zirconate-containing compound. Most preferably, the zirconate-containing compound is tetra (2,2 diaryloxymethyl) butyl, di (ditridecyl) phosphito zirconate (KZ55 from Kenrich), neopentyl (diaryl) oxy, Trineodecanoyl zirconate (NZ01 from Kenrich), neopentyl (diaryl) oxy, tri (dodecyl) benzene-sulfony zirconate (NZ09 from Kenrich), neopentyl (diaryl) oxy, tri (Dioctyl) phosphato zirconate (NZ12 from Kenrich), neopentyl (diaryl) oxy, tri (dioctyl) pyro-phosphato zirconate (NZ38 from Kenrich), neopentyl (diaryl) oxy , Tri (N-ethylenediamino) ethyl zirconate (NZ44 from Kenrich), neopentyl (diaryl) oxy, tri (m-amino) phenyl zirconate (NZ97 from Kenrich), neopentyl (diaryl ) Oxy, trimethacryl zirconate (NZ33 from Kenrich), neopentyl (diaryl) oxy, triacryl zirconate (NZ39 from Kenrich), Dynepentyl (diaryl) oxy, diparamino, benzoyl zirconate (NZ37 from Kenrich), Dynepentyl (aiaryl) oxy, di (3-mercapto) propionic zirconate (NZ66A from Kenrich) ) And mixtures thereof.
    [84] Preferably, the zirconate containing compound contains at least one UV curing functional group. More preferably, the functional group is a (meth) acrylate or acrylate functional group. However, it is not necessary for the zirconate containing compound to contain UV curing groups.
    [85] Preferably the adhesion promoter is present in an amount of 0.1 to 10 parts by weight, more preferably 0.25 to 4 parts by weight, most preferably 0.5 to 3 parts by weight.
    [86] In addition to the compounds described above, the first coating composition of the present invention may optionally include a number of additives such as reactive diluents, antioxidants, catalysts, lubricants, co-polymers, low molecular weight non-crosslinked resins, and stabilizers. Some additives (eg chain transfer agents) can be controlled to control the polymerization process and thus affect the physical properties (eg modulus, glass transition temperature) of the polymerization products formed from the first coating composition. have. Other additives affect the integrity of the polymerization product of the first coating composition (eg, protection against polymerisation or oxidative degradation).
    [87] Preferred catalysts are tin-catalysts used to catalyze the formation of urethane bonds in some oligomeric components. Whether the catalyst is mixed with the oligomeric component or the composition of the present invention in an additional amount of catalyst, the presence of the catalyst serves to stabilize the oligomeric component in the composition.
    [88] Preferred antioxidants are thiodiethylene bis (3,5-di-tert-butyl) -4-hydroxyhydrocinnamate (eg Irganox1035 from Ciba Specialty Chemicals).
    [89] Preferred co-monomers are the polar monomers N-vinyl-pyrrolidone of International Specialty Products, Wayne, NJ.
    [90] A second aspect of the invention relates to a composition containing an adhesion promoter comprising a polymerizable oligomer, a monomer suitable for controlling the viscosity of the composition, and a compound containing a reactive silane and a carrier.
    [91] The carrier is preferably a carrier that acts as a carrier surfactant or an amphiphilic reactive or non-reactive surfactant. More preferred are reactive surfactants that are partially soluble or insoluble in the composition. Without being bound by a particular theory, it is known that carriers that act as reactive surfactants react with compounds containing reactive silanes by depositing these compounds on glass fibers that enable the reaction. The carrier is preferably present in an amount of 0.01 to 10 parts by weight, more preferably 0.25 to 3 parts by weight.
    [92] Suitable carriers, more particularly those which act as reactive surfactants, include polyalkoxypolysiloxanes. Preferred carriers are the trade name Tegord2200 from Goldschmidt Chemicals, Hopewell, Va., And also Tegorad2700 (acrylated siloxane) from Goldschmidt Chemicals.
    [93] Other types of carriers include polyols and non-reactive surfactants. Examples of suitable polyols and non-reactive surfactants include polyol Aclaim 3201 (poly (ethylene oxide-co-propylene oxide) from Bayer (known as Leondell), Newtown Square, Pennsylvania, and non-reactive from Goldschmidt Chemicals. Surfactant Tegoglide 435 (polyalkoxy-polysiloxane) The polyol or non-reactive surfactant is present in a preferred amount of 0.01 to 10 parts by weight Suitable carriers may also be amphiphilic molecules. Amphiphilic molecules may be hydrophilic and A hydrophobic moiety is a molecule having a hydrophobic moiety.
    [94] Tackifiers are also examples of suitable carriers. In addition to the carrier, the tackifier is also a molecule that can modify the time-sensitive rheological properties of the polymer product. In general, the adhesive additives make the polymer product work harder at higher strain rates or shear rates and soften at low strain rates or shear rates. Adhesives are additives commonly used in the adhesion industry that enhance the ability of a coating to create bonds with objects applied to the coating. For further background on adhesives and adhesive resins, see pages 36, 37, 57-61, 169, 171-184, and 609-631 of the Pressure Sensitive Adhesive Technology Handbook, 3rd Edition (Rhode Island, Warwick) (1999). , Incorporated by reference of the present invention.
    [95] Preferred adhesives are classified into terpene resins, coumarone resins, petroleum resins, hydrogenated petroleum resins, styrene resins, phenol resins, or rosin resins. It is preferable that an adhesive is non-epoxidized. The rosin-based resins include unmodified rosin (eg, wood, gum, or tall oil) and rosin derivatives. Rosin-based resins can be classified into their rosin acids, which are abietic acid or pymal acid. Abiotic acid type rosin is preferred. Rosin derivatives include polymeric rosin, disproportionated rosin, hydrogenated rosin and esterified rosin. Representative examples of such rosin derivatives include pentaerythritol esters of tall oil, gum rosin, wood rosin or mixtures thereof.
    [96] The terpene-based resins include α-pinene, β-pinene, dipentel, limonene, myrcene, bonylene and camphor, and terpene polymers, and phenol-modified terpene-based resins can be obtained by modifying the terpene-based resin with phenol. have.
    [97] The coumarone-based resins include, for example, coumarone-indene resins and phenol-modified coumarone-indene resins.
    [98] Petroleum and hydrogenated petroleum resins include fatty petroleum resins, arylcyclic petroleum resins, aromatics using α-methylstyrene, vinyltoluene, indene, methylindene, butadiene, isoprene, fiphenylene and pentylene as raw materials. Petroleum resins, and homopolymers or copolymers of cyclopentadiene. The petroleum resin is a polymer using a fraction having 5 to 9 carbon atoms as a main component.
    [99] The styrenic resins include homopolymers, which are low molecular weight polymers containing styrene as main components, such as styrene copolymers with α-methylstyrene, vinyltoluene, and butadiene rubber.
    [100] The phenolic resins are rosin-modified products and reaction products of phenols such as phenol, cresol, xylenol, resorcinol, p-tert-butylphenol, and p-phenylphenol with aldehydes such as formaldehyde, acetalaldehyde and perfural. Phenolic resins.
    [101] More preferred adhesives are Uni-Tack® R-40 (hereinafter "R-40", International Paper, Pearl Chase, New York.) R-40 is a tall oil rosin containing a polyether moiety, which is derived from the chemical family of aviet esters. Preferably, the pressure sensitive adhesive is present in the composition in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight Suitable alternative pressure sensitive adhesives are the Escorez series of hydrocarbon pressure sensitive adhesives from Exxon. The above mentioned carriers can also be mixed and used Other preferred tackifiers are Silvatac RE-40E (Rosin Ester) from Arizona Chemicals, Jacksonville, Florida, Silvatac RE-40 from Arizona Chemicals, Pennsylvania, Neville Island Nevtac 10 (fatty hydrocarbon resin) from Neville Chemical, and Piccovar AP10 (directional) from Eastman Chemical of Kingsport, Tennessee Hydrocarbon resin).
    [102] Preferably the adhesion promoter used in admixture with the pressure sensitive adhesive carrier is poly (alkoxy) silane. However, the present invention is not limited only to the poly (alkoxy) silane adhesion promoter when mixed with the pressure-sensitive adhesive carrier. Preferred poly (alkoxy) silane adhesion promoter is bis (trimethoxysilylethyl) benzene. It is also preferred that the poly (alkoxy) silane adhesion promoter is present in the composition in an amount of 0.1 to 10 parts by weight. Although the adhesion promoter may be any adhesion promoter including a compound having a reactive silane, the adhesion promoter is preferably the aforementioned adhesion promoter (ie, a cyclic structure located between at least two reactive silanes, independently alkoxysilanes or halocillins). Containing compounds). Other suitable adhesion promoters are disclosed in US Pat. Nos. 4,921,880 and 5,188,864 to Lee et al., Which are incorporated by reference herein.
    [103] For a description of more specific adhesion promoters, US Pat. No. 09 / 476,151, filed Dec. 30, 1999, is incorporated by reference.
    [104] The first coating is preferably a soft cushion layer having a Young's modulus of less than 5 MPa, more preferably less than 1.2 MPa, most preferably less than 0.9 MPa.
    [105] Preferably the% elongation comprises at least 100%, more preferably greater than 131%, even more preferably greater than 140%, and most preferably at least 150%. The percent elongation comprises greater than 175% or greater than 200%.
    [106] In one embodiment of the coating 16, the Young's modulus comprises less than 0.65 MPa and the% elongation comprises more than 140%, more preferably the Young's modulus comprises 0.5 MPa or less and more preferably% Elongation rate includes at least 150%, and most preferably at least 200%.
    [107] In another embodiment of coating 16, the coating comprises a composition that is substantially tack free. In another embodiment of coating 16, the coating comprises a composition that is substantially polymer free.
    [108] The second coating material 18 is typically the polymerization (ie, curing) product of the coating composition containing urethane acrylate liquid molecules that crosslink during polymerization. Considerations related to the selection of such materials as well as other suitable materials for use in the second coating are well known in the art and are described in US Pat. Nos. 4,962,992 and 5,104,433 to Chapin, which are incorporated herein by reference. Include. Various additives may be present that enhance one or more properties of the coating, including the additives described above mixed into the compositions of the present invention.
    [109] Typical second coatings will comprise at least one UV curable monomer and at least one photoinitiator. The second coating may also comprise 0 to 90% by weight of at least one UV cured oligomer. Preferably, the second coating is not a thermoplastic resin. Preferably, both the monomers and oligomers are compounds that may be involved in further polymerization. The monomer or oligomer may be the main component of the second coating. Examples of suitable monomers are ethylenically unsaturated monomers. Ethylenically unsaturated monomers contain various functional groups that can cross-link. Monofunctional monomers may also be mixed into the composition, but the ethylenically unsaturated monomers are preferably polyfunctional (ie, containing two or more functional groups). Thus, the ethylenically unsaturated monomer may be a polyfunctional monomer, a single functional monomer and mixtures thereof. Suitable functional groups for the ethylenically unsaturated monomers used in accordance with the invention are acrylates, methacrylates, acrylamides, N-vinyl amides, styrenes, vinyl ethers, vinyl esters, acid esters and mixtures thereof (ie multifunctional groups). Monomers), but is not limited to such.
    [110] In general, each monomer capable of at least 80% conversion (ie, upon curing) is preferred over monomers having a low conversion. The degree of low conversion monomers incorporated into the composition depends on the specific requirements (ie strength) of the final cured product. Typically higher conversions produce stronger curing products.
    [111] Suitable polyfunctional ethylenically unsaturated monomers are alkoxylated bisphenol A diacrylates (e.g., Pennsylvania, West Chester) such as ethoxylated bisphenol A diacrylate ethoxylated in at least two, preferably in the range from 2 to 30 SR349 and SR601 from Sartomer, PA and Photomer 4025 and Photomer 4028 from Cognis (Pennsylvania, Ambler), and propoxylated propoxylated bisphenols in at least two, preferably in the range from 2 to 30 A diacrylate; Methylolpropane polyacrylates, such as alkoxylated or unsubstituted at least 3, preferably ethoxylated ethoxylated trimethylolpropane triacrylate (e.g., Photomer 4149 from Cognis and SR499 from Sartomer), propoxylated trimethylolpropane triacrylate propoxylated to at least 3, preferably in the range from 3 to 30 (eg, Phonomer 4072 from Cognis, and SR492 from Sartomer), And ditrimethylolpropane tetraacrylate (eg, Photomer 4355 from Cognis); Alkoxylated glyceryl triacrylates, such as propoxylated glyceryl triacrylate, propoxylated to at least 3 (eg Photomer 4096 from Cognis and SR9020 from Satomer); Pentaerythritol tetraacrylate (e.g. SR295 from Satomer, Pennsylvania, West Chester), ethoxylated pentaerythritol tetraacrylate (e.g., SR494 from Sartomer), and dipentaerythritol pentaacrylic Erythritol polyacrylates with or without alkoxylation, such as rates (e.g., Photomer 4399 from Cognis, and SR399 from Sartomer); Suitable functional groups, such as tris- (2-hydroxyethyl) isocyanurate triacrylate (e.g. SR368 from Satomer) and tris- (2-hydroxyethyl) isocyanurate diacrylate Isocyanurate polyacrylates formed by reacting anurates with acrylic acid or acryloyl chloride: alcohol alkoxylated or non-alkoxy polyacrylates such as tricyclodecane dimethanol diacrylate (e.g., CD406 from Sartomer). And ethoxylated polyethylene glycol diacrylate ethoxylated in at least 2, preferably in the range from 2 to 30; Epoxy acrylates formed by adding acrylates to bisphenol A diglycidyl ether and its equivalents (eg, Photomer 3016 from Cognis); And single and multi-ring cyclic aromatic or non-aromatic polyacrylates such as dicyclopentadiene diacrylate and dicyclopentane diacrylate.
    [112] It is also desirable to use an amount of single functional ethylenically unsaturated monomer, which can be mixed to affect the extent to which the cured product absorbs water, adheres to other coating materials, or acts under stress. Examples of single functional ethylenically unsaturated monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl-acrylate, 2-hydroxypropyl-acrylate, and 2-hydroxybutyl-acrylate; Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl Acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate, octadecyl acrylic Long- and short-chain alkyl acrylates such as rate and stearyl acrylate; Dimethylaminoethyl acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 7-amino-3,7-dimethyloctyl acrylate; Alkoxyalkyl acrylates such as butoxyl ethyl acrylate, phenoxyethyl acrylate (e.g., SR339 from Sartomer), and ethoxyethoxyethyl acrylate; Cyclohexyl acrylate, benzyl acrylate, dicyclopentadiene acrylate, dicyclopentanyl acrylate, tricyclodecanyl acrylate, carbonyl acrylate, isobornyl acrylate (e.g., SR285 from Sartomer), caprolactone Single and multi-ring cyclic aromatic or non-aromatic acrylates such as acrylates (eg, SR495 from Sartomer), and acryloylmorpholine; Alcohol-based acrylates such as polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxyethylene glycol acrylate, methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, and Various alkoxylated alkylphenol acrylates such as ethoxylated (4) nonylphenol acrylate (eg, Photomer 4003 from Cognis); Acrylamides such as diacetone acrylamide, isobutoxymethyl acrylamide, N, N'-dimethyl-aminopropyl acrylamide, N.N-dimethyl acrylamide, N, N-diethyl acrylamide, and t-octyl acrylamide; Vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; And acid esters such as malic acid esters and fumaric acid esters.
    [113] Most suitable monomers are commercially available or can be readily synthesized using reactions known in the art. For example, most of the aforementioned single functional monomers can be synthesized by reacting alcohols or amines with acrylic acid or acryloyl chloride.
    [114] As mentioned above, an optional component of the second coating composition is an oligomer component. The oligomer component may comprise a single type of oligomer or a mixture of two or more oligomers. The oligomer component to be mixed in the composition of the present invention preferably comprises an ethylenically unsaturated oligomer.
    [115] In use, multifunctional oligomers are preferred, but suitable oligomers may be monofunctional or multifunctional oligomers. The oligomer component may also be a mixture of monofunctional and multifunctional oligomers.
    [116] Preferably the bifunctional oligomer has a structure as shown in the following formula (1).
    [117] F 1 -R 1- [Diisocyanate-R 2 -Diisocyanate] mR 1 -F 1
    [118] In Formula 1 F 1 is independently selected from acrylates methacrylates, acrylamide, N- vinyl amide, styrene, vinyl ether, reactive functional groups such as vinyl ester, or other functional group is known in the art; R 1 is independently -C 2-12 O-,-(C 2-4 O) -n, -C 2-12 O- (C 2-4 O) n, -C 2-12 O- (CO- C 2-5 O) n, or —C 2-12 O— (CO—C 2-5 NH) n, wherein n is a number from 1 to 30, preferably from 1 to 10; R 2 is polyether, polyester, polycarbonate, polyamide, polyurethane, polyurea or mixtures thereof; m is a number from 1 to 10, preferably from 1 to 5. In Formula 1, the diisocyanate group is a reaction product formed through post-bonding of diisocyanate to R 2 and / or R 1 .
    [119] Preferably another multifunctional oligomer has the structure of formula (2) or (3).
    [120] Multiple isocyanates- (R 2 -R 1 -F 2 ) x
    [121] Polyol-[(diisocyanate-R 2 -diisocyanate) mR 1 -F 2 ] x
    [122] F 2 in the above formula represents 1 to 3 functional groups such as acrylate, methacrylate acrylamide, N-vinyl amide, styrene, vinyl ether, vinyl ester or other functional groups known in the art; R 1 is independently -C 2-12 O-,-(C 2-4 O) -n, -C 2-12 O- (C 2-4 O) n, -C 2-12 O- (CO- C 2-5 O) n, or —C 2-12 O— (CO—C 2-5 NH) n, n is 1 to 10, preferably 1 to 5; R 2 is polyether, polyester, polycarbonate, polyamide, polyurethane, polyurea or mixtures thereof; x is 1 to 10, preferably 2 to 5; m is 1 to 10, preferably 1 to 5. In Formula 2, the plurality of isocyanate groups are reaction products formed through post-bonding of a plurality of isocyanates to R 2 . Similarly, the diisocyanate group in the structure of formula (3) is a reaction product formed through the post-bonding of diisocyanate to R 2 and / or R 1 .
    [123] Urethane oligomers are typically provided by reaction of aliphatic diisocyanates with dihydric polyethers or polyesters, most commonly polyoxyalkylene glycols such as polyethylene glycol. Such oligomers typically have 4 to 10 urethane groups and are, for example, high molecular weights of 2000 to 8000. However, low molecular weight oligomers having a molecular weight in the range of 500 to 2000 can also be used. US Patent No. 4,608,409 to Cody et al. And US Patent No. 4,609,718 to Bishop et al. Specifically disclose such synthesis and are incorporated by reference in the present invention.
    [124] If it is desired to use moisture resistant oligomers, they are synthesized in a similar manner except that polar polyethers or polyester glycols are mainly avoided to become saturated and nonpolar aliphatic diols. The diols are, for example, alkanes or alkylene diols of 2 to 250 carbon atoms, and are preferably substantially free of ether or ester groups.
    [125] The polyurea component can be mixed with oligomers prepared by replacing diols or polyols with diamines or polyamines during synthesis. The presence of small amounts of polyurethane components in the coating system of the present invention is not considered detrimental to coating performance and is provided only if the diamines or polyamines used in the synthesis are sufficiently nonpolar and saturated to not degrade the moisture resistance of the system.
    [126] Suitable oligomers include BR301, an aromatic urethane acrylate oligomer from Boma Specialty, Photomer 6010, an aliphatic urethane acrylate from Henkel, KWS5021, an aliphatic urethane acrylate oligomer from Boma Specialty, RCC12-892, a polyfunctional aliphatic urethane acrylate oligomer from Henkel, Henkel's aromatic urethane diacrylate oligomer RCC13-572, and Boma Specialty's aliphatic urethane acrylate oligomer KWS4131.
    [127] The second coating composition of the optical fiber also contains a polymerization initiator suitable for causing polymerization (ie, curing) of the composition after application to the glass fiber or on the precoated glass fiber. Suitable polymerization initiators for use in the compositions of the present invention include thermal initiators, chemical initiators, electron beam initiators, microwave initiators, chemical-spinning initiators and photoinitiators. Especially preferably, it is a photoinitiator. For most acrylate-based coating formulations, conventional photoinitiators such as the well known ketone photoinitiators and / or phosphine oxide additives are preferred. When used in the compositions of the present invention, the photoinitiator is present in an amount sufficient to provide fast ultraviolet curing. Generally, 0.5 to 10.0% by weight, more preferably 1.5 to 7.5% by weight.
    [128] When used in small amounts or in amounts effective to promote photocuring, the photoinitiator should provide a reasonable cure rate that does not cause premature gelation of the coating composition. Preferred cure rates are those sufficient to cause substantial cure of the coating composition (ie, greater than about 90%, more preferably 95%). As measured in the usage vs. modulus graph, the curing rate for a coating thickness of 25 to 35 μm is, for example, less than 1.0 J / cm 2, preferably less than 0.5 J / cm 2. The second coating composition comprises about 10 to 90% of a monomer; About 0 to 90% of an oligomer; And about 0.5 to 10% photoinitiator.
    [129] Suitable photoinitiators include 1-hydroxycyclohexylphenyl ketones (e.g. Irgacure184 from Ciba Specialty Chemicals, Tarrytown, NY), (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine Oxides (e.g., trade names Irgacure 1800, 1850, and 1700 from Ciba Specialty Chemicals), 2,3-dimethoxyl-2-phenylacetophenone (e.g., Irgacure 651 from Ciba Specialty Chemicals), bis (2,4 , 6-trimethylbenzoyl) phenyl phosphine oxide (e.g. Irgacure 819 from Ciba Specialty Chemicals), (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (e.g. Darocur 4265 from Ciba Specialty Chemicals ), 2-hydroxy-2-methyl-1-phenylpropane-1-one (eg, the tradename Darocur4265 from Ciba Specialty Chemicals), and mixtures thereof. Other photoinitiators are constantly being developed and used as coating compositions for glass fibers. Any suitable photoinitiator can also be mixed in the compositions of the present invention.
    [130] In addition to the components described above, the second coating composition of the present invention may optionally comprise an additive or a mixture of additives. Suitable additives include, but are not limited to, antioxidants, catalysts, lubricants, low molecular weight non-crosslinked resins, adhesion promoters, and stabilizers. Some additives can act to control the polymerization process, affecting the physical properties (eg modulus, glass transition temperature) of the polymerization products formed from the composition. Others can affect the integrity of the polymerization product of the composition (eg, protect it from polymerization or oxidative degradation).
    [131] Preferred antioxidants are thiodiethylene bis (3,5-di-tert-butyl) -4-hydroxyhydrocinnamate (eg Irganox1035 from Ciba Specialty).
    [132] Other suitable materials for use in the second coating materials and considerations for the selection of these materials are described in Chapin US Pat. Nos. 4,962,992 and 5,104,433, which are incorporated by reference herein. Various additives may also be present that enhance one or more of the properties of the coating, and include the aforementioned additives blended into the compositions of the present invention. A more specific reference for the second coating is filed on July 26, 2000 by Botero et al., Entitled US Patent Application No. 60 / 173,874, filed December 30, 1999, and the second coating composition for optical fibers. US Provisional Application is incorporated herein by reference. Preferably, the second coating 18 has a Young's modulus of at least about 50 MPa, more preferably at least about 500 MPa, and most preferably at least about 1000 MPa. In one embodiment of the fiber 10, the outer diameter of the second coating 18 is about 245 μm. However, the outer diameter of the coating 18 is not limited to about 245 μm. More specific embodiments of coating 18 have an outer diameter of less than or greater than 245 μm, eg, about 150 μm, 175 μm, 200 μm, 275 μm, 300 μm or 350 μm.
    [133] The second coating 18 may be a tight buffer or optionally a loose tube coating. Regardless of the type of second coating used, it is desirable that the outer surface of the second coating 18 be tacky so that adjacent convolutions of the optical fiber (ie on the running spool) can be released.
    [134] The optical fiber of the present invention may also be formed from an optical fiber ribbon containing a plurality of substantially arranged, substantially coplanar optical fibers, wrapped in a matrix material. The matrix material may consist of a single layer or a composite configuration. Suitable matrix materials include polyvinyl chloride or other thermoplastics as well as materials known to be useful as second coating materials. In one embodiment, the matrix material may be a polymerization product of the composition used to form the second coating material.
    [135] In brief, the method for producing a coated optical fiber according to the present invention comprises the steps of manufacturing the glass fiber 10 (core 12 and the cladding layer 14), coating the glass fiber with the first coating composition of the present invention And polymerizing the composition to form a first coating material 16. Optionally, second coating composition 18 may be applied to the coated fibers before or after polymerizing the first coating. If applied after polymerization of the first coating, a second polymerization step is required. The first and optional second coating compositions are coated on the glass fibers using conventional methods.
    [136] It is well known to draw glass fibers from specially manufactured cylindrical preforms which have been locally and symmetrically heated to, for example, a temperature of about 2000 ° C. The preforms are placed in a furnace and heated to draw glass fibers from the dissolved material. The first coating and the second coating composition are drawn from the preform and then more preferably applied to the glass fibers upon cooling. The coating composition is then cured into a coated optical fiber. The curing method may be thermal, chemical, or light induced, such as exposing the uncured coating composition on glass fibers to heat or ultraviolet light or electron beam, depending on the nature of the coating composition and the polymerization initiator used. It is preferred to apply the first coating composition and the second coating composition continuously after the drawing process. Methods of applying a bilayer of coating compositions to mobile glass fibers are disclosed in Taylor, US Pat. No. 4,474,830, and in US Patent No. 4,851,165, including Rennell, and incorporated herein by reference. Of course, after applying and curing the first coating composition to form the first coating material 16, the second coating composition may be applied and cured to form the second coating material 18.
    [137] One embodiment of the method for manufacturing the coated optical fiber according to the present invention is further described in FIG. As shown in FIG. 2, the sintered preform 22 (shown as a partial preform) was drawn into the optical fiber 24. The fiber 24 passed through the coating parts 26 and 28. Preferably coating 16 was applied to fiber 24 in part 26 and Corning 18 was applied to fiber 24 in part 28. The hardened component 30 is located below the component 26 and the hardened component 32 is positioned below the component 28 to cure the coating applied to the fibers 24. Optionally, a coating applied to the part 26 will then cure the fibers 24 passing through the part 28. A tractor 36 is used to pull the coated optical fiber 34 through the part 32.
    [138] Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.
    [139] Various Tess coatings with pressure sensitive adhesive properties were prepared. Test coatings and control coatings are shown in Tables 1 and 2. The percentages in Tables 1 and 2 are by weight unless otherwise indicated.
    [140] Urethane Acrylate-Based Formulations Test coatingMono-%D-%Oligo-%Photoinitiator-%Adhesion Promoter- (part by weight)Additive-(part by weight)Additive-(middle part) Test Coating 1Ph4003-40Ph4127-5BR3731-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0) 3-Mer-(. 3)Irganox1035- (1.0)SylvatacRE-40N- (20) Test Coating 2Ph4003-43Ph4127-2BR3731-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0) 3-Mer-(. 3)Irganox1035- (1.0)SylvatacRE-40N- (15) Test Coating 3Ph4003-40Ph4127-5BR3731-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0)Irganox1035- (1.0)SylvatacRE-40N- (20) Test Coating 4Ph4003-40Ph4127-5BR3731-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0)Irganox1035- (1.0)SylvatacRE-40N- (20) Test Coating 5Ph4003-43Ph4127-2BR3731-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0)Irganox1035- (1.0)SylvatacRE-40N- (15) Test Coating 10Ph4003-25Tone-20BR3741-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0)Irganox1035- (1.0)N / A Test Coating 11Ph4003-30Tone-15BR3741-52Irg184-1.5 Irg819-1.5Acryl Sil- (1.0)Irganox1035- (1.0)SylvaliteRE 10L (0.5) Test Coating 12Ph4003-45.22Tone-13.04BR3731-39.13Irg184-1.5 Irg819-1.53-Mer-(. 3)Irganox1035- (1.0)SylvaliteRE 10L (0.5)
    [141] Rubber-Based Formulations Test coatingPolymerAcrylated monomerCross-linking agent-(part by weight)Photoinitiator-(part by weight)Additive (part by weight)Adhesion resin (part by weight) Test Coating 6D1101 (15%)Lauryl acrylate (30%) Ph4003 (55%)SR492 (2)Irg184 (1.5) Irg819 (1.5)Irganox1035 (1) TRIS (1)Nevtac10 (5) Test coatingD1107 (15%)Lauryl acrylate (30%) Ph4003 (55%)SR492 (3)Irg184 (1.5) Irg819 (1.5)Irganox1035 (1) TRIS (1)Nevtac10 (5) Test Corning 8D1101 (15%)Lauryl acrylate (30%) Ph4003 (55%)SR492 (1)Irg184 (1.5) Irg819 (1.5)Irganox1035 (1) TRIS (1)PiccovarAP10 (5) Test Coating 9D1107 (21%) Isolene400 (25%)Lauryl acrylate (20%) Ph4003 (25%)SR492 (1)Irg184 (1.5) Irg819 (1.5)Irganox1035 (1) TRIS (1)none
    [142] Test coating raw materials
    [143] Monomer:
    [144] Ph4003-photomer4003 (nonyl phenol ethoxylated monoacrylate) from Cognis (coating and ink part) (Ambler, Pennsylvania)
    [145] Ph4127-Photomer 4127 (Neopentyl Glycol Propoxylated Diacrylate) from Cognis (Coating and Ink Division) (Ambler, Pennsylvania)
    [146] SR492-Saromer 492 (propoxylated 3 -trimethylolpropane triacrylate) from Sartomer, Exton, Pennsylvania
    [147] Tone-Tone M-100 (Caprolactone acrylate) of Union Carbide (Danbury, Connecticut)
    [148] Oligomer / Polymer:
    [149] BR3731-BR3731 (urethane oligomer) from Boma Specialty, Winstead, Pennsylvania
    [150] BR3741-BR3741 (polyether urethane oligomer) from Boma Specialty, Winstead, Pennsylvania
    [151] D1101-Kraton D1101 (Styrene-Butadiene Linear Block Copolymer-SBS) from Kraton Polymers, Houston, Tex.
    [152] D1107-Kraton D1107 (Styrene-isoprene linear block copolymer-SIS) from Kraton Polymers, Houston, Tex.
    [153] Isoprene400-Hardman Isolene © 400 (Liquid Polyisoprene) by Elementis Performance Polymers, Bellville, NJ
    [154] Photoinitiator:
    [155] Irg184-Irgacure184 (1-hydroxycyclohexyl phenyl ketone) from Ciba Specialty Chemicals, Tarrytown, NY
    [156] Irg819-Irgacure 819 (2,4,6-trimethybenzoyl) -phenylphosphine oxide from Ciba Specialty Chemicals, Tarrytown, NY
    [157] Antioxidants:
    [158] Irganox1035-Thiodiethylene bis (3,5-dibutylbutyl-4-hydroxy hydrocinnamate) from Ciba Specialty Chemicals, Tarrytown, NY
    [159] Adhesion Promoter:
    [160] Acryl Sil-3-acryloxypropyltrimethoxysilane from Gelist (Teletown, Pennsylvania)
    [161] 3-Mer-3-mercaptopropyltrimethoxysilane from Gelist Corporation (Teletown, Pennsylvania)
    [162] adhesive:
    [163] Sylvtac RE-40N (Sylvatac RE-40N (Rosin Ester) from Arizona Chemical, Jacksonville, FL)
    [164] Sylvalite RE 10L-Sylvarit RE-40N (Rosin Ester) from Arizona Chemical, Jacksonville, FL
    [165] Nevtac 10-Fatty Hydrocarbon Resin from Neville Chemicals, Neville Island, Pennsylvania
    [166] Piccovar AP 10-aromatic hydrocarbon resin from Eastman Chemical, Kingsport, Tennessee, formerly Delaware, Hercules, Wilmington
    [167] additive:
    [168] TRIS-trimethylolpropane-tris-3-mercapto propionate from Aldrich Chemicals, Milwaukee, Wisconsin
    [169] The control is the first coating of the urethane acrylate double coating system of DSM Desotech (Elgin, IL). Physical properties of the second coating and control were evaluated according to ASTM 882-97. The test results are shown in Table 3 below.
    [170] FormulationYoung's Modulus (MPa)% Elongation Control 1.0-1.3 80-130 Test coatings 60.33178.6 Test coatings 70.2883.48 Test coatings 80.27172.13 Test coatings 90.29247.33 Test Coating 10.52226.8 Test coatings 20.55218.36 Test coatings 30.6169.03 Test coatings 40.8134.09 Test coatings 50.52201.45
    [171] Window viscoelastic windows for test coatings 3, 5 and 7-12 and control were prepared as shown in FIGS. 4 and 5. The frequencies for determining the coordinates for G 'and G "are 0.01R / S and 100R / S. The test was carried out at room temperature and the Poisson's ratio was measured at about 0.5.
    [172] The test coating demonstrated classic pressure sensitive adhesive (PSA) characteristics. The test coating includes desirable properties such as good adhesion to glass and suitable physical properties. The test coating also has the advantage of low cost and flexibility in formulation, depending on the low cost raw material.
    [173] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope of the present invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
    权利要求:
    Claims (47)
    [1" claim-type="Currently amended] A radiation curable composition comprising a reactive monomer and a photoinitiator; The composition is selected so that, upon curing, the Chang viscoelastic window of the composition exhibits at least one set of coordinates, the coordinates being viscous shear modulus (G ") and elastic shear modulus (G) in units of Pascals. An optical fiber coating characterized in that it is logarithmic and is located in at least one of the following windows defined by the following set of window coordinates:
    (1) (about 3.000, about 4.480), (about 3.000, about 3.000), (6.000, about 4.480) and (about 6.000, about 3.000); (2) (greater than about 3.840, about 5.180), (greater than about 3.84, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); And (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, 5.729).
    [2" claim-type="Currently amended] The coating of claim 1, wherein at least a second set of coordinates is located in one of the set of window coordinates.
    [3" claim-type="Currently amended] The coating of claim 1, wherein at least one set of coordinates of the composition is located in one of the following second set of window coordinates: (3) (about 5.112, about 6.000), (about 5.112, about 5.180 ), (About 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (7) (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850); (8) (about 5.440, about 4.480), (about 5.440, about 3.000), (about 6.000, about 4.480), and (about 6.000, about 3.000); (9) (about 4.530, about 3.850), (about 4.530, about 3.000), (about 5.440, about 3.850), and (about 5.440, about 3.000); (10) (about 4.106, about 5.474), (about 4.106, about 5.350), (about 4.930, about 5.474), and (about 4.930, about 5.350); (11) (about 4.232, about 5.375), (about 4.232, about 5.235), (about 4.958, about 5.375), and (about 4.958, about 5.235); And (12) (about 4.139, about 5.488), (about 4.139, about 5.409), (about 4.894, about 5.488), and (about 4.894, about 5.409).
    [4" claim-type="Currently amended] The coating of claim 2, wherein the second set of coordinates is present in at least one of the following third set of window coordinates: (3) (about 5.112, about 6.000), (about 5.112, about 5.180) , (About 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); And (7) (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850).
    [5" claim-type="Currently amended] The method of claim 4, wherein the third set of window coordinates comprises (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); And (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480).
    [6" claim-type="Currently amended] The coating of claim 1, wherein the composition has a Young's modulus of less than about 1.2 MPa upon curing.
    [7" claim-type="Currently amended] The coating of claim 6, wherein the Young's modulus comprises less than about 0.9 MPa.
    [8" claim-type="Currently amended] The coating of claim 1 wherein the composition further comprises a thermoplastic elastomer.
    [9" claim-type="Currently amended] The coating of claim 1 wherein the composition is substantially free of tackifiers.
    [10" claim-type="Currently amended] The coating of claim 1 wherein the composition comprises an adhesive.
    [11" claim-type="Currently amended] The coating of claim 1 wherein the composition comprises at least one compound selected from rosin esters, fatty hydrocarbon resins, aromatic hydrocarbon resins, and mixtures thereof.
    [12" claim-type="Currently amended] The coating of claim 1 wherein the composition comprises at least one compound selected from styrene-diene block copolymers, homopolymers, and mixtures thereof.
    [13" claim-type="Currently amended] The coating of claim 12, wherein the composition comprises a soft block, the soft block comprising at least one selected from butadiene, isoprene, polyisoprene, and mixtures thereof.
    [14" claim-type="Currently amended] The coating of claim 1, wherein the Young's modulus comprises less than about 0.65 MPa and the% elongation comprises greater than about 140%.
    [15" claim-type="Currently amended] 15. The coating of claim 14, wherein said Young's modulus comprises 0.5 MPa or less.
    [16" claim-type="Currently amended] 15. The coating of claim 14, wherein said percent elongation comprises at least 150%.
    [17" claim-type="Currently amended] The coating of claim 1, wherein the percent elongation of the curable composition comprises greater than about 131%.
    [18" claim-type="Currently amended] A photocurable composition comprising a reactive monomer and a photoinitiator; The composition is selected such that the composition is such that when the composition is cured, at least one of the set of coordinates of the window viscoelastic window is not located in a window defined by the following set of window coordinates, the coordinates being in units of Pascals. Optical fiber coating, characterized in that the logarithmic ") and the elastic shear modulus (G ');
    (A) (about 3.000, about 5.180), (about 3.000, about 4.480), (less than about 3.850, about 5.180), and (less than about 3.85, about 4.480); (B) (about 3.000, about 6.000), (about 3.000, about 5.180), (about 4.530, about 6.000), and (about 4.530, about 5.180); And (C) (about 4.530, about 5.729), (about 4.530, about 5.604), (about 5.112, about 5.729), and (about 5.112, about 5.604).
    [19" claim-type="Currently amended] The coating of claim 18 wherein the composition has a Young's modulus of less than about 1.2 MPa upon curing.
    [20" claim-type="Currently amended] 20. The composition of claim 19, wherein the Young's modulus comprises less than about 0.9 MPa.
    [21" claim-type="Currently amended] 19. The composition of claim 18, wherein the composition further comprises a thermoplastic elastomer.
    [22" claim-type="Currently amended] 19. The composition of claim 18, wherein the composition is substantially free of tackifiers.
    [23" claim-type="Currently amended] 19. The composition of claim 18, wherein the composition comprises an adhesive.
    [24" claim-type="Currently amended] 24. The composition of claim 23, wherein the pressure sensitive adhesive comprises at least one mixture selected from rosin esters, fatty hydrocarbon resins, aromatic hydrocarbon resins, and mixtures thereof.
    [25" claim-type="Currently amended] 22. The composition of claim 21, wherein the elastomer comprises at least one compound selected from styrene-diene block copolymers, homopolymers, and mixtures thereof.
    [26" claim-type="Currently amended] 27. The composition of claim 25, wherein the elastomer comprises a diene comprising at least one selected from butadiene, isoprene, and mixtures thereof.
    [27" claim-type="Currently amended] 19. The composition of claim 18, wherein the Young's modulus comprises less than about 0.65 MPa and the% elongation comprises greater than about 140%.
    [28" claim-type="Currently amended] The composition of claim 27, wherein the Young's modulus comprises about 0.5 MPa or less.
    [29" claim-type="Currently amended] The composition of claim 27, wherein said percent elongation comprises at least 150%.
    [30" claim-type="Currently amended] The composition of claim 18, wherein the percent elongation of the composition comprises greater than about 131%.
    [31" claim-type="Currently amended] core;
    Cladding surrounding the core; And
    A coating surrounding the core, the coating comprising a reactive monomer and a photoinitiator;
    The composition is selected such that at least one set of coordinates appears in at least one of the following windows in which the window viscoelastic window upon curing of the composition is defined as at least the following window coordinates, wherein the coordinates are in Pascals. Coated optical fiber, characterized in that the logarithmic modulus (G ") and elastic shear modulus (G ') of:
    (1) (about 3.000, about 4.480), (about 3.000, about 3.000), (6.000, about 4.480) and (about 6.000, about 3.000); (2) (greater than about 3.840, about 5.180), (greater than about 3.840, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); And (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729).
    [32" claim-type="Currently amended] 32. The fiber of claim 31 wherein the fiber has a second set of coordinates located in one of the window set of coordinates.
    [33" claim-type="Currently amended] 32. The fiber of claim 31 wherein the set of coordinates of the at least one composition is located in at least one of the following set of second window coordinates:
    (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); (7) (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850); (8) (about 5.440, about 4.480), (about 5.440, about 3.000), (about 6.000, about 4.480), and (about 6.000, about 3.000); (9) (about 4.530, about 3.850), (about 4.530, about 3.000), (about 5.440, about 3.850), and (about 5.440, about 3.000); (10) (about 4.106, about 5.474), (about 4.106, about 5.350), (about 4.930, about 5.474), and (about 4.930, about 5.350); (11) (about 4.232, about 5.375), (about 4.232, about 5.235), (about 4.958, about 5.375), and (about 4.958, about 5.235); And (12) (about 4.139, about 5.488), (about 4.139, about 5.409), (about 4.894, about 5.488), and (about 4.894, about 5.409).
    [34" claim-type="Currently amended] The method of claim 33, wherein the second set of window coordinates comprises (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480); And (7) (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850).
    [35" claim-type="Currently amended] The method of claim 33, wherein the second set of window coordinates comprises (3) (about 5.112, about 6.000), (about 5.112, about 5.180), (about 6.000, about 6.000), and (about 6.000, about 5.180); (4) (about 4.530, about 5.604), (about 4.530, about 5.180), (about 5.112, about 5.604), and (about 5.112, about 5.180); (5) (about 4.530, about 6.000), (about 4.530, about 5.729), (about 5.112, about 6.000), and (about 5.112, about 5.729); And (6) (about 5.440, about 5.180), (about 5.440, about 4.480), (about 6.000, about 5.180), and (about 6.000, about 4.480).
    [36" claim-type="Currently amended] The fiber of claim 31, wherein the effective area of the fiber comprises greater than about 70 μm 2 at about 1550 nm.
    [37" claim-type="Currently amended] The fiber of claim 36, wherein the effective area comprises at least about 80 μm 2 at 1550 nm.
    [38" claim-type="Currently amended] The method of claim 1, wherein the set of window coordinates comprises (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850). Characterized by coating.
    [39" claim-type="Currently amended] The set of window coordinates of claim 18, wherein the composition is in a set of window coordinates comprising (greater than about 3.840, about 5.180), (greater than about 3.840, about 3.850), (about 5.440, about 5.180), and (about 5.440, about 3.850). A coating having at least one set of coordinates positioned.
    [40" claim-type="Currently amended] The coating of claim 8 wherein said elastomer comprises a thermoplastic polyurethane.
    [41" claim-type="Currently amended] The coating of claim 1 wherein the composition further comprises a carrier.
    [42" claim-type="Currently amended] The coating of claim 18 wherein the composition further comprises a carrier.
    [43" claim-type="Currently amended] The coating of claim 18 wherein the composition comprises a homopolymer.
    [44" claim-type="Currently amended] The coating of claim 1 wherein the composition comprises a homopolymer.
    [45" claim-type="Currently amended] 22. The coating of claim 21, wherein the elastomer comprises a thermoplastic polyurethane.
    [46" claim-type="Currently amended] 19. The coating of claim 18, wherein at least said second set of coordinates represented by said composition is not in said set of window coordinates.
    [47" claim-type="Currently amended] 19. The coating of claim 18, wherein at least two additional coordinate sets represented by the composition are not in the window coordinate set.
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    同族专利:
    公开号 | 公开日
    WO2003027037A2|2003-04-03|
    US20030095770A1|2003-05-22|
    JP2005503593A|2005-02-03|
    CN1288105C|2006-12-06|
    CN1556776A|2004-12-22|
    US6869981B2|2005-03-22|
    EP1436236A1|2004-07-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-09-21|Priority to US32362201P
    2001-09-21|Priority to US60/323,622
    2002-03-01|Priority to US10/087,481
    2002-03-01|Priority to US10/087,481
    2002-08-08|Application filed by 코닝 인코포레이티드
    2002-08-08|Priority to PCT/US2002/025309
    2004-04-29|Publication of KR20040035851A
    2018-10-30|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    US32362201P| true| 2001-09-21|2001-09-21|
    US60/323,622|2001-09-21|
    US10/087,481|2002-03-01|
    US10/087,481|US6869981B2|2001-09-21|2002-03-01|Optical fiber coatings with pressure sensitive adhesive characteristics|
    PCT/US2002/025309|WO2003027037A2|2001-09-21|2002-08-08|Optical fiber coatings with pressure sensitive adhesive characteristics|
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