# Patent

## Title
Radiation-curable composition for optical fiber coating materials

## Abstract

Compositions for use in optical fiber coatings and optical fibers and optical fiber arrays using these coatings are disclosed, as are methods for making the same. The compositions comprise a combination of two different radiation curable urethane oligomers, and can further comprise one or more reactive monomers. One of the oligomers has at least three functional groups that can undergo radiation cure, and comprises a lactone modified polyol.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 10/360,176, filed Feb. 6, 2003 now U.S. Pat. No. 6,872,760.


FIELD OF THE INVENTION
The present invention relates to radiation-curable compositions useful as coatings for optical fibers. More specifically, these compositions comprise a unique combination of two different radiation curable urethane oligomers; one or more mono- or polyfunctional reactive monomers can also be included.
BACKGROUND OF THE INVENTION
Optical glass fibers have become integral to the telecommunications industry. While the fibers are exceptionally strong, they are easily flawed such as by exposure to environmental factors including dust and moisture. It is therefore desired to coat the fibers almost immediately after formation with one or more coating materials. In some cases these fibers have one coating material and in other cases two or more coatings may be used. For example, the fibers may be coated with a soft inner primary coating and a tougher secondary coating; the secondary coating typically provides a more durable exterior for the optical fiber. The outermost coating layer is often colored, such as by application of an ink layer or through addition of a colorant to the coating material itself. Color coding of the fibers allows for easier identification of the individual coated optical glass fibers. This is particularly relevant in industries where a plurality of fibers are aggregated into a cable. In such applications, the fibers are typically bonded together in a matrix material. For example, the matrix material can encase the optical fibers or can edge bond the optical fibers together.
It is generally desired that the matrix material used in optical fiber assemblies will provide both the desired level of “toughness” while still allowing for flexibility. The physical properties of the matrix components, such as the polymers, can be related to the performance of the matrix material. For example, a suitable matrix material will typically have a glass transition temperature (“Tg”) high enough to allow acceptable heat strip for peelable optical fiber ribbon and to provide resistance to environmental attacks such as by moisture and/or chemicals. The matrix material should also have an elongation sufficient to render the ribbon robust in various handling operations, such as in heat strip operations. Since the matrix material will most typically be in direct contact with the outermost coating on the fibers, it is also desirable that the matrix material release from the fibers when necessary, such as when repairing or branching is needed. The ability to access individual fibers in a ribbon matrix without damaging the fiber or any coating or identification thereon is an important feature. The ability to release, however, must be countered against the ability to adhere to the fibers during use. The matrix material should also have high resistance to thermal, oxidative and hydrolytic degradation. The ability to cure rapidly, such as upon exposure to UV radiation, can also be an important feature. Thus, there are a number of desirable characteristics for a matrix material, and it is often the case with compositions known in the art that improvement of one characteristic results in the sacrifice of another.
Similarly, secondary coatings used with optical fibers have a number of desirable characteristics. For example, such coatings should function as a hard, tough protective outer layer, preventing damage to the glass fiber during processing and use. A secondary coating should undergo minimal changes in physical properties upon exposure to organic solvents and moisture. A secondary coating should also have a coefficient of friction that facilitates winding and unwinding of the fibers on spools and allows the fibers to slide easily along each other in a cable structure, thus relieving stress, yet also allows the fibers to stay aligned on the spool.
SUMMARY OF THE INVENTION
The present invention provides a curable composition that finds particular application as an optical fiber coating material and is especially suitable as a matrix material and/or a secondary coating. The composition comprises two different radiation curable urethane components. The first of these components imparts to the composition a high Tg, that is, a Tg equal to or greater than about 50° C. The second of these components imparts a high elongation to the composition, that is, an elongation equal to or greater than about 15 percent. The composition can further comprise one or more reactive monomers; these monomers can be monofunctional, polyfunctional or combinations thereof. Various additives can also be included, such as photoinitiators, thermal initiators, releasing agents, anti-oxidants, stabilizers, UV absorbers, adhesion promoters and the like.
The present compositions therefore combine the characteristics of high Tg and high elongation. These properties are particularly desirable in matrix and secondary fiber coatings. Other desired characteristics of optical fiber matrix materials and fiber coatings, such as good curing speed and high resistance to various environmental factors, are also provided by the present compositions.
The present invention is further directed to optical fiber ribbon arrays containing secondary coatings and/or matrices prepared from the present compositions, and to processes for preparing these arrays.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a composition comprising a combination of two different radiation curable urethane components. A “radiation curable urethane component” is a compound having urethane linkages and at least one functional group that can be cured by exposure to radiation. The first of these components generally imparts a high Tg to the compositions of the invention, and comprises at least three radiation curable functionalities. The second of these components generally imparts a high elongation to the present compositions. The second component is generally different from the first and may, but need not, have at least three radiation curable functionalities; in certain embodiments it has at least one such functionality. The present compositions can also include one or more mono- or poly-functional reactive monomers that can also influence the properties of the coating compositions. Additives standard in the art, such as photoinitiators, thermal initiators, releasing agents, anti-oxidants, UV absorbers, stabilizers and the like can also optionally be added.
The first radiation curable urethane generally imparts a Tg to the final composition of equal to or greater than about 50° C. Particularly suitable for matrix coatings are those that impart a Tg of equal to or greater than about 85° C.; particularly suitable for secondary coatings are those that impart a Tg of equal to or greater than about 55° C. The Tg of the composition can be measured using a dynamic mechanical analyzer following methods standard in the art, such as those described in the examples below. As used herein, “Tg” is defined as the temperature at the peak of Tan δ during a dynamic thermo mechanical test. It should be noted that “high Tg” refers to the Tg of the final composition and not the Tg of the radiation curable urethane itself.
The high Tg imparting radiation curable urethane can be formed by means standard in the art, such as through the reaction of a curable functionality-terminating aromatic-containing polyol oligomer, a polyisocyanate and an endcapping monomer. A particularly suitable starting material is one where the polyol oligomer is a diphenylmethane-containing polyol oligomer. A “diphenylmethane-containing polyol oligomer” refers to a compound containing at least one diphenylmethane moiety and comprising two terminating curable functionalities and at least two hydroxyl functionalities. The diphenylmethane-containing polyol generally comprises from 1 to 4 diphenylmethane groups and can be depicted by formula I:




In formula I, R1, R1′, R1′′, and R1′′′ are the same or different and are selected from hydrogen or a linear or branched lower alkyl group having 1 to 16 carbon atoms; R2 and R2′ are the same or different and are selected from linear or branched alkyl groups having 2 to 8 carbon atoms; R3 and R3′ are the same or different and comprise reactive moieties selected from acrylic, methacrylic, vinylic, allylic, styrenic, acrylamide, norbornenyl, acetylenic, epoxy, mercapto, amino, itanoic and crotonic moieties; a and c are the same or different and are from 0 to 20; and b is from 0 to 3. The “R1” structures are typically hydrogen, methyl, ethyl, propyl, butyl and the like. In a particularly suitable embodiment, R3 and R3′ are acrylic ester structures, b is 0 and a and c are 0 to 6. Even more suitable is an embodiment wherein all of the “R1” structures are methyl and a, b, and c are all 0. Typically, these polyols are derived from diacrylated bisphenol diglycidyl ethers or their alkoxylated derivatives, i.e. compounds where there are alkoxyl chains between the bisphenol structure and the glycidyl structure. In a particularly suitable embodiment, the bisphenols used in producing these polyols are bisphenol A. Examples of such polyols include the so-called epoxy acrylate oligomers from Sartomer Company (Exton, Pa.) known as CN-104 and CN-120 and UCB in their EBECRYL line of products. When a diphenylmethane-containing polyol is used, it will be understood that the oligomer is not wholly aliphatic.

In one embodiment, the polyol oligomer has been modified with a lactone. In a specific embodiment, the diphenylmethane-containing polyol oligomer as described above has been modified with a lactone. Typically, the diphenylmethane-containing polyol oligomer contains secondary hydroxyl groups that are relatively hindered and unreactive. By reacting the secondary hydroxyl groups with a cyclic lactone, the secondary hydroxyl groups are transformed into primary hydroxyl groups. Any cyclic lactone can be used according to the present invention; particularly suitable are ε-caprolactone and its derivatives. Polyol oligomers that have been reacted with a lactone are referred to herein as “modified with a lactone”, “lactone modified” or similar terms. The primary hydroxyl groups derived from this reaction can then be reacted with an isocyanate group. It will be appreciated that transforming a secondary hydroxyl group into a primary hydroxyl group facilitates its reaction with an isocyanate group. In addition to the favorable impact on the reaction, modification with the cyclic lactone also results in a more flexible oligomer having better or higher elongation. Surprisingly, better elongation is achieved this way without impacting the Tg of the oligomer or composition.
The polyisocyanate component can be either aromatic or aliphatic. Aliphatic polyisocyanates of from 4 to 20 carbon atoms may be employed. Suitable saturated aliphatic polyisocyanates include but are not limited to isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate. Isophorone diisocyanate and methylenebis(4-cyclohexyl isocyanate) are particularly suitable. Suitable aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, and mixtures thereof.
The endcapping monomer may be one that is capable of providing at least one radiation curable functionality, which, for example, may be acrylic, methylacrylic, vinylic, allylic, styrenic, acrylamide, norbornenyl, acetylenic, epoxy, mercapto, amino, itanoic, and crotonic moieties. The radiation-curable functionality typically used is ethylenic unsaturation, which can be polymerized through radical polymerization or cationic polymerization. Specific examples of suitable ethylenic unsaturation are groups containing (meth)acrylate, styrene, vinylether, vinyl ester, N-substituted acrylamide, N-vinyl amide, maleate esters, and fumarate esters. “(Meth)acrylate” refers to both methacrylate and acrylate. Acrylate functionality is particularly suitable. Endcapping monomers that provide acrylate or methacrylate termini are particularly suitable and include but are not limited to hydroxyalkyl(meth)acrylates such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth )acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. A particularly suitable endcapping monomer is hydroxyethyl(meth)acrylate. 4-hydroxybutyl vinyl ether is a particularly suitable endcapping group for introducing vinyl ether termini.
The molar ratio of the polyol, polyisocyanate and endcapping monomer used in preparing the high Tg imparting component in one embodiment is typically about 1:2–3:1–2. A particularly suitable ratio is 1:2.5:1.5. A high Tg urethane acrylate based on the polyol of general formula I will have a structure as depicted in formula II:




All the hydroxyl groups from formula I are shown in formula II as an “R4” structure (R4, R4′, and R4′′). R4, R4′, and R4′′ can be the same or different and are selected from hydroxy groups and the reactive groups containing curable functionalities as defined above for R3 and R3′ and at least one of the “R4” structures contains any of the reactive groups as defined above for R3 and R3′. It will be understood that only one of the hydroxyl groups shown in formula I needs to be functionalized to be within the present invention; such a molecule would contain three radiation-curable functionalities. The remaining “R4” structures, if not further functionalized, would just be hydroxyl groups.
It is evident that one skilled in the art can devise other methods to synthesize the urethane compounds having structures as shown in formula II. For example, such a product can be derived from a suitable alkoxylated bisphenol A diol, a diisocyanate, and a suitable endcapping monomer having more than one radiation curable moiety.
The high Tg imparting urethane component is typically present in the compositions of the invention in amounts from 20 to 80 weight percent, such as from 30 to 70 weight percent, with weight percent being based on the total weight of the two urethane oligomers, or from 10 to 40 weight percent, with weight percent being based on the total weight of the composition.
The second component of the present composition is a radiation curable urethane oligomer that imparts high elongation to the present compositions. By “high elongation” is meant an elongation at break of equal to or greater than about 15 percent. The elongation will typically be less than 100 percent. In one embodiment, the coating is a matrix coating having an elongation of 35 to 65 percent and in another embodiment the coating is a secondary coating having an elongation of 15 to 25 percent.
Whether a particular radiation curable urethane polymer imparts a high elongation to a composition can be determined by one skilled in the art using standard methods. More specifically, the radiation curable urethane can be prepared and added into the present compositions, which can then be tested for elongation on an Instron according to ASTM D-882 using 5 mil films. It should be noted that “high elongation” refers to the elongation of the final composition and not the elongation of the radiation curable urethane itself.
The high elongation imparting component can be prepared by reacting a polyol, a polyisocyanate and an endcapping monomer. More specifically, the high elongation imparting urethane component of the present compositions is the reaction product of an aliphatic or aromatic polyol, an aliphatic or aromatic polyisocyanate, and an endcapping monomer capable of supplying a reactive terminus. The polyol used in the reaction will typically be based on a diol having an Mn of at least about 2000 daltons. This includes polyether polyols such as polyols obtained by ring-opening polymerization or copolymerization of at least one type of compound selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyl-tetrahydrofuran, oxetane, and substituted oxetane. Other suitable polyols include propylene glycol and polypropylene glycol. Mixtures of all of these polyols can also be used. Examples of desirable polyol compounds are polytetramethylene glycol with an Mn of at least 2000 daltons. Particularly suitable polyols are polyTHF 2000 and polyTHF 2900 from BASF Corporation as well as TERATHANE 2000 and TERATHANE 2900 from DuPont. Other examples of desirable polyol compounds are polypropylene glycols with a number average molecular weight of at least 2000 such as PPG 2025 from Bayer or PLURACOL 4000 from BASF Corporation. Aromatic polyols can also be used here provided their Mn is at least 2000. Smaller polyols with more than two hydroxyl groups are also often used in addition to these relatively high molecular weight diols. Such polyols include 1,1,1-trimethylolpropane and its dimer, pentaerythritol and its dimer, glycerine and ribose, with 1,1,1-trimethylolpropane being particularly suitable.
Many of the aliphatic and aromatic polyisocyanates listed above for the high Tg imparting component can also be used here. Tetramethylxylylene diisocyanate (TMXDI) is especially suitable. Additional suitable aliphatic polyisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, and mixtures thereof. It will be appreciated that many of the aliphatic isocyanates listed here are more suited to the high elongation imparting component than the high Tg imparting component; that is because these isocyanates are very flexible and give low Tg materials.
The endcapping monomer is also described above for the high Tg imparting component; hydroxy alkyl acrylates are again particularly suitable.
The molar ratio of polyol, polyisocyanate and endcapping monomer used in preparing the high elongation imparting component is typically 0.8–3.0:1.0–4.0:1; a particularly suitable ratio is 1.0–2.2:1.5–3.0:1.
A particularly suitable high elongation imparting component combines polytetramethylene glycol having an Mn of 2000 with trimethylolpropane, TMXDI, and hydroxyethyl acrylate in a molar ratio of 2.1:2.8:1. TERATHANE 2000 is a polytetramethylene glycol having an Mn of 2000. It will be appreciated that this molecule contains aromaticity and is therefore not wholly aliphatic. In one embodiment, both the high Tg and high elongation imparting components have aromatic moieties and thus neither are wholly aliphatic.
The high elongation imparting radiation curable urethane is typically present in the compositions of the invention in an amount from about 20 to 70 weight percent, such as from 30 to 60 weight percent, with weight percent being based on the total weight of the urethane components, or from 10 to 40 weight percent, with weight percent being based on the total weight of the composition. In one embodiment, the amount of high elongation imparting component is less than 30 weight percent and in another embodiment is less than 20 weight percent of the total weight of the composition. The ratio of high Tg imparting radiation curable urethane to high elongation imparting radiation curable urethane typically ranges from about 1:3 to about 3:1.
In one embodiment, neither of the radiation curable urethane oligomers contain an isocyanurate structure. In another embodiment they contain no silicone-modified moieties, aliphatic diisocyanate residues or propoxylated acrylates, and in yet another embodiment, neither of the oligomers has the structure described as the second oligomer of U.S. Pat. No. 5,837,750, which is hereby incorporated by reference.
Both of the radiation curable urethane components of the present compositions can be prepared using methods standard in the art. There are generally two protocols for making the radiation curable urethane oligomers described herein. One protocol involves reacting the isocyanate component with the polyol first and then reacting the resulting product with the endcapping monomer. It is particularly suitable to synthesize the high Tg imparting oligomer using this protocol. The other protocol involves reacting the isocyanate component with the endcapping monomer followed by reaction with the polyol. It is particularly suitable to prepare the high elongation imparting oligomer using this protocol. The “polyol”, in the case of the first radiation curable urethane, refers to the aromatic-containing polyol oligomer. Suitable catalysts can be used to increase the reaction rate between the hydroxyl group and the polyisocyanate; such catalysts are known in the art and include, for example, dibutyltindilaurate, dibutyltinoxide, dibutyl tin di-2-hexoate, stannous oleate, stannous octoate, lead, octoate, ferrous acetoacetate, and amines such as triethyleneamine, diethylmethylamine, triethylenediamine, dimethylethylamine, morpholine, N-ethyl morpholine, piperazine, N,N-dimethyl benzylamine, N,N-dimethyl lauralamine and mixtures thereof.
The composition of the present invention can also be prepared using methods standard in the art. For example, the two urethane oligomers can be prepared separately and blended or one oligomer can be made in the presence of the other, such as sequentially.
It will be appreciated that the high elongation imparting radiation curable urethane component imparts elongation properties to the present compositions. It is therefore possible to achieve a composition having suitable elongation without the use of various thiol elongation promoters, such as the mercapto or sulfide elongation promoters described in U.S. Pat. No. 6,265,476.
The present compositions can further comprise one or more mono- or polyfunctional reactive monomers. These monomers can perform numerous functions in the present compositions; for example, the reactive monomer(s) can be used to adjust the viscosity of the coating compositions or to increase the crosslinking density of the compositions. The monomers are reactive, which means they contain at least one functional group capable of polymerization under radiation curable conditions.
The monomers can be mono-, or polyfunctional. A particularly suitable combination is one in which two monofunctional monomers are combined with one polyfunctional monomer, such as a tri- or tetra-functional mix. A particularly suitable combination within this embodiment is one that includes isobornyl acrylate, N-vinylpyrrolidone (“NVP”) and dipentaerythritol pentaacrylate. In this combination, the isobornyl acrylate can be added to the composition to lower the viscosity and contribute to Tg; NVP can be added to contribute to the high Tg, a fast cure, and the reduced viscosity of the composition; and dipentaerythritol pentaacrylate can be added to improve the equilibrium modulus by increasing the crosslinking density. Suitable monomers may be straight or branched chain alkyl, cyclic or partially aromatic monomers, and can comprise, for example, a monomer or monomers having an acrylate or vinyl ether functionality and a C4–C20 alkyl or polyether moiety. Examples of such reactive monomers include hexyl acrylate, 2-ethylhexylacrylate, isobornylacrylate, decylacrylate, laurylacrylate, stearylacrylate, ethoxyethoxy-ethylacrylate, laurylvinylether, 2-ethylhexylvinyl ether, N-vinyl formamide, isodecyl acrylate, isooctyl acrylate, vinylcaprolactam, N-vinylpyrrolidone, acrylamide, nonylphenol acrylate and the like. In one embodiment, none of the monomers are transesterified.
Another suitable type of reactive monomer is a compound comprising an aromatic group. Examples include, but are not limited to, ethyleneglycolphenyletheracrylate, polyethyleneglycolphenyletheracrylate, polypropyleneglycolphenyletheracrylate, phenoxyethylacrylate, and alkyl-substituted phenyl derivatives of the above monomers, such as polyethyleneglycolnonylphenyletheracrylate.
Further examples of suitable monomers include C2–C18 hydrocarbondioldiacrylates, C4–C18 hydrocarbondivinylethers, C3–C18 hydrocarbontrioltriacrylates, the polyether analogs thereof, and the like, such as 1,6-hexanedioldiacrylate, trimethylolpropanetriacrylate, hexanedioldivinylether, triethyleneglycol diacrylate, and alkoxylated bisphenol A diacrylate. Typically, the reactive monomers will be added in an amount ranging between about 25 and 75 weight percent of the total composition, such as 30 and 65 weight percent. If more than one reactive monomer is present, the amounts of monomers are added together to determine the amount of this component in the present compositions. One embodiment of the present invention specifically excludes compositions wherein one of the monomers is that taught in U.S. Pat. No. 5,998,497 when a polyether urethane acrylate and photoinitiator are also present; also, the monomers used in the present composition do not have to be specially purified as in U.S. Pat. No. 6,323,255.
When there are three or more cyclic rings in 20 to 85 weight percent of the radiation curable urethane components, and there is also a polymerizable mono-functional vinyl monomer having a Tg greater than about 50° C., the urethane bonds are present in the composition at a concentration of less than 2.0×10−3 mol per gram.
It is a feature of the present invention that the compositions disclosed herein can be cured by free radical cure. Those skilled in the art will understand that free radical cure includes the steps of initiation, propagation, chain transfer and termination. When cationic curable functional groups are included in the composition, they can also be cured by cationic polymerization processes. Cure can be provoked by the use of actinic light, electron beam or heat depending on the application requirements; suitable initiators may also be included to effect initiation.
When radiation cure is desired, the present compositions may further comprise at least one photoinitiator. Conventional photoinitiators can be used, including benzophenones, acetophenone derivatives, such as alpha-hydroxyalkylphenylketones, benzoin alkyl ethers and benzyl ketals, monoacylphosphine oxides, and bisacylphosphine oxides. The conventional photoactive onium salts can be used to effect cationic cure. Particularly suitable free radical photoinitiators are combinations of an acetophenone derivative and a bisacylphosphine oxide, although in one embodiment, the bisacrylphosphine oxides described in U.S. Pat. No. 6,359,025 are specifically excluded.
When the liquid curable resin composition of the present invention is to be heat cured, a thermal polymerization initiator such as a peroxide or an azo compound can be used. Specific examples include benzoyl peroxide, t-butyl oxybenzoate and azobisisobutyronitrile.
The amount of photoinitiator or thermal inhibitor in the present compositions will typically range from about 0 to 15 weight percent, such as from about 1 to 8 weight percent, with weight percent being based on the total weight of the composition.
The present compositions can also optionally comprise additives standardly known in the art. These additives typically comprise less than about 15 weight percent of the present compositions. For example, a release agent can be added. Examples include γ-aminopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, and polydimethylsiloxane derivatives. Typically, the release agent or agents will be present in an amount of between about 2 and 3 weight percent. In one embodiment, a portion of the release agent is particulate, and would be in particulate form even after the present compositions are cured.
To improve shelf life or storage stability of the composition prior to cure, as well as to increase thermal and oxidative stability of the cured compositions, one or more stabilizers or anti-oxidants can be included in the composition.
Examples of suitable stabilizers include tertiary amines such as diethylethanolamine and trihexylamine; hindered amines; organic phosphites; hindered phenols; mixtures thereof; and the like. Some particular examples of antioxidants that can be used include propionates such as octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate and hydrocinnamates such as thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy) hydrocinnamate and tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. Suitable commercially available antioxidants include IRGANOX 1010, 1035, 1076, and 1222, manufactured by Ciba Specialty Chemicals Corporation.
UV absorption agents can also be included including those commercially available from Ciba Geigy as TINUVIN P234, 320, 326, 327, 328, 329, and 213.
Still other additives or components that may appear in the final coating include pigments, lubricants, wetting agents, adhesion promoters and leveling agents. These additives may be present in an effective amount that is usual for the additive when used in optical fiber coatings or protective materials. The person skilled in the art can determine the additives and amounts that are appropriate for a given use.
The viscosity of the coating composition will typically be between about 1000 and 10,000 centipoises (cps) as measured using a Brookfield cone and plate viscometer No. 52 spindle at 5 rpm and 25° C.; a viscosity of between 4000 and 8000 cps is particularly suitable for optical ribbon matrix and secondary coating applications. Viscosity can be adjusted by any means known in the art.
The present compositions can be formulated using techniques and methods that are standard in the art.
In addition to high Tg and high elongation, the compositions of the present invention have numerous additional characteristics that render them suitable for use as optical ribbon coating materials. For example, the present compositions will typically have an equilibrium modulus after cure of greater than about 1 MPa and as high as 60 MPa or more. For matrix coatings, an equilibrium modulus of 1 to 20 is particularly suitable and for secondary coatings 20 to 60 is particularly suitable. Equilibrium modulus can be measured using a dynamic mechanical analyzer. It has been determined that the use of a radiation curable oligomer comprising three or four radiation curable functionalities imparts a higher equilibrium modulus to the final composition than does a radiation curable oligomer comprising only two radiation curable functionalities. Because there are more functional groups on the present oligomers, there is a higher crosslink density and hence a higher equilibrium modulus. The higher the crosslink density the “harder” the coating and the harder it will be for water, oil and the like to penetrate the coating. Thus, the present compositions are particularly suitable for applications in which penetration of water, oil, etc. is not desired; in contrast, a difunctional oligomer may not provide this desired characteristic.
The Youngs modulus of the present compositions, when cured, is typically greater than about 400 MPa and is typically from 500 to 1200 MPa. Youngs modulus is also derived from dynamic mechanical analysis.
The Secant modulus of the present compositions, when cured, is typically greater than about 300 MPa and is typically from 300 to 1000 MPa. Secant modulus is measured using an Instron according to ASTM D-882.
The Tensile stress at break of the present compositions, when cured, is typically greater than about 22 MPa and is typically between 25 and 50 MPa. Tensile stress is measured at 25° C. using an Instron according to ASTM D-882.
One embodiment of the present invention includes compositions that specifically exclude unsaturated substituted siloxane adhesion promoters and/or the adhesion promoters described in U.S. Pat. Nos. 5,977,202; 6,316,516; and 6,355,751, all of which are incorporated by reference herein. In other embodiments, the present compositions do not include a phospholipid, nor do they include a chromaphoric indicator.
The present invention is further directed to an optical fiber-bonded ribbon array wherein one or more of the coatings are of the present invention and method for making such an array. The array generally comprises a plurality of optical fibers that can be coated with any coatings standardly used in the art for this purpose, such as those that are radiation cured, or the present compositions. Any standard optical fiber can be used according to the invention, such as those having a glass core and a glass cladding layer. For example, the core may comprise silica doped with oxides of germanium or phosphorus and the cladding can be a pure or doped silicate, such as a fluorosilicate. The fibers may alternatively comprise a polymer clad silica glass core, such as an organosiloxane polymer cladding. The coated fibers are then secured in the desired configuration, such as in a parallel and planar or other prescribed arrangement, and are embedded in the composition of the present invention. For example, the fibers can be arranged in the desired manner, the liquid matrix can be applied to the fibers, and the matrix composition can be cured. The matrix composition, when cured, adheres to the fibers during use, but can be stripped therefrom without substantially damaging the integrity of the coated optical fibers, including any ink layer that has been deposited thereon. Specific embodiments of the present invention include those wherein the second coating layer on the fiber, the matrix coating layer, or both are comprised of the composition of the present invention. When both the secondary and matrix coatings are within the present invention, they can be the same or different embodiments. The primary coating underlying the secondary coating can be any primary coating known in the art, which coatings are widely commercially available.
As used herein, unless otherwise expressly specified all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Plural encompasses singular and vice versa. Also, as-used herein, the term “polymer” is meant to refer to oligomers and both homopolymers and copolymers. The prefix “poly” as used herein refers to two or more.


EXAMPLES
The following examples are intended to illustrate the invention, and should not be construed as limiting the invention in any way. “Parts” refers to parts by weight.
Example 1
Preparation of High Tg Imparting Oligomer (1)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer and a condenser were charged 242.0 parts of CN-120 (an epoxy diacrylate from Sartomer), 1.4 parts of 2,6-di-t-butyl-4-methylphenol, 0.5 parts of dibutyltindilaurate, 0.2 parts of phenothiazine, and 219.2 phenoxyethylacrylate. After the mixture was heated to 55° C., 277.5 parts of isophorone diisocyanate was added while maintaining the reaction temperature at 80° C. or below. The mixture was subsequently held at 85° C. for two hours. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. After all the hydroxyl functionality was consumed according to the NCO equivalent measurement result, 354.6 parts of hydroxyethyl acrylate and 0.5 parts of dibutyltindilaurate were added to the reactor while controlling the temperature at around 80° C. The mixture was held at 80° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements. The NCO equivalent weight measurements were performed, which were accomplished by reacting any residual NCO functionality with an excess amount dibutylamine. The amount of amine consumed (if any) can be then calculated from titrating the amine with a standard acidic solution.
Example 2
Preparation of High Tg Imparting Oligomer (2)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer and a condenser were charged 242.0 parts of CN-104 (an epoxy diacylate from Sartomer), 1.4 parts of 2,6-di-t-butyl-4-methylphenol, 0.5 parts of dibutyltindilaurate, 0.2 parts of phenothiazine, and 219.2 phenoxyethylacrylate. After the mixture was heated to 55° C., 277.5 parts of isophorone diisocyanate was added while maintaining the reaction temperature at 80° C. or below. The mixture was subsequently held at 85° C. for two hours. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. After all the hydroxyl functionality was consumed according to the NCO equivalent measurement result, 354.6 parts of hydroxyethyl acrylate and 0.5 parts of dibutyltindilaurate were added to the reactor while controlling the temperature at around 80° C. The mixture was held at 80° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements.
Example 3
Preparation of High Elongation Imparting Oligomer (3)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer and a condenser were charged 190.4 parts of meta-tetramethylene diisocyanate, 327.6 parts of isobornyl acrylate, 9.6 parts of trimethylolpropane, 0.5 parts of dibutyltindilaurate, 1.4 parts of 2,6-di-t-butyl-4-methylphenol and 0.2 parts of phenothiazine. The mixture was heated up and held at 80° C. until the NCO equivalent weight was within the theoretical value. The mixture was then cooled to 35° C. and 32.4 parts of hydroxyethyl acrylate was added to the reactor. Cooling was applied to the reactor during the addition as necessary to control the reaction temperature to below 40° C. The mixture was then held at 38° C. for two hours. A sample was taken for isocyanate equivalent weight measurement to confirm the completeness of the reaction. Thereafter, 1053.4 parts of PolyTHF2000 and 0.5 parts of dibutyltindilaurate were added to the reactor while controlling the temperature to around 65° C. The mixture was then held at 65° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements.
Example 4
Formulation (1)
Into a three liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer, and a condenser were charged 673.6 parts of N-vinyl-2-pyrrolidone (ISP), 164.2 parts of phenoxyethylacrylate (Sartomer), 126.6 parts of isobornyl acrylate (Sartomer), 286.4 parts of dipentaerythritol pentaacrylate (Sartomer), 1005.7 parts of oligomer (1) as synthesized in Example 1 above, and 768.2 parts of oligomer (3) as synthesized in Example 3 above. The mixture was heated to 66° C. The mixture was stirred at 66° C. until it became clear; 119.0 parts of DAROCUR 4265 (Ciba Additives) were then added. Afterwards, the mixture was stirred at 66° C. for 30 minutes. The formulation had a viscosity of 4423 cps when measured with a Brookfield viscometer at 25° C.
A five mil coating of this composition was applied to a flat of glass plate using a Bird applicator and cured at 1 J/cm2 under a D-lamp in a nitrogen atmosphere. The resulting free film gave a tensile stress at break of 46 MPa and an elongation of 43 percent when tested according to ASTM D-882. Dynamic mechanical analysis carried out at a frequency of 1 Hz, speed of 2° C. per minute from −50° C. to 180° C. on the free film gave a Tg of 126° C. and an equilibrium modulus of 12.9 MPa.
Formulation (2)
Into a three liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer, and a condenser were charged 673.6 parts of N-vinyl-2-pyrrolidone (ISP), 164.2 parts of phenoxyethylacrylate (Sartomer), 126.6 parts of isobornyl acrylate (Sartomer), 286.4 parts of dipentaerythritol pentoacrylate (Sartomer), 1005.7 parts of oligomer (2) as synthesized in Example 2 above, and 768.2 parts of oligomer (3) as synthesized in Example 3 above. The mixture was heated to 66° C. The mixture was stirred at 66° C. until it became clear; 119.0 parts of DAROCUR 4265 were then added. Afterwards, the mixture was stirred at 66° C. for 30 minutes. The formulation had a viscosity of 3814 cps when measured with a Brookfield viscometer at 25° C.
A five mil coating of this composition was applied to a flat of glass plate using a Bird applicator and cured at 1 J/cm2 under a D-lamp in a nitrogen atmosphere. The resulting free film gave a tensile stress at break of 47 MPa and an elongation of 45 percent when tested according to ASTM D-882. Dynamic mechanical analysis carried out at a frequency of 1 Hz, speed of 2° C. per minute from −50° C. to 180° C. on the free film gave a Tg of 140° C. and an equilibrium modulus of 16.5 MPa.
Example 5
Preparation of High Tg Imparting Oligomer (4)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer and a condenser were charged 242.00 parts of CN-104 (a bisphenol A epoxy based di-acrylate from SARTOMER), 1.43 parts of 2,6-di-t-butyl-4-methylphenol, 0.50 parts of dibutyltin dilaurate, 0.20 parts of phenothiazine, and 219.20 parts of phenoxyethyl acrylate. After the mixture was heated to 55° C., 277.50 parts of isophorone diisocyanate were charged to the reactor. The mixture was heated to 65° C. and held at that temperature for two hours. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, a mixture of 174.00 parts of hydroxyethyl acrylate, 180.61 parts of phenoxyethyl acrylate, and 0.50 parts of dibutyltindilaurate were added dropwise to the reactor while controlling the temperature at around 80° C. The mixture was held at 80° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements. The NCO equivalent weight measurements were accomplished by reacting any residual NCO functionality in the sample with an excess amount of dibutylamine. The amount of amine consumed (if any) can be then calculated from titrating the amine with a standard acidic solution.
Example 6
Preparation of High Elongation Imparting Oligomer (5)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer, and a condenser were charged 190.38 parts of meta-tetramethylenexylyl diisocyanate, 327.62 parts of isobornyl acrylate, 0.54 parts of dibutyltindilaurate, 1.51 parts of 2,6-di-t-butyl-4-methylphenol, 0.21 parts of phenothiazine and 9.60 parts of trimethylol propane. The mixture was heated to 65° C. and held at that temperature for one hour. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, the mixture was cooled down to 35° C. and 32.42 parts of hydroxyethyl acrylate were added dropwise to the reactor. Cooling was applied to the reactor during the addition as necessary to maintain the reaction temperature below 40° C. The mixture was then held at 38° C. for two hours. A sample was taken for NCO equivalent weight measurement to confirm the completeness of the reaction. Thereafter, 1053.38 parts of polytetramethylene glycol with a number average molecular weight of 2000 (PolyTHF2000, BASF Corporation), 383.78 parts of phenoxyethyl acrylate, and 0.5 parts of dibutyltindilaurate were added to the reactor while controlling the temperature at around 65° C. The mixture was then held at 65° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements.
Example 7
Formulation (3)
The following ingredients were used to formulate a secondary coating according to the present invention; 101.7 parts of oligomer (4) as synthesized above, 54.1 parts of oligomer (5) as synthesized above, 17.6 parts of isobornyl acrylate (SARTOMER), 3.3 parts of phenoxyethyl acrylate (SARTOMER), 23.5 parts of Photomer 8061 (COGNIS), 70.4 parts of di-trimethylolpropane tetra-acrylate (DiTMPTA) (SARTOMER), and 9.4 parts of Darocur 4265 (CIBA). The formulation had a viscosity of 4679 cps when measured with a Brookfield viscometer at 25° C.
A five mil coating of this composition was applied to a flat, glass plate using a Bird applicator and cured at 1 J/cm2 under a D-lamp in a nitrogen atmosphere. The resulting free film gave a tensile stress at break of 40 MPa and an elongation of 10 percent when tested according to ASTM D-882. Dynamic mechanical analysis carried out at a frequency of 1 Hz, speed of 2° C. per minute from −50° C. to 180° C. on the free film gave a Tg of 100° C. and an equilibrium modulus of 34 MPa.
Example 8
Synthesizing of Lactone Modified Bisphenol A Epoxy Acrylate
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer and a condenser were charged 484.00 parts of a bisphenol A epoxy diacrylate CN-104 (SARTOMER), 228.00 parts of ε-caprolactone, and 2.00 parts of tin octoate. The mixture was heated to 135° C. under a constant nitrogen blanket and was held at that temperature for 6 hours. The reaction progress was monitored by sampling for 110° C. solid measurements. The end point was reached when the 110° C. solid data is higher than 98 percent.
Synthesizing Oligomer from the Lactone Modified Bisphenol A Epoxy Acrylate (6)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer, and a condenser were charged 37.0 parts of meta-tetramethylenexylyl diisocyanate, 63.7 parts of isobornyl acrylate, 0.3 parts of dibutyltindilaurate, 0.8 parts of 2,6-di-t-butyl-4-methylphenol, 0.2 parts of phenothiazine and 1.9 parts of trimethylol propane. The mixture was heated to 80° C. and held at that temperature for one hour. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, the mixture was cooled down to 35° C. and 6.3 parts of hydroxyethyl acrylate were added dropwise to the reactor. Cooling was applied to the reactor during the addition as necessary to maintain the reaction temperature below 40° C. The mixture was then held at 38° C. for two hours. A sample was taken for NCO equivalent weight measurement to confirm the completeness of the reaction. Thereafter, a blend of 204.7 parts of polytetramethylene glycol with a number average molecular weight of 2000 (PolyTHF2000, BASF Corporation), 238.0 parts of the modified CN-104 as synthesized in Example 8, 341.1 parts of phenoxyethyl acrylate, 185.0 parts of isopherone diisocyanate, and 0.3 parts of dibutyltindilaurate was added to the reactor. The mixture was heated up to 80° C. slowly and held at that temperature for two hours. A sample was then taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, 116.0 parts of hydroxyethyl acrylate and 0.3 parts of dibutyltindilaurate were added dropwise to the reactor. Cooling was applied to the reactor during the addition as necessary to maintain the reaction temperature at 80° C. The mixture was then held at 80° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements.
Synthesizing Oligomer from un-modified Bisphenol A Epoxy Acrylate (7)
Into a two-liter, four-necked reaction kettle equipped with a thermometer, a mechanical stirrer, and a condenser were charged 37.0 parts of meta-tetramethylenexylyl diisocyanate, 63.7 parts of isobornyl acrylate, 0.3 parts of dibutyltindilaurate, 0.8 parts of 2,6-di-t-butyl-4-methylphenol, 0.2 parts of phenothiazine and 1.9 parts of trimethylol propane. The mixture was heated to 80° C. and held at that temperature for one hour. A sample was taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, the mixture was cooled down to 35° C. and 6.3 parts of hydroxyethyl acrylate were added dropwise to the reactor. Cooling was applied to the reactor during the addition as necessary to maintain the reaction temperature below 40° C. The mixture was then held at 38° C. for two hours. A sample was taken for NCO equivalent weight measurement to confirm the completeness of the reaction. Thereafter, a blend of 204.7 parts of polytetramethylene glycol with a number average molecular weight of 2000 (PolyTHF2000, BASF Corporation), 161.3 parts of CN-104 (SARTOMER), 341.1 parts of phenoxyethyl acrylate, 185.0 parts of isopherone diisocyanate, and 0.3 parts of dibutyltindilaurate was added to the reactor. The mixture was heated up to 80° C. slowly and held at that temperature for two hours. A sample was then taken for isocyanate (“NCO”) equivalent weight measurement to confirm the completeness of the reaction. Thereafter, 116.0 parts of hydroxyethyl acrylate and 0.3 parts of dibutyltindilaurate were added dropwise to the reactor. Cooling was applied to the reactor during the addition as necessary to maintain the reaction temperature at 80° C. The mixture was then held at 80° C. until it was significantly free of isocyanate functionality as revealed by NCO equivalent weight measurements.
Formulations (4) and (5)
Two formulations were made according to the procedures as outlined for formulation (3) above and the film properties were measured under the same conditions as used in formulation (3). The composition information and film properties are included in the following table.











TABLE 1









Comparative




Formulation (4)
Formulation (5)




















Composition





Oligomer (6)
64.4



Oligomer (7)

66.8



Phenoxyethyl acrylate
4.4
2.0



(SARTOMER)



DiTMPTA (SARTOMER)
24.0
24.0



Darocur 4265 (CIBA)
3.3
3.2



Formulation viscosity (cps)
4354
5042



Film Properties



Tg (° C.)
72
82



Equilibrium Modulus (MPa)
43
47



2.5% Secant Modulus (MPa)
1065
1200



Tensile (Mpa)
41
44



Elongation (%)
20
10



Toughness (mJ/mm3)
7
4










As demonstrated in Table 1, use of a lactone modified epoxy resulted in increased elongation without significantly impacting other parameters negatively.
Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.

## Claims

1. A composition comprising:
a. a first radiation curable urethane oligomer comprising at least three radiation curable functionalities; and
b. a second radiation curable urethane oligomer different from the first radiation curable urethane, wherein the first radiation curable urethane oligomer comprises a diphenylmethane-containing polyol oligomer modified with a lactone.

2. The composition of claim 1, wherein the first radiation curable urethane oligomer comprises two or more aromatic rings.

3. The composition of claim 1, wherein the lactone comprises ε-caprolactone and/or derivatives thereof.

4. The composition of claim 1, wherein a free film produced from said composition has a Tg ≧50° C. and an elongation ≧15 percent.

5. The composition of claim 1, wherein said second radiation curable urethane oligomer comprises the reaction product of tetramethylxylene diisocyanate, a polyol having an Mn of greater than 2000 daltons, and hydroxylethylacrylate.

6. The composition of claim 5, wherein said polyol comprises polytetramethylene glycol and trimethylolpropane.

7. The composition of claim 1, further comprising one or more reactive monomers.

8. The composition of claim 7, wherein at least one of the reactive monomers is monofunctional.

9. The composition of claim 1, wherein said first radiation curable urethane oligomer comprises the reaction product of isophorone diisocyanate, lactone modified epoxy diacrylate, and 2-hydroxyethyl acrylate.

10. The composition of claim 1, wherein said first radiation curable urethane oligomer has three radiation curable functionalities.

11. The composition of claim 1, wherein said first radiation curable urethane oligomer has four radiation curable functionalities.

12. A glass fiber coated with the composition of claim 1.

13. An optical fiber ribbon array containing a plurality of glass fibers bonded together in a matrix material, wherein the matrix material is a cured composition of claim 1.

14. The array of claim 13, wherein one or more of the glass fibers are also coated with a composition comprising:
a. a first radiation curable urethane oligomer comprising either three or four radiation curable functionalities; and
b. a second radiation curable urethane oligomer different from the first radiation curable urethane; wherein the first radiation curable urethane oligomer comprises a lactone modified polyol.

15. The glass fiber of claim 12, wherein the coating is a secondary coating.

16. A glass fiber comprising a secondary coating comprising:
a. a first radiation curable urethane oligomer comprising four radiation curable functionalities; and
b. a second radiation curable urethane oligomer different from the first radiation curable urethane, wherein the first radiation curable urethane oligomer comprises a lactone modified polyol.