CA2237393A1 - Matrix compounds for forming optical fiber ribbons - Google Patents
Matrix compounds for forming optical fiber ribbons Download PDFInfo
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- CA2237393A1 CA2237393A1 CA002237393A CA2237393A CA2237393A1 CA 2237393 A1 CA2237393 A1 CA 2237393A1 CA 002237393 A CA002237393 A CA 002237393A CA 2237393 A CA2237393 A CA 2237393A CA 2237393 A1 CA2237393 A1 CA 2237393A1
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- Prior art keywords
- composition
- matrix
- oligomer
- monomer
- acrylate
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/1065—Multiple coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
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- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
Abstract
A removable matrix for retaining one or more optical fibers which have an outermost layer made of a first polymer having a first initiator system, e.g., a free-radical initiated, ultraviolet curable acrylate polymer, where the matrix is made from a second polymer having a second initiator system substantially different from the first initiator system, e.g., a cationically initiated, ultraviolet curable vinyl ether polymer. An optical fiber and matrix ribbon, where the ribbon is made from optical fibers which have an outermost layer of a free-radical initiated, ultraviolet radiation curable acrylate polymer, and a removable matrix for retaining the optical fibers, wherein the matrix comprises a cationically initiated, ultraviolet radiation curable polymer. An optical fiber and matrix ribbon which is made from optical fibers having an outermost layer made of a cationically initiated, ultraviolet radiation curable polymer, and a removable matrix for retaining the optical fibers, where the matrix is made from a free-radical initiated, ultraviolet radiation curable acrylate polymer. An ink for use on an acrylate polymer coated optical fiber, wherein the ink contains an inhibitor of cationically initiated polymerization. A matrix comprised of a cationically initiated, ultraviolet radiation curable vinyl ether polymer.
Description
CA 02237393 l998-05-l2 W O 97/18493 PCT~US96/17800 ~IATEUC~ C O M PO mNlDS FO R FOR~n~G OEYrICA~L
FIBER RIBBONS
Background of the Invention 5 Field of the Invention:
The invention relates to optical fibers. In particular, the present invention relates to novel ribbon ~y~L~llls composed of optical fibers and a removable matrix wherein the polymer systems of the optical fibers and the removable matrix use dirr~le,~l il~iLialor systems.
10 Back~round Art:
In the typical ribbon design for optical flber (glass) cables, a number of coated optical fibers or color-coded, coated optical fibers are first arranged in a flat array. The fiber coating is generally an ultraviolet (W) curable acrylate and the optional color-coding m~ter~l is either a 15 solvent based vinyl ink or a UV curable acrylate based ink. The fiber array is then overcoated with a thin layer of what is referred to as a "matrix coating," which is then cured. The purpose of the cured m~trri~l is to provide integrity to the ribbon structure. The most common matrix m~t~ri~ls are UV curable ac~lates and such matrix materials are present 20 in, e.g., the AT&T Accuribbon~. The AT&T Accuribbon'9 product liL~ e shows a matrix material having a thic.kn~ of as little as 0.03 mm at the top of the fiber up to as great as 0.125 mm in the valleys between adjacent fibers.
There is not common agreement in the industry as to the specific 25 mrch~nical properties the matrix cu~ uund must havé to be functional over the wide k;~ ture ranges the cable might experience, from about -40~C to approximately 80~C. Both low mûdulus mzltrri~ , less than 100 MPa, and high modulus materials, above 900 MPa, are ~les~lllly ~ employed by various cable m~nllf~rtllrers. However, it is generally 30 accepted that the compound must be stable at conditions of high CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 Le~ el~Lul~ and high relative hllmi~lity for some cable design applications.
For example, Bellcore Tec~ l Reference TR-NWT-000020 requires testing some cable components at 85~C and 85% relative hllmirlity for 30 days. Additionally, it must abe possible to easily remove the coated S optical fibers or color coded, coated optical fibers from the ribbon without~l~m~gin~ the coated fibers or removing the color coding where a color code is present. The latter requirement is important for fiber splicing and connectorization .
In another prior art ribbon, a layer of pressure sel~si~ e tape on each side of the fiber array was used to form the ribbon. This construction provided for easy fiber removal. However, because of high signal attem-~tio~ and high costs associated with this design, the industry has now switched to UV curable acrylates to bond the fiber array, as opposed to the pressure sensiLiv~; tape. This change has led to ~lifflrlll~ips in fiber breakout (s~alalion) from the ribbon without d~m~ging the fiber.
l~or i~ re, in the case of the AT&T Accuribbon'!9, the ribbon must first be treated with an alcohol-based gel to swell the matrix coating sufficiently to accomplish fiber removal in the required lllamlel.
An ~lterrl~te prior art ribbon design, which avoids the need for the ch~mir~l tre~tm~nt experienced with the Accuribbon'19, is disclosed in U.S. Patent 4,828,349. In the '349 disclosure, a peel layer is placed around the outside of tlle optical fiber and then a covering layer (matrix layer) is overlayed to form the ribbon structure. The peel layer is comprised of a thermosetting or ultra violet curable fluorocarbon or silicone resin. Because of the presence of the peel layer, the matrix or covering layer can be easily removed without ~l~m~ing the peel layer.
Cationic and free-radical based polymerization is discussed general in Rudin, A., The Elements of Polymer Science and Engineering, ~c~,~lemic Press, Inc., NY (1982).
For these reasons, it is highly desirable to provide a ribbon having a readily removable matrix while overcoming the disadvantages of the CA 02237393 1998-0~-12 W O 97f~84g3 PCTAUS96/t7800 prior art, such as not npe~lin~ a gel trP~tment or a special application of a peel layer, to facilitate easy removal of the fibers from the ribbon.
SUMMA~Y OF TH}~ INVENTION
The present invention provides a system which overcomes the 5 prior art disadvantages because the present invention, for example, does not re~uire gel tre~tmPnt or a special peel layer to permit easy removal of the fibers from the ribbon. In particular, the present invention provides a removable matrix for ret~ining one or more optical fibers having an outermost layer cu~ l;si,lg a first polymer with a first h,i~iakl system, 10 the matrix CO~ iSillg a second polymer having a second initiator system substantially different from the first initiator system.
In addition, the present invention provides an optical fiber and matrix ribbon, the ribbon COlll~ lg one or more optical fibers, wherein the fibers have an o~ltermost layer comprising a free-radical initi~te~
15 ultraviolet radiation curable acrylate polymer, and a removable matrix for .i..i"g the one or more optical fibers, wL~.cill the matrix colll~3lises a cationically inhi~tPcl, ultraviolet radiation curable polymer.
In yet another embodiment, the present invention provides an ink for use on an acrylate polymer coated optical fiber, wherein the ink 20 COlll~liSe:S an inhibitor of cationically initiated polyllltli~lion.
Furthermore, the present invention provides a matrix comprised of a cationically initi~tP-l, ultraviolet radiation curable vinyl ether polymer.
Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the 25 description, or may be learned by practice of the invention. The advantages of the invention will be realized and at~inP-l by means of the elemPnt~ and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only 30 and are not restrictive of the invention, as claimed.
, CA 02237393 1998-0~-12 W O 97/18493 PCT~US96117800 Deta~ed Des~ ion ofthe r~r~ d E mbo.~
The present invention may be understood more readily by reference to the following ~et~ile-l description of ~l~r~llCd embo-1iment~
of the invention.
S Before the present devices and methods are disclosed and described, it is to be lln-lPr~tnod that the t~.rminnlogy used herein is for the purpose of describing particular embo-limP-nt~ only and is not intended to be limiting. It must be noted that, as used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural l~r~;lcnL~. unless the con~ext clearly dictates otherwise.
As used herein, the term "removable" means that the matrix and the optical fiber may be sel)al~L~d or peeled apart without ~l~m~ging the outermost layer of the optical fiber. Also, as used herein, the "outermost layer" of the optical fiber may either be the actual outer polymer coating of the fiber or, when present, the coating layer formed by any ink applied to the optical fiber, whichever is outermost. Furthermore, as used herein, the term "inilialol system" is used to describe the various polymerization initiation reactions, including, but not limited to, cationic illiLialol systems, anionic initiator systems and free-radical h~LiaLor systems. As 2() used herein, the term "r~ ti-)n" is applied to a cure system for polymers which requires the input of energy, e.g., heat, micl~Jw~ve, or ultraviolet radiation. Thclercjre, a "radiation curable" polymer is one which can be cured by the application of radiation and an "ultraviolet radiation curable polymer" is one which is cured by the application of ultraviolet radiation.
In addition, the term "ribbon" is used herein to refer to an article res-llting from one or more optical fibers, with or without an ink coating, coated with a matrix compound. While the "ribbon" is generally described as a flat cable of multiple optical fibers, such limit~ti~n is not nPcess~ry and shall not be construed as a limitation on the present invention.
In addition, as used herein, "substantially dirrclcllL" initiator systems means that the initiator systems of the major portions of the W O 97/18493 PCTAJS96~7800 specified polymers are dirrc;r~ . For i~ re, a polymer having a major portion of a free-radical initi~t~l acrylate and a minor portion of a cationically i~ ;;.lPfl polyol would have a subst~nti~lly dir~en~ il~iLiaL~~
system from a polymer having a major portion of a cationically inhi~ttod S polyol, cycloaliphatic epoxide or vinyl ether and a minor portion of a free-radical initi~tP(l acrylate polymer.
The present invention provides a removable matrix for ret~inin~
one or more optical fibers having an outermost layer co~ a first polymer with a first illi~ system, the matrix comprising a second 10 polymer having a second hliti~tol system subst~nti~lly dir~cnl from the first initiator system. In a further embo-limPnt, the first and second polymers are radiation curable polymers. In yet a fur~er embo~liment, the first polymer co~ es a free radical initi~tP~l, ultraviolet radiation curable polymer and the second polymer co~ ise~; a c~tinnir~lly 15 initi~tP~, ultraviolet radiation curable polymer.
The present invention also discloses the matrix wherein the free radical initi~tPd, ultraviolet radiation curable first polymer is an acrylate polymer. In a further embo-limPnt, the matrix second polymer further comprises a partial adhesion promoting amount of a free-radical initi~t~, 20 radiation curable acrylate polymer and wherein the c:~tionir~lly initi~t~pd~
ultraviolet r~ tic~n curable polymer comprises a major portion of the matrix and the free-radical initi~t~-l, ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initi~te~l, ultraviolet radiation curable acrylate polymer 25 promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
In yet another embodiment, the cationically initi~trc~, ultraviolet radiation curable second polymer comprises a mixture of cyclo~liph~tir epoxide and a polyol. In a further embodiment, the cationically initi~tPcl, 30 ultraviolet radiation curable second polymer con~ es a vinyl ether polymer. In a further embodiment, the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped u~.,lllane oligomer, CA 02237393 1998-0~-12 a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a llli~tUle thereof. Specifically, the vinyl ether encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped u~cLl~alle oligomer is Vectomer 2032, the vinyl ether encapped monomer is bis-(4-vinyloxybutyl) isophth~l~te and the vinyl ether encapped monomer is 4-vinyloxybutyl benzoate.
In a further embodiment of the invention, the first polymer comprises a cationically initi~t~d7 ultraviolet radiation curable polymer and the second polymer colll~lises a free radical inhi~t~d~ ultraviolet radiation curable polymer. In yet another embo-lim~nt the free radical inhi~tP-1, ultraviolet radiation curable polymer is an acrylate polymer. In another embodiment, the matrix further comprises a partial adhesion promoting amount of a cationically initi~t~cl, ultraviolet radiation curable polymer and wherein the free-radical initi~-l ultraviolet radiation curable polymer coml~lises a major portion of the matrix and the cationically inhi~ted, ultraviolet radiation curable polymer comprises a minor portion of the matrix, whereby the presence of the cationically initi~t~d, ultraviolet radiation curable polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
In addition, the present invention provides an optical ~lber and matrix ribbon, the ribbon COlllpliSil~ one or more optical fibers, wherein the fibers have an outermost layer cOlll~ g a free-radical initi~t~
ultraviolet radiation curable acrylate polymer, and a removable matrix for retzlinin~ the one or more optical fibers, wherein the matrix co",plises a cationically initi~t~-l, ultraviolet radiation curable polymer. In a further embo-iimPnt the matrix further cu",~,iscs a free-radical initis-t~?ti, radiation curable acrylate polymer and wll~lcill the cationically initi~t~r1, ultraviolet radiation curable polymer cu~ lises a major portion of the matrix and the free-radical initi~ted ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initi~t~d, ultraviolet radiation curable acrylate polymer promotes partial adhesion between the outermost layer of the one or more W O 97~18493 PCTAUS96/17800 fibers and the matrix. In yet another embo~iment the cationically initi~ttofl, ultraviolet radiation curable polymer c~ ises a vinyl ether polymer. In a further embodiment, the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped urclllalle oligomer, 5 a vinyl ether enca~l)ed ester monomer, a vinyl ether encapped alcohol, or a mixture thereof. Specifically, the vinyl ether encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped ul~lalle oligomer is Vectomer 2032, the vinyl ether encapped monorner is bis-(4-vinyloxybutyl) isophth~l~te and the vinyl ether encapped monomer is 4-10 vinylo~ybulyl benzoate.
In addition, the present invention provides a ribbon whelcill theoutermost layer of the one or more fibers comprises an ink coating, wherein the ink c~ plises a free-radical initi~t~(l, radiation curable acrylate polymer. In a further embodiment, the ink further colll~lises an 15 inhibitor of cationically initi~tecl polymerization. In yet another embodiment, the inhibitor is water, a basic compound, or a ~ Lul~:
thereof. More specifically, the inhibitor is a pigment capable of interacting with the cation, or a hindered amine light stabilizer, such as bis-(2,2,6,6-lt;L,dlllc~lyl-4-piperidyl) sebacate, or the inhibitor is 1-vinyl-2-20 pyrrolidone.
In yet another embodiment of the ribbon, the ribbon comprises oneor more optical fibers, wh~.cill the fibers have an outermost layer Colll~ illg a cationically inhi~t~cl, ultraviolet r~ ti~n curable polymer, and a removable matrix for lC~;.i,.i"~ the one or more optical fibers, 25 wherein the matrix co~ lises a free-radical initi~t~cl, ultraviolet radiationcurable acrylate polymer. In a further embo~lim~nt the matrix further comprises a cationically initi~tP-l, ultraviolet radiation curable polymer ~ and wherein the free-radical initisltecl~ ultraviolet radiation curable acrylate polymer comprises the major portion of the matrix and the ç:lti~nicz~lly 30 initi~terl, ultraviolet radiation curable polymer comprises the minor portion of the matrix, whereby the presence of the cationically initi~t~
ultraviolet radiation curable polymer promotes partial adhesion between W O 97/18493 PCT~US96117800 the outermost layer of the one or more fibers and the matrix. In yet another embollimPnt the cationically inh;~tP-l, ultraviolet ra~ tion curable polymer co~ lises a vinyl ether polymer. Moreover, in an alternate embodiment, the outermost layer of the one or more fibers colllplises an 5 ink coating, wherein the ink culll~,lises a cationically initi~te~l ultraviolet radiation curable polymer. In an alternate embo-1ime~t the ink further comprises an inhibitor of free-radical inhi~tP~l polymerization. In another emborliment, the inhibitor comprises a benzoquinone deliv~live, such as hydroquinone, naphthaquinone, or a llli~Ul~ thereof.
In yet another embo-limP-nt, the present invention provides an ink for use on an acrylate polymer coated optical fiber, wll~c;il~ the ink comprises an inhibitor of cationically initi~t~cl polymerization. In an ~ltPrn~tP emborlimpnt~ the hlhibi~ l is water, a basic compound, or a Ul'e thereof. In yet anolllel embo(1imPnt the inhibitor is a pigment capable of interacting with the cation. In yet allolll.,L embo~limP-nt the basic compound c~ lises a hindered amine light stabilizer, such as bis-(2,2,6,6-LeLl~ulle~lyl~piperidyl) sebacate. In an alternate embo-limPnt the inhibitor is l-vinyl-2-pyrrolidone. In another alternate embo-1iment the inhibitor is an illiLiaLor of free radical initi~tPd polymerization, such as2-methyl- 1 -[4-(methylthio)phenyl] -2-morpholinol)l opallone- 1 .
The present invention also provides a matrix col~lised of a cationically ini~ P-l, ultraviolet radiation curable vinyl ether polymer. In a fur~er embo-liment, the vinyl e~er polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped ule~lalle oligomer, a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a llliX.IUlc;
~ereof. Specifically, the vinyl etber encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped urethane oligomer is Vectomer 2032, the vinyl ether encapped monomer is bis-(4-vinyloxybutyl) isophth~l~t~ and the vinyl ether encapped monomer is 4-vinyloxybutyl benzoate.
The present invention involves the selection and formulation of the matrix material or both the matrix material and the ink such that an CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 optical fiber cable m~nllf~ctllrer may choose the level of adhesion between the coated or the color-coded, coated optical fibers and the matrix coating used in the fiber ribbon. Using the methods of the present invention, neither a gel tre~tm~nt nor a special application of a peel layer is required S to facilitate easy removal of the fibers from the ribbon.
Most optical fibers in use in the industry today use an outer coating composed of free-radical initi~t~cl UV curable acrylate polymers.
For such optical fibers, the present invention proposes the use of a cationically initi~t~i, UV curable material as the major portion of the 10 matrix coating formnl~til n. The use of polymers having distinct hliLiaL
systems prevents e~ lsiv~ cross-linking or other binding between the outermost layer of the optical fiber and the matrix. Moreover, the matrix coating may also contain free-radical initi~t~l, UV curable acrylates to properly balance the ~lihPsion~ i.e., to increase the adhesion to the ink or 15 fiber coating to a desired level. Additionally, the use of some acrylate materials reduces the raw m~teri~l cost of the completed matrix compound because acrylate materials are presently less ~ e then cationically initi~t~ m~teri~le.
Moreover, in embo.li~ where acrylate polymers are used to 20 increase the partial adhesion, the use of high molecular weight acrylates and the functionality of the acrylate may be manipulated to increase or decrease ~-1hPeio~ For in.et~n~e, a higher molecular weight acrylate would provide for less adhesion because the functional equivalent weight (i. e., weight divided by degree of functionality) would be higher. The 25 degree of functionality of the acrylate polymer used can also be chosen to increase or reduce the adhesion, where an increase in the degree of functionality would increase the ~lh~
Additionally, formulation latitude is further increased if the ink (which forms the outermost layer of the optical fiber) used to optionally 30 color-code the fiber contains a component which slightly inhibits the cure of the matrix compound at the interface between the matrix compound and the ink. The degree of inhibition of cure inflll~n~es the level of adhesion -at the interface and hence the relative ease of removing the fiber from the matrix coating.
~he ink used to color-code the fiber can have many dirr~lc ch~mi~tries with the exception that, for systems using a cationically 5 initi~tefl, UV curable polymer in the matrix, the major components cannot be cationically initi~t~tl W curable m~t~ri~l~. Examples of commonly used inks are solvent based vinyl inks and free-radical ini*~t~ W
curable acrylate inks.
Generally, cationically initi~terl m~t~ri~l~ are inhibited by molecules which can hydrogen bond or react with the cation and th~eroIc, remove it from its role in the reaction. Examples of inhibitors include, but are not limited to, water, bases (even very weak bases present in the fiber coating, such as hindered amine light stabilizers), other colllpo~
often present in W curable ac.ylaL~s such as N vinyl pyrrolidone (1-vinyl-2-pyrrolidone), and even selected pi~n~t~ capable of interacting with the cation. The degree of inhibition can vary widely by component and with co~celllla~ion.
l:~or the case where the outer coating on the optical fiber (as opposed to the matrix) is a cationically initi~t~rl UV curable vinyl ether material (see, e.g., U.S. Patent No. 5,139,872), the ink can be comprised sub~ lly of cationically initi~t~cl UV materials where a UV ink is used. The matrix compound in this case is comprised sl-hst~nti~lly of free radical initi~t~-l, UV curable acrylate components. The important ~i~tinrtion is that while the ink, if used, and optical fiber outer coating share the same initiator system, the matrix polymer must use a distinct or dirr~ lL i"iLiak~l system than the outermost layer, either the ink, if used, or the outer polymer coating of the optical fiber. Similar to the cationic cure matrix in~t~nre, inhibition of cure can be controlled by including a low level of a free-radical scavenger in the ink or the fiber coating where the color coding inks are not used. For in~t~nre, a benzoquinone derived free-radical scavenger such as hydro4uhlolle or naphthaquinone can be added to the ink.
=
FIBER RIBBONS
Background of the Invention 5 Field of the Invention:
The invention relates to optical fibers. In particular, the present invention relates to novel ribbon ~y~L~llls composed of optical fibers and a removable matrix wherein the polymer systems of the optical fibers and the removable matrix use dirr~le,~l il~iLialor systems.
10 Back~round Art:
In the typical ribbon design for optical flber (glass) cables, a number of coated optical fibers or color-coded, coated optical fibers are first arranged in a flat array. The fiber coating is generally an ultraviolet (W) curable acrylate and the optional color-coding m~ter~l is either a 15 solvent based vinyl ink or a UV curable acrylate based ink. The fiber array is then overcoated with a thin layer of what is referred to as a "matrix coating," which is then cured. The purpose of the cured m~trri~l is to provide integrity to the ribbon structure. The most common matrix m~t~ri~ls are UV curable ac~lates and such matrix materials are present 20 in, e.g., the AT&T Accuribbon~. The AT&T Accuribbon'9 product liL~ e shows a matrix material having a thic.kn~ of as little as 0.03 mm at the top of the fiber up to as great as 0.125 mm in the valleys between adjacent fibers.
There is not common agreement in the industry as to the specific 25 mrch~nical properties the matrix cu~ uund must havé to be functional over the wide k;~ ture ranges the cable might experience, from about -40~C to approximately 80~C. Both low mûdulus mzltrri~ , less than 100 MPa, and high modulus materials, above 900 MPa, are ~les~lllly ~ employed by various cable m~nllf~rtllrers. However, it is generally 30 accepted that the compound must be stable at conditions of high CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 Le~ el~Lul~ and high relative hllmi~lity for some cable design applications.
For example, Bellcore Tec~ l Reference TR-NWT-000020 requires testing some cable components at 85~C and 85% relative hllmirlity for 30 days. Additionally, it must abe possible to easily remove the coated S optical fibers or color coded, coated optical fibers from the ribbon without~l~m~gin~ the coated fibers or removing the color coding where a color code is present. The latter requirement is important for fiber splicing and connectorization .
In another prior art ribbon, a layer of pressure sel~si~ e tape on each side of the fiber array was used to form the ribbon. This construction provided for easy fiber removal. However, because of high signal attem-~tio~ and high costs associated with this design, the industry has now switched to UV curable acrylates to bond the fiber array, as opposed to the pressure sensiLiv~; tape. This change has led to ~lifflrlll~ips in fiber breakout (s~alalion) from the ribbon without d~m~ging the fiber.
l~or i~ re, in the case of the AT&T Accuribbon'!9, the ribbon must first be treated with an alcohol-based gel to swell the matrix coating sufficiently to accomplish fiber removal in the required lllamlel.
An ~lterrl~te prior art ribbon design, which avoids the need for the ch~mir~l tre~tm~nt experienced with the Accuribbon'19, is disclosed in U.S. Patent 4,828,349. In the '349 disclosure, a peel layer is placed around the outside of tlle optical fiber and then a covering layer (matrix layer) is overlayed to form the ribbon structure. The peel layer is comprised of a thermosetting or ultra violet curable fluorocarbon or silicone resin. Because of the presence of the peel layer, the matrix or covering layer can be easily removed without ~l~m~ing the peel layer.
Cationic and free-radical based polymerization is discussed general in Rudin, A., The Elements of Polymer Science and Engineering, ~c~,~lemic Press, Inc., NY (1982).
For these reasons, it is highly desirable to provide a ribbon having a readily removable matrix while overcoming the disadvantages of the CA 02237393 1998-0~-12 W O 97f~84g3 PCTAUS96/t7800 prior art, such as not npe~lin~ a gel trP~tment or a special application of a peel layer, to facilitate easy removal of the fibers from the ribbon.
SUMMA~Y OF TH}~ INVENTION
The present invention provides a system which overcomes the 5 prior art disadvantages because the present invention, for example, does not re~uire gel tre~tmPnt or a special peel layer to permit easy removal of the fibers from the ribbon. In particular, the present invention provides a removable matrix for ret~ining one or more optical fibers having an outermost layer cu~ l;si,lg a first polymer with a first h,i~iakl system, 10 the matrix CO~ iSillg a second polymer having a second initiator system substantially different from the first initiator system.
In addition, the present invention provides an optical fiber and matrix ribbon, the ribbon COlll~ lg one or more optical fibers, wherein the fibers have an o~ltermost layer comprising a free-radical initi~te~
15 ultraviolet radiation curable acrylate polymer, and a removable matrix for .i..i"g the one or more optical fibers, wL~.cill the matrix colll~3lises a cationically inhi~tPcl, ultraviolet radiation curable polymer.
In yet another embodiment, the present invention provides an ink for use on an acrylate polymer coated optical fiber, wherein the ink 20 COlll~liSe:S an inhibitor of cationically initiated polyllltli~lion.
Furthermore, the present invention provides a matrix comprised of a cationically initi~tP-l, ultraviolet radiation curable vinyl ether polymer.
Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the 25 description, or may be learned by practice of the invention. The advantages of the invention will be realized and at~inP-l by means of the elemPnt~ and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only 30 and are not restrictive of the invention, as claimed.
, CA 02237393 1998-0~-12 W O 97/18493 PCT~US96117800 Deta~ed Des~ ion ofthe r~r~ d E mbo.~
The present invention may be understood more readily by reference to the following ~et~ile-l description of ~l~r~llCd embo-1iment~
of the invention.
S Before the present devices and methods are disclosed and described, it is to be lln-lPr~tnod that the t~.rminnlogy used herein is for the purpose of describing particular embo-limP-nt~ only and is not intended to be limiting. It must be noted that, as used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural l~r~;lcnL~. unless the con~ext clearly dictates otherwise.
As used herein, the term "removable" means that the matrix and the optical fiber may be sel)al~L~d or peeled apart without ~l~m~ging the outermost layer of the optical fiber. Also, as used herein, the "outermost layer" of the optical fiber may either be the actual outer polymer coating of the fiber or, when present, the coating layer formed by any ink applied to the optical fiber, whichever is outermost. Furthermore, as used herein, the term "inilialol system" is used to describe the various polymerization initiation reactions, including, but not limited to, cationic illiLialol systems, anionic initiator systems and free-radical h~LiaLor systems. As 2() used herein, the term "r~ ti-)n" is applied to a cure system for polymers which requires the input of energy, e.g., heat, micl~Jw~ve, or ultraviolet radiation. Thclercjre, a "radiation curable" polymer is one which can be cured by the application of radiation and an "ultraviolet radiation curable polymer" is one which is cured by the application of ultraviolet radiation.
In addition, the term "ribbon" is used herein to refer to an article res-llting from one or more optical fibers, with or without an ink coating, coated with a matrix compound. While the "ribbon" is generally described as a flat cable of multiple optical fibers, such limit~ti~n is not nPcess~ry and shall not be construed as a limitation on the present invention.
In addition, as used herein, "substantially dirrclcllL" initiator systems means that the initiator systems of the major portions of the W O 97/18493 PCTAJS96~7800 specified polymers are dirrc;r~ . For i~ re, a polymer having a major portion of a free-radical initi~t~l acrylate and a minor portion of a cationically i~ ;;.lPfl polyol would have a subst~nti~lly dir~en~ il~iLiaL~~
system from a polymer having a major portion of a cationically inhi~ttod S polyol, cycloaliphatic epoxide or vinyl ether and a minor portion of a free-radical initi~tP(l acrylate polymer.
The present invention provides a removable matrix for ret~inin~
one or more optical fibers having an outermost layer co~ a first polymer with a first illi~ system, the matrix comprising a second 10 polymer having a second hliti~tol system subst~nti~lly dir~cnl from the first initiator system. In a further embo-limPnt, the first and second polymers are radiation curable polymers. In yet a fur~er embo~liment, the first polymer co~ es a free radical initi~tP~l, ultraviolet radiation curable polymer and the second polymer co~ ise~; a c~tinnir~lly 15 initi~tP~, ultraviolet radiation curable polymer.
The present invention also discloses the matrix wherein the free radical initi~tPd, ultraviolet radiation curable first polymer is an acrylate polymer. In a further embo-limPnt, the matrix second polymer further comprises a partial adhesion promoting amount of a free-radical initi~t~, 20 radiation curable acrylate polymer and wherein the c:~tionir~lly initi~t~pd~
ultraviolet r~ tic~n curable polymer comprises a major portion of the matrix and the free-radical initi~t~-l, ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initi~te~l, ultraviolet radiation curable acrylate polymer 25 promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
In yet another embodiment, the cationically initi~trc~, ultraviolet radiation curable second polymer comprises a mixture of cyclo~liph~tir epoxide and a polyol. In a further embodiment, the cationically initi~tPcl, 30 ultraviolet radiation curable second polymer con~ es a vinyl ether polymer. In a further embodiment, the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped u~.,lllane oligomer, CA 02237393 1998-0~-12 a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a llli~tUle thereof. Specifically, the vinyl ether encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped u~cLl~alle oligomer is Vectomer 2032, the vinyl ether encapped monomer is bis-(4-vinyloxybutyl) isophth~l~te and the vinyl ether encapped monomer is 4-vinyloxybutyl benzoate.
In a further embodiment of the invention, the first polymer comprises a cationically initi~t~d7 ultraviolet radiation curable polymer and the second polymer colll~lises a free radical inhi~t~d~ ultraviolet radiation curable polymer. In yet another embo-lim~nt the free radical inhi~tP-1, ultraviolet radiation curable polymer is an acrylate polymer. In another embodiment, the matrix further comprises a partial adhesion promoting amount of a cationically initi~t~cl, ultraviolet radiation curable polymer and wherein the free-radical initi~-l ultraviolet radiation curable polymer coml~lises a major portion of the matrix and the cationically inhi~ted, ultraviolet radiation curable polymer comprises a minor portion of the matrix, whereby the presence of the cationically initi~t~d, ultraviolet radiation curable polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
In addition, the present invention provides an optical ~lber and matrix ribbon, the ribbon COlllpliSil~ one or more optical fibers, wherein the fibers have an outermost layer cOlll~ g a free-radical initi~t~
ultraviolet radiation curable acrylate polymer, and a removable matrix for retzlinin~ the one or more optical fibers, wherein the matrix co",plises a cationically initi~t~-l, ultraviolet radiation curable polymer. In a further embo-iimPnt the matrix further cu",~,iscs a free-radical initis-t~?ti, radiation curable acrylate polymer and wll~lcill the cationically initi~t~r1, ultraviolet radiation curable polymer cu~ lises a major portion of the matrix and the free-radical initi~ted ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initi~t~d, ultraviolet radiation curable acrylate polymer promotes partial adhesion between the outermost layer of the one or more W O 97~18493 PCTAUS96/17800 fibers and the matrix. In yet another embo~iment the cationically initi~ttofl, ultraviolet radiation curable polymer c~ ises a vinyl ether polymer. In a further embodiment, the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped urclllalle oligomer, 5 a vinyl ether enca~l)ed ester monomer, a vinyl ether encapped alcohol, or a mixture thereof. Specifically, the vinyl ether encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped ul~lalle oligomer is Vectomer 2032, the vinyl ether encapped monorner is bis-(4-vinyloxybutyl) isophth~l~te and the vinyl ether encapped monomer is 4-10 vinylo~ybulyl benzoate.
In addition, the present invention provides a ribbon whelcill theoutermost layer of the one or more fibers comprises an ink coating, wherein the ink c~ plises a free-radical initi~t~(l, radiation curable acrylate polymer. In a further embodiment, the ink further colll~lises an 15 inhibitor of cationically initi~tecl polymerization. In yet another embodiment, the inhibitor is water, a basic compound, or a ~ Lul~:
thereof. More specifically, the inhibitor is a pigment capable of interacting with the cation, or a hindered amine light stabilizer, such as bis-(2,2,6,6-lt;L,dlllc~lyl-4-piperidyl) sebacate, or the inhibitor is 1-vinyl-2-20 pyrrolidone.
In yet another embodiment of the ribbon, the ribbon comprises oneor more optical fibers, wh~.cill the fibers have an outermost layer Colll~ illg a cationically inhi~t~cl, ultraviolet r~ ti~n curable polymer, and a removable matrix for lC~;.i,.i"~ the one or more optical fibers, 25 wherein the matrix co~ lises a free-radical initi~t~cl, ultraviolet radiationcurable acrylate polymer. In a further embo~lim~nt the matrix further comprises a cationically initi~tP-l, ultraviolet radiation curable polymer ~ and wherein the free-radical initisltecl~ ultraviolet radiation curable acrylate polymer comprises the major portion of the matrix and the ç:lti~nicz~lly 30 initi~terl, ultraviolet radiation curable polymer comprises the minor portion of the matrix, whereby the presence of the cationically initi~t~
ultraviolet radiation curable polymer promotes partial adhesion between W O 97/18493 PCT~US96117800 the outermost layer of the one or more fibers and the matrix. In yet another embollimPnt the cationically inh;~tP-l, ultraviolet ra~ tion curable polymer co~ lises a vinyl ether polymer. Moreover, in an alternate embodiment, the outermost layer of the one or more fibers colllplises an 5 ink coating, wherein the ink culll~,lises a cationically initi~te~l ultraviolet radiation curable polymer. In an alternate embo-1ime~t the ink further comprises an inhibitor of free-radical inhi~tP~l polymerization. In another emborliment, the inhibitor comprises a benzoquinone deliv~live, such as hydroquinone, naphthaquinone, or a llli~Ul~ thereof.
In yet another embo-limP-nt, the present invention provides an ink for use on an acrylate polymer coated optical fiber, wll~c;il~ the ink comprises an inhibitor of cationically initi~t~cl polymerization. In an ~ltPrn~tP emborlimpnt~ the hlhibi~ l is water, a basic compound, or a Ul'e thereof. In yet anolllel embo(1imPnt the inhibitor is a pigment capable of interacting with the cation. In yet allolll.,L embo~limP-nt the basic compound c~ lises a hindered amine light stabilizer, such as bis-(2,2,6,6-LeLl~ulle~lyl~piperidyl) sebacate. In an alternate embo-limPnt the inhibitor is l-vinyl-2-pyrrolidone. In another alternate embo-1iment the inhibitor is an illiLiaLor of free radical initi~tPd polymerization, such as2-methyl- 1 -[4-(methylthio)phenyl] -2-morpholinol)l opallone- 1 .
The present invention also provides a matrix col~lised of a cationically ini~ P-l, ultraviolet radiation curable vinyl ether polymer. In a fur~er embo-liment, the vinyl e~er polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped ule~lalle oligomer, a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a llliX.IUlc;
~ereof. Specifically, the vinyl etber encapped ester oligomer is Allied Signal 150B, the vinyl ether encapped urethane oligomer is Vectomer 2032, the vinyl ether encapped monomer is bis-(4-vinyloxybutyl) isophth~l~t~ and the vinyl ether encapped monomer is 4-vinyloxybutyl benzoate.
The present invention involves the selection and formulation of the matrix material or both the matrix material and the ink such that an CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 optical fiber cable m~nllf~ctllrer may choose the level of adhesion between the coated or the color-coded, coated optical fibers and the matrix coating used in the fiber ribbon. Using the methods of the present invention, neither a gel tre~tm~nt nor a special application of a peel layer is required S to facilitate easy removal of the fibers from the ribbon.
Most optical fibers in use in the industry today use an outer coating composed of free-radical initi~t~cl UV curable acrylate polymers.
For such optical fibers, the present invention proposes the use of a cationically initi~t~i, UV curable material as the major portion of the 10 matrix coating formnl~til n. The use of polymers having distinct hliLiaL
systems prevents e~ lsiv~ cross-linking or other binding between the outermost layer of the optical fiber and the matrix. Moreover, the matrix coating may also contain free-radical initi~t~l, UV curable acrylates to properly balance the ~lihPsion~ i.e., to increase the adhesion to the ink or 15 fiber coating to a desired level. Additionally, the use of some acrylate materials reduces the raw m~teri~l cost of the completed matrix compound because acrylate materials are presently less ~ e then cationically initi~t~ m~teri~le.
Moreover, in embo.li~ where acrylate polymers are used to 20 increase the partial adhesion, the use of high molecular weight acrylates and the functionality of the acrylate may be manipulated to increase or decrease ~-1hPeio~ For in.et~n~e, a higher molecular weight acrylate would provide for less adhesion because the functional equivalent weight (i. e., weight divided by degree of functionality) would be higher. The 25 degree of functionality of the acrylate polymer used can also be chosen to increase or reduce the adhesion, where an increase in the degree of functionality would increase the ~lh~
Additionally, formulation latitude is further increased if the ink (which forms the outermost layer of the optical fiber) used to optionally 30 color-code the fiber contains a component which slightly inhibits the cure of the matrix compound at the interface between the matrix compound and the ink. The degree of inhibition of cure inflll~n~es the level of adhesion -at the interface and hence the relative ease of removing the fiber from the matrix coating.
~he ink used to color-code the fiber can have many dirr~lc ch~mi~tries with the exception that, for systems using a cationically 5 initi~tefl, UV curable polymer in the matrix, the major components cannot be cationically initi~t~tl W curable m~t~ri~l~. Examples of commonly used inks are solvent based vinyl inks and free-radical ini*~t~ W
curable acrylate inks.
Generally, cationically initi~terl m~t~ri~l~ are inhibited by molecules which can hydrogen bond or react with the cation and th~eroIc, remove it from its role in the reaction. Examples of inhibitors include, but are not limited to, water, bases (even very weak bases present in the fiber coating, such as hindered amine light stabilizers), other colllpo~
often present in W curable ac.ylaL~s such as N vinyl pyrrolidone (1-vinyl-2-pyrrolidone), and even selected pi~n~t~ capable of interacting with the cation. The degree of inhibition can vary widely by component and with co~celllla~ion.
l:~or the case where the outer coating on the optical fiber (as opposed to the matrix) is a cationically initi~t~rl UV curable vinyl ether material (see, e.g., U.S. Patent No. 5,139,872), the ink can be comprised sub~ lly of cationically initi~t~cl UV materials where a UV ink is used. The matrix compound in this case is comprised sl-hst~nti~lly of free radical initi~t~-l, UV curable acrylate components. The important ~i~tinrtion is that while the ink, if used, and optical fiber outer coating share the same initiator system, the matrix polymer must use a distinct or dirr~ lL i"iLiak~l system than the outermost layer, either the ink, if used, or the outer polymer coating of the optical fiber. Similar to the cationic cure matrix in~t~nre, inhibition of cure can be controlled by including a low level of a free-radical scavenger in the ink or the fiber coating where the color coding inks are not used. For in~t~nre, a benzoquinone derived free-radical scavenger such as hydro4uhlolle or naphthaquinone can be added to the ink.
=
3 PCT~US96/1780 Preferred matrix material formnl~tinn~ useful for the present invention are given in Tables 1 and 2. Table 1 details form~ ti~ns where the reactive components are based on vinyl ether chPmictry. Table 2 contains formlll~tions based on cycloaliphatic epoxides and polyols 5 chemistry and mixed systems of the two çl~ ies.
In Table 1, Allied Signal 150B (Allied Signal, Inc., Morristown, NJ) is a vinyl ether encapped polyester oligomer having a viscosity of 340,000 cps at 60~C and a weight average molecular weight of from 2000 to 3500. Vectomer 2032 (Allied Signal, Inc., Mo~ Lc,wll, NJ) is a vinyl ether encapped ult;lllalle oligomer which has a viscosity of 30,000 cps at 70~C and a weight average molecular weight of 4800 to 6600. Bis-(4-vinyloxybutyl) isophth~l~t~ is a difunctional (with respect to cationic cure) vinyl ether monomer with a viscosity of 85 cps at 25~C and is sold under the trade name Vectomer 4010 (Allied Signal, Inc., Molli~Lowll, NJ). 4-15 vinyloxybutyl benzoate is a monofunctional vinyl ether monomer (with respect to cationic cure) having a viscosity of 7 cps at 25~C and is available under the trade name Vectomer 3010 (Allied Signal, Inc., Morristown, NJ).
Other pl~f~,llcd vinyl ether compounds that are particularly 20 suitable for ~e matrix composi~ions of the present invention include, but are not limited to, 1,4-bis[(vinyloxy)methyl]-cycl-hP~n~ (1,4-cyclohP~nr-limPth~n-)l divinyl ether), sold under the trade name Rapi-Cure CHVE (In~ alional Specialty Products, Inc., Wayne N.J.) and having a viscosity of 5.0 cps at 25~C; 3,6,9,12-tetraoxatetradeca-1,13-25 diene (triethylene glycol divinyl ether), sold uIlder the trade name Rapi-Cure DVE-3 (IllLt~ alional Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 2.67 cps at 25~C; hydroxybutyl vinyl ether, sold under the trade name Rapi-Cure HBVE (T,.~ nal Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 7.5 cps at 25~C; n-dodecyl ~ 30 vinyl ether, sold under the trade name Rapi-Cure DDVE (Tnt~rn~tional Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 2.81 cps at 25~C; bis-(4-vinyloxymethylcyclohexyl methyl) glutarate, sold under W O 97/18493 PCTrUS96/17800 the trade name Vectomer 4020 (Allied Signal Corp., Molli..L~wll, N.J.) and having a viscosity of 430 cps at 25~C; and bis-(4-vinyloxybutyl) succinate (IllL~ lional Specialty Products, Inc., Wayne, N.J.) having a viscosity o~ 43 cps at 25~C. Other suitable vinyl ethers include, but are 5 not limited to, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, butyl vinyl ether, ethyleneglycol vinyl ether, diethyleneglycol divinyl ether, b -t~n~Ai~l monovinyl ether, b~tAn~iol divinyl ether, ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinyl ether, cyclohtox~n~Aim~th~n~ l monovinyl ether, 2-ethylhexyl vinyl ether, Poly-THF-divinyl ether 290, pluriol-E-200-divinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl etner, ethyleneglycol divinyl ether, diethyleneglycol mol~villyl ether, h.o~n.-Aiol monovinyl ether, tetraethyleneglycol divinyl ether, trimethylol~lo~le trivinyl ether, aminopropyl vinyl ether, or 2-diethyl~minnethyl vinyl ether (prece-lin~ vinyl ethers available from BASF, Mount Olive, N.J.).
In addition, there are many acrylate polymers ("acrylates") in use today which are suitable for the purposes described herein. More particularly, for the purposes of the examples ~ c~l~seA. herein, Ebecryl 8804 is the trade name for an ~lirh~t;l' urethane acrylate oligomer with a viscosity of 10,000 - 24,000 cps at 65~C, a molecular weight of 1,400 and a functionality of 2.4 (UCB Radcure Inc., Smyrna, GA).
Tlipl~ylene glycol diacrylate (TRPGDA) is a dirull~;Lional mollolllel with a viscosity of 12 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
Trimethylo~rol~alle triacrylate (TMPTA) is a Llirulu;lional monomer with a viscosity of 85 cps at 25~C (UCB Radcure Inc., Smyrna, GA). 1,6-hexanediol diacrylate (HDODA) is a difunctional monomer with a viscosity of 6 cps at 25~C (UCB Radcure Inc., Smyrna, GA). ~-carboxyethyl acrylate (~-CEA) is a monofunctional monomer with a viscosity of 75 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Isobornyl acrylate (IBOA) is a monofunctional monomer with a viscosity of 9.5 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Octylfdecyl acrylate (ODA) is a monorullcLional monomer with a viscosity of 2 cps at 25~C (UCB
CA 02237393 l998-05-l2 W O 97rl8493 PCT~US96rI78~0 Radcure Inc., Smyrna, GA). O~y~lylated phenol acrylate (Ebecryl~9 110) is a monofllnf~tinn~l monl~m~r with a viscosity of 75 cps at 25~C
(UCB Radcure Inc., Smyrna, GA). Tetrae~ylene glycol diacrylate (TTEGDA) is a difunrti~-n:~l monomer with a viscosity of 20 cps at 25~C
5 (UCB Radcure Inc., Smyrna, GA). Bisphenol-A derivative diacrylate (Ebecryl~ 150) is a difunctional monomer with a viscosity of 1,500 cps at 25~C (UCB Radcure Inc., Smyrna, GA). OTA480 is a llifull;Lional monomer with a viscosity of 85 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Penta~ ol triacrylate (PETA-K) is a lliÇullcLional monomer with a viscosity of 500 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
PETA-LQ is a lower functionality version of PETA-K with a viscosity of 1,500 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
Trimethylolpropane ethoxy triacrylate (TMPEOTA) is a L~ir~ Lion~l monomer with a viscosity of 20 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Acrylated di-penta~:ly~ ilol (DPHPA) is a m~ ir.l.-. ~ional monomer with a viscosity of 20,000 cps at 25~C (UCB Radcure Inc., Smyrna, GA). In ~d-1iti~ n, other Ebecryl'l9 acrylates suitable for the present purposes include, but are not limited to, Ebecryl'l9 80, 81, 82, 220, 230, 244, 264, 265, 270, 284, 285, 436, 438, 450, 505, 524, 525, 584, 585, 586, 588, 600, 605, 616, 629, 639, 657, 745, 754, 767, 770, 810, 830, 860, 870, 1290, 1608, 1657, 1701, 1755, 1810, 3200, 3201, 3409, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3702, 3703, 4827, 4830, 4833, 4834, 4849, 4866, 4881, 4883, 6602, 6700, 8301, 8402, 8800, 8800-20R, or 8803 (All Ebecryla9 product numbers available from UCB
Radcure Inc., Smyrna, GA).
Ar3SPF6 in the presence of W light can serve as the initiator in the cationic polymerization of vinyl ether oligomers and monomers and is sold under the trade name UVI 6990 (Union Carbide, Danbury, CT).
2,2-dimethoxy-2-phenylacetophenone is a Norish Type 1 Cleavage photo initiator with a melting point of 63-66~C and is available sold under the trade name Irgacure 651 (Ciba-Geigy Corp., Hawthorne, N~). Irgacure CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 651 serves as the free radical source on exposure to UV light for the polymerization of acrylate monomers and oligomers. Octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate is a ~herm~l oxidative stabilizer which is available under the trade name Irganox 1076 (Ciba-Geigy Corp., S Hawthorne, NY). The l,ro~,lyl ether of propylene carbonate (RAPI-CURE PE~PC) has a molecular weight of 158 and a viscosity of 13 cps at 25~C (Intcl,~lional Specialty Products, Wayne, NJ or Charlotte, NC).
PEPC helps to solubilize the UV 6990.
SF 1188 is the trade name for the copolymer of a polyllleLllyl siloxane and a polyoxy alkene ether having a viscosity of 600-1200 cps at 25~ C, a density of 1.04 g/cc avg., and a surface tension of 25.5 dynes/cm2 (GE Silicones, WaLelrold, NY). SF 1188 is an anti-blocking agent which prevents tacking together of 5~ rlt layers of ink or matrix when the product is wound upon itself.
In Table 2, UVR~6110 is the kade name for 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate which has an epoxy equivalent weight of 131 - 143 and a viscosity at 25~C of 350 -450 cps (Union Carbide, Danbury, CT.). See Carroy, Antoine, Aspects of Photoinitiaion: Cationic UV-Curing Eff~iciency of Cycloaliphatic Epoxide-Based Systems Through Photoinitiator and UV-Wavelength Selection (1993). UVR-6128 is the kade name for bis-(3,4-epoxycyclohexyl) adipate which has an epoxide equivalent weight of 350-450 and a viscosity at 25~C 190 - 210 cps (Union Carbide, Danbury, CT.). Tone 0301 is the trade name for an ~-caprolactone kiol which has an hydroxyl equivalent weight of 98 - 103 and a viscosity of 2250 cps at 55~C (Union Carbide, Danbury, CT.). Tone 0301 is kifunctional with respect to reactivity. Tone 0201 is the trade name for a caprolactone diol having an average molecular weight of 530 and a viscosity of 65 cps at 55~C (Union Carbide, Danbury, CT.). Tone 0201 is difunctional with respect to lca.;LiviLy.
Various other components at low addition levels such as wetting and anti-blocking agents and other components known in the art, such as CA 02237393 l998-05-l2 W O 97/184g3 PCTAUS96~7800 fillers, diluents, pigm~nt.e, etc. can be added to these form~ tions as required.
Physical test data on lc;~ltscllLaliv~ form~ tions are also provided in Tables 1 and 2. Tensile data were obtained on films 2 - 3 mils in 5 thi~knP~s using a 50 % strain rate in a test procedure similar (a 3 inch gauge length was used for the test data reported herein) to ASTMD 882-91, Standard Test Methods for Tensile Properties of Thin Plastic Sheeting.
The cure dose was 500 mj/cm2 on a Fusion Systems bench top conveyor (Fusion Systems, Inc., Rockville, MD) with an H bulb under a nitrogen 10 blanket. The cure temperature was 60~C. Tensile mea~u.cl,.ents were made a "~i"i..~ of 24 hours after curing using a Thwing-Albert Intelect 500 Tensile Tester (Thwing-Albert Instrument Co., Philadelphia, PA).
Ambient laboratory conditions for tensile measurements were in the range of 23 - 35~C at a relative hllmi-lity of 45 - 55%. Modulus data reported 15 are for t_e tangent modulus at the inLcl-;c~t of the stress-strain curve.
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CA 02237393 l998-05-l2 W O 97/18493 PCT~US96rl7800 .
MATRIX FORMULATIONS
FORMULATION
IDENTIFICATION (PARTS BY
WEIGHT) COMPONENTS: 2A 2B 2C 2D 2E 2F
ÇYCLOALIPHATIC EPOXIDES:
POLYOLS:
VINYL k;l~KS:
~T T .TFn 150B 13.5 VECTOMER 4010 4.5 VECTOMER 3010 2.0 ACRYLATES:
ADDITIVES:
IRGANOX 1076 1.0 1.0 1.0 1.0 1.0 1.0 WI 6990 4.0 4 0 4 0 4 0 4 0 3 0 IRC~ACURE 651 1.0 PROPERTIES:
MODULES (MPa): 1117 703 200 103 579 ELONGATION MAX(%): 5.3 7.0 75 36 27 BREAK STRENGTH (MPa): 37.2 25.514.5 3.4 15.2 MODULUS CHANGE, (%), -76 95C/95RH 6 DAYS) VISCOSITY 25 C (Poise) 3.9 3.0 2.6 3.8 CA 02237393 l998-0~-l2 W O 97/18493 PCTrUS96/17800 The 95~C/95% relative hnmi~lity (RH~ conditioning was done in a Blue M Power-0-Matic 60 (Blue M Electric, Blue Island, IL) L~ cldlulc/1.~....icljly oven. Samples were co~ t~ for at least 24 hours at ambient after removal from the oven before testing. Viscosity was deL~ illed using either a Brookfield model LVF or a model RVT
(Brookfield F.ngi~ .illg Laboratory, Inc., Stoughton, MA) viscometer.
Tensile data show a range of values from about 100 to 1000 MPa.
The data show the usual variation in ploL:ellies with crosslink density and the backbone flexibility. The effect of crosslink density is illustrated in Table 1 where use of the monofunctional monomer Vectomer 3010 in place of the difunctional mo~ me.r Ve~;lolllel 4010 (Formulations lA and lN) leads to decrease in modulus associated with the decrease in crosslink density. The same can be seen in Table 2 where difunctional Tone 0201 is used in place of the trifunctional Tone 0301 (Form~ til~ns 2A and 2C).
The example of backbone flexibility can be seen in Table 2 where WR-6128 is used in place of the more rigid UVR 6110 molecule (Formlll~ti-ns 2C and 2E).
Stability data, as measured by modulus change after conditioning at 95~C/95% RH for 20 and 30 days are given in Table 1 and after 6 days in Table 2. For the purposes of the present invention, the modulus should not change by more than about 20% after 30 days at 85~C/85%
RH. The precision of the modulus measurement is approximately +/-5%. Therefore, the precision of the modulus change measurement will be greater than 5%. The data ~lcsellLcd in the tables infljc~te good retention of mo(l~ ls for vinyl ether formlll~tion lA. At 20 days the vinyl ether formulations with approximately 20% acrylate nionomer are reasonably stable as is the vinyl ether formulation lB based on the vinyl ether ulcLllalle oligomer. However, at 30 days all these latter materials have m~rkeAly increased in modulus. The use of the Vectomer 2032 type oligomer may, therefore, be limited by stability requirements in the particular application of the system. Nonetheless, the basic and underlying concept of the present invention has been shown.
W O 97/18493 PCT~US96/17800 This is also a practical limitation in the amount of acrylate monomer that can be added while m~int~inin~ qll~t~ temperature and hllmi~lhy stability for many applications. Ch~mi~l kinetics would suggest that all of the above formulations would have been acceptable after 30 5 days at 85~C/85% RH. Moreover, the color stability of the vinyl ether cullly~>ullds based on the ester type oligomer (Formulations lA, lF, lG
and lH) was good, showing only a slight off color tint after the 30 day test. Matrix culll~uulld lB was ~ y off color and would not be acceptable without further stabilization in applications where color stability is an important criteria.
A matrix compound (formula 2A) based on cycloaliphatic epoxides and polyols showed poor l,clr~"lllallce in the 95~C/95% RH test in~ ting that ~is type compound is limited to applications where high temperature, high hllmi~lity stability is not critical.
~pecific formulations for the in~s tested are given in Table 3. As used in that Table, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholhlu~lopallolle-l is a free radical-type pholoilliLi~lcr which is sold under the trade name Irgacure 9û7 (Ciba-Geigy Corp., Hawthorne, NY).
TiO~ is a white pigment available from multiple sources, e.g., Tronox CR-800 from Kerr-McGee ChPmir~l Corp. Bis-~2,2,6,6-tetramethyl-4-piperidyl) sebacate is a hindered amine light stabilizer sold under the trade name Tinuvin 770 (Ciba-Geigy Corp., Hawthorne, NY). The other blend components listed in Table 3 have been previously described.
W INK FORMULATIONS:
INK IDENTIFICATION
(PARTS BY WEIGHT) COMPONENTS: UV1 ¦ W2 ¦ UV3 ¦ W4 ¦ UV5 EBECRYL 8804 68.25 68.25 68.25 68.25 68.25 TMPTA 18.9 18.9 18.9 18.9 18.9 HDODA 10.5 10.5 10.5 10.5 10.5 TRPGDA 7.35 7.3s 7.35 7.35 7.35 TIO2 5.0 5.0 5.0 5.0 5.0 IRGANOX 1076 1.0 1.0 1.0 1.0 1.0 IRGACURE 907 3.0 -- 1.5 0.75 --IRGACURE 651 -- 3 1.5 2.25 3.0 SF-1188 0.5 0.5 0.5 0.5 0 5 TINUVIN 770 -- -- -- -- 1.0 Test plaques for dele.. i~lion of T-peel Adhesion were pl~al~d as follows. An a~lvxi...~t~ 75 micron thir'~n~s~ of Desolite'9 Product Code 950-044 optical fiber coating (DSM Desotech Inc., Elgin, IL), an industry-known UV curable acrylate coating, having a viscosity of 5000 cps at 25~C and a tensile modulus upon curing of 690 MPa at 23~C, 50%
10 relative hllmitlity, is cured at a cure dose of 500 mj/cm2 using a Fusion Systems D bulb under a nitrogen blanket. The cured film is held for at least one day before procee-lin~ to the next step. After the holding period, an approximate 10 micron thickness layer of a UV curable acrylate polymer based ink is then applied and cured under a nitrogen 15 blanket with a Fusion Systems H bulb at a cure dose of 250 mj/cm2 (this step is skipped for non-color coded testing). The color coded composite is then held for at least one day before proceerling. In the final step, an approximately 75 micron thick layer of matrix compound is applied at a W O 97/18493 PCT~S96/17800 I~"lpe.aLul~ of 60~C and then cured with a Fusion Systems H bulb at a cure dose of 500 mj/cm2 under a nitrogen blanket. In some tests, a release layer is applied to the top of the composite to provide a nom-bonded layer at the top of the test composite. The fini~h~-l composite is 5 again held for at least 48 hours. Tape (Scotch'l9 3M m~iling tape, 3M, Minneapolis, MN) is then applied to both sides of the sample for support to prevent tensile failure of the composite, a 1 inch wide test strip is cut, and a separation made by hand at the interface between the ink and the matrix compound in the non-bonded region. A T-peel test is then run on 10 a Thwing-Albert tensile tester at a crosshead rate of 2 in./min. The peel level is recorded along with the failure int~ e.
Test data for the various matrix compound and ink combinations are given in Table 4. As can be seen, formulations lA and lB (which contain no acrylate components) have very low adhesion to the optic fiber 15 coating material when no ink is present. When the UVl or UV2 ink is applied, adhesion of lA (which contains a vinyl ether encapped urethane oligomer) remains low. However, adhesion of lB (which contains a vinyl ether ellcayyed oligomer) ~ aills low. However, ~t1h~osinn of lB (which COll~illS a vinyl ether encapped ester oligomer) increases signiftr~ntly.
W O 97/18493 PCT~US96/17800 MATRIX ADHESION
(T-PEEL ADHESION, pounds/inch width) FIBER COATING D950-044 13ASE lA
INK ID NONE Wl W2 UV3 UV4 UV5 NONE UV2 %
MATRIX ACRYLATE
ID:IN MATRIX
lA o 0.01o o4'o l~l' 0.01 0.03 lB 0 0.020.55 0.57 lN 0 0.010.02 0.09 0.04 lL 100d >2.04 > 1.42 0.02 0.02 lE 10a 0.06 0.09 lH 20a 0.22 0.15 lK 50~ > 3.15 0.70 lC 10 0.13 0.10 lF 20~) 0.10 0.20 lI 50~ > 1.86 > 1.83 lD 10C 0.06 0.10 lG 20C 0.07 0.09 lJ 50c 0.25 0.40 lM 50d 0.5 > 2.19 2A 0 0.040.14> 1.42 2B lOa >1.72 > 1.48 2C 0 0.34f 2D 0 0.66f 2E 0 > 1.51f 2F 0 0.07' a: TRPGDA
b: HDODA
c: TMPTA
d: MONOMER + OLIGOMER
e: Matrix layer cured at 40~C
f: Matrix layer cured at ambient UVl and UV2 both contain an urethane acrylate oligomer.
Therefore, the inks in ~hose cases contain an oligomer which is more chemically similar to the lB matrix compound than the lA matrix compound. Hence, the adhesion of lB to the ink is greater than lA to the ink.
W O 97/18493 PCT~US96/I7800 As various acrylate components are added to the lA type matrix (matrix materials lC through lM), the a&esion can be increased to obtain a desired level. The greater the acrylate content of the matrix, the greater the ch~mir~l .simil~rity be~w~en the matrix and the ink and, S therefore, the greater the adhesion. Once the matrix acrylate content has reached about 50%, the adhesion is too high to obtain a m.-~nin~fiul test.
Where the greater than ( > ) sign is shown in Table 4, the peel occurs between the back-up tape and the matrix compound in-1ic~tin~ that the peel adhesion level between the ink and the matrix compound is at a higher level than can be ~l.ot~rmin~o~ by this test co~ ul~lion. In all other test samples, the peel interface is 'v~ween the ink and tbe matrix compound or belwec;ll the matrix compound and fiber coating material where no ink is present.
It is a~alell~ from the above-data that combinations of vinyl ether ell~apped u~ e and ester oligomers can also be used to control the peel adhesion.
~ldition~lly~ the data shows that if the ink is based on a ester acrylate oligomer, that the matrix compound lB above would have lower peel adhesion to the ink than would matrix compound lA.
Moreover, in a mixed acrylate/vinyl ether or other cationic cure system, both cationic and free radical type UV activated initiators are required.
To dt;L~ e the viability of embo~ime~ t~ where the ink contains an inhibitor of the c~tionir cure matrix materials, four llifrel~llL blends of ink were ~,~al~d by adding 1.0 percent by weight of four components to forrnulation lA in Table 1. These materials were Irgacure 651, Irgacure 907 (previously described as an initiator for acrylate systems), 1-vinyl-2-pyrrolidone (NVP), and a hindered amine light stabilizer bis-(2,2,6,6-tetr~m~thyl-4-piperidyl) sebacate which is sold under the trade name Tinuvin 770 (Ciba-Geigy Corp., Hawthorne, NY). The materials were cured as previously described for matrix compounds. In these tests, the blends cont~inin~ Tinuvin 770 and Irgacure 907 did not cure but remained VVO 97/18493 PCTnUS96/17800 viscous liquids even after exposure to UV light. The blend corlt~ining NVP, upon exposure to W light, yielded a undercured, tacky film which was too fragile for tensile analysis. The blend cc ~ g Irgacure 651 was well-cured.
The viability of cure inhibition in a free-radical based polymer matrix was tested by the addition of 0.5% and 0.25% by weight of naphthaquinone to the acrylate coating Desotech19 950 44. A similar amount was added in the reverse case for matrix lN. On exposure to a 500 mj/cm2 dose of W radiation, the 950-044 with 0.5% n~phth~-luinone 10 produced a low modulus, greatly undercured product. The lN matrix was slightly undercured. At a 0.25% naphthaquinone level, the 950-044 again was undercured with a modulus of 18 MPa. The lN matrix with 0.25% naphth~ in~ ne was well-cured with a modulus of 418 MPa.
Table 4 sets forth peel adhesion data for Matrix lA from inks 15 cont~ining 3 parts by weight of Irgacure 907 (UV1) and Irgacure 651 (UV2). As can be seen, there is a decrease in adhesion when going from the Irgacure 651 to the Irgacure 907 cont~ining ink. F.Y~min~ti-)n of the molecular structure of Irgacure 907 shows it to be a hindered amine.
UV3 and UV4 inks have a combination of Irgacure 651 and ~rgacure 907 initiators. In combination with matrix lA, both of these inks also show lower adhesion relative to UV2 and Matrix lA. When the hindered amine light stabilizer Tinuvin 770 is added to the ink ~W5) and Matrix lN is used, a similar drop in peel adhesion is seen relative to the UV2/lN
combination.
Table 4 also describes peel adhesion data for cationic cure systems based on cycloaliphatic epoxide/polyol combinations. As can be seen from tests con~ t~l with Matrix m~ter~ 2A through 2E, values are somewhat higher than those obtained using formulations based on vinyl ether ch~ tty. In fact, it appears nPcess~ry to use Irgacure 907 in the ink to properly reduce the peel adhesion. Furtherrnore, use of the Llirun~;Lional polyol 0301 results in lower adhesion than does polyol 0201.
Increasing the level of 0201 also increases the adhesion. When combinations of the two chemistries are used as in formula 2F, the adhesion reading falls between the values reported for the non-mixed formlllAti~ns. These data support the finding, based upon the present disclosure, one of skill in the art could fornml~te the various components S to obtain a desired adhesion level without undue experimentation. Other properties, such as modulus and stability, will dictate which combinations are most desirable in obtaining the final ~r~ lies depending upon the desired application.
Based upon the disclosure of the present invention, if the optical 10 fiber coating is a cationic material, it would be desirable to use a C~t;oniccure ink for adhesion to the ~lber coating and an acrylate based matrix for release from the cationic ink. Table 4 also demol~LlaL~s that this is the case. For example, when Matrix lA was cured first, i.e., as the optical fiber coating, subseq~lent cure of the acrylate ink UV2 or acrylate matrix 15 lL on the vinyl ether coating surface resulted in poor adhesion. Hence the ink used where the fiber coating is ~ut~ l;Ally a cationic cure compound should also be comprised substAnti~lly of a cationic cure components and the matrix compounds should be co~ lised subst~nti~lly of free radical initi~t~l acrylate type components.
In Table 1, Allied Signal 150B (Allied Signal, Inc., Morristown, NJ) is a vinyl ether encapped polyester oligomer having a viscosity of 340,000 cps at 60~C and a weight average molecular weight of from 2000 to 3500. Vectomer 2032 (Allied Signal, Inc., Mo~ Lc,wll, NJ) is a vinyl ether encapped ult;lllalle oligomer which has a viscosity of 30,000 cps at 70~C and a weight average molecular weight of 4800 to 6600. Bis-(4-vinyloxybutyl) isophth~l~t~ is a difunctional (with respect to cationic cure) vinyl ether monomer with a viscosity of 85 cps at 25~C and is sold under the trade name Vectomer 4010 (Allied Signal, Inc., Molli~Lowll, NJ). 4-15 vinyloxybutyl benzoate is a monofunctional vinyl ether monomer (with respect to cationic cure) having a viscosity of 7 cps at 25~C and is available under the trade name Vectomer 3010 (Allied Signal, Inc., Morristown, NJ).
Other pl~f~,llcd vinyl ether compounds that are particularly 20 suitable for ~e matrix composi~ions of the present invention include, but are not limited to, 1,4-bis[(vinyloxy)methyl]-cycl-hP~n~ (1,4-cyclohP~nr-limPth~n-)l divinyl ether), sold under the trade name Rapi-Cure CHVE (In~ alional Specialty Products, Inc., Wayne N.J.) and having a viscosity of 5.0 cps at 25~C; 3,6,9,12-tetraoxatetradeca-1,13-25 diene (triethylene glycol divinyl ether), sold uIlder the trade name Rapi-Cure DVE-3 (IllLt~ alional Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 2.67 cps at 25~C; hydroxybutyl vinyl ether, sold under the trade name Rapi-Cure HBVE (T,.~ nal Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 7.5 cps at 25~C; n-dodecyl ~ 30 vinyl ether, sold under the trade name Rapi-Cure DDVE (Tnt~rn~tional Specialty Products, Inc., Wayne, N.J.) and having a viscosity of 2.81 cps at 25~C; bis-(4-vinyloxymethylcyclohexyl methyl) glutarate, sold under W O 97/18493 PCTrUS96/17800 the trade name Vectomer 4020 (Allied Signal Corp., Molli..L~wll, N.J.) and having a viscosity of 430 cps at 25~C; and bis-(4-vinyloxybutyl) succinate (IllL~ lional Specialty Products, Inc., Wayne, N.J.) having a viscosity o~ 43 cps at 25~C. Other suitable vinyl ethers include, but are 5 not limited to, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, butyl vinyl ether, ethyleneglycol vinyl ether, diethyleneglycol divinyl ether, b -t~n~Ai~l monovinyl ether, b~tAn~iol divinyl ether, ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinyl ether, cyclohtox~n~Aim~th~n~ l monovinyl ether, 2-ethylhexyl vinyl ether, Poly-THF-divinyl ether 290, pluriol-E-200-divinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl etner, ethyleneglycol divinyl ether, diethyleneglycol mol~villyl ether, h.o~n.-Aiol monovinyl ether, tetraethyleneglycol divinyl ether, trimethylol~lo~le trivinyl ether, aminopropyl vinyl ether, or 2-diethyl~minnethyl vinyl ether (prece-lin~ vinyl ethers available from BASF, Mount Olive, N.J.).
In addition, there are many acrylate polymers ("acrylates") in use today which are suitable for the purposes described herein. More particularly, for the purposes of the examples ~ c~l~seA. herein, Ebecryl 8804 is the trade name for an ~lirh~t;l' urethane acrylate oligomer with a viscosity of 10,000 - 24,000 cps at 65~C, a molecular weight of 1,400 and a functionality of 2.4 (UCB Radcure Inc., Smyrna, GA).
Tlipl~ylene glycol diacrylate (TRPGDA) is a dirull~;Lional mollolllel with a viscosity of 12 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
Trimethylo~rol~alle triacrylate (TMPTA) is a Llirulu;lional monomer with a viscosity of 85 cps at 25~C (UCB Radcure Inc., Smyrna, GA). 1,6-hexanediol diacrylate (HDODA) is a difunctional monomer with a viscosity of 6 cps at 25~C (UCB Radcure Inc., Smyrna, GA). ~-carboxyethyl acrylate (~-CEA) is a monofunctional monomer with a viscosity of 75 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Isobornyl acrylate (IBOA) is a monofunctional monomer with a viscosity of 9.5 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Octylfdecyl acrylate (ODA) is a monorullcLional monomer with a viscosity of 2 cps at 25~C (UCB
CA 02237393 l998-05-l2 W O 97rl8493 PCT~US96rI78~0 Radcure Inc., Smyrna, GA). O~y~lylated phenol acrylate (Ebecryl~9 110) is a monofllnf~tinn~l monl~m~r with a viscosity of 75 cps at 25~C
(UCB Radcure Inc., Smyrna, GA). Tetrae~ylene glycol diacrylate (TTEGDA) is a difunrti~-n:~l monomer with a viscosity of 20 cps at 25~C
5 (UCB Radcure Inc., Smyrna, GA). Bisphenol-A derivative diacrylate (Ebecryl~ 150) is a difunctional monomer with a viscosity of 1,500 cps at 25~C (UCB Radcure Inc., Smyrna, GA). OTA480 is a llifull;Lional monomer with a viscosity of 85 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Penta~ ol triacrylate (PETA-K) is a lliÇullcLional monomer with a viscosity of 500 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
PETA-LQ is a lower functionality version of PETA-K with a viscosity of 1,500 cps at 25~C (UCB Radcure Inc., Smyrna, GA).
Trimethylolpropane ethoxy triacrylate (TMPEOTA) is a L~ir~ Lion~l monomer with a viscosity of 20 cps at 25~C (UCB Radcure Inc., Smyrna, GA). Acrylated di-penta~:ly~ ilol (DPHPA) is a m~ ir.l.-. ~ional monomer with a viscosity of 20,000 cps at 25~C (UCB Radcure Inc., Smyrna, GA). In ~d-1iti~ n, other Ebecryl'l9 acrylates suitable for the present purposes include, but are not limited to, Ebecryl'l9 80, 81, 82, 220, 230, 244, 264, 265, 270, 284, 285, 436, 438, 450, 505, 524, 525, 584, 585, 586, 588, 600, 605, 616, 629, 639, 657, 745, 754, 767, 770, 810, 830, 860, 870, 1290, 1608, 1657, 1701, 1755, 1810, 3200, 3201, 3409, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3702, 3703, 4827, 4830, 4833, 4834, 4849, 4866, 4881, 4883, 6602, 6700, 8301, 8402, 8800, 8800-20R, or 8803 (All Ebecryla9 product numbers available from UCB
Radcure Inc., Smyrna, GA).
Ar3SPF6 in the presence of W light can serve as the initiator in the cationic polymerization of vinyl ether oligomers and monomers and is sold under the trade name UVI 6990 (Union Carbide, Danbury, CT).
2,2-dimethoxy-2-phenylacetophenone is a Norish Type 1 Cleavage photo initiator with a melting point of 63-66~C and is available sold under the trade name Irgacure 651 (Ciba-Geigy Corp., Hawthorne, N~). Irgacure CA 02237393 1998-0~-12 W O 97/18493 PCT~US96/17800 651 serves as the free radical source on exposure to UV light for the polymerization of acrylate monomers and oligomers. Octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate is a ~herm~l oxidative stabilizer which is available under the trade name Irganox 1076 (Ciba-Geigy Corp., S Hawthorne, NY). The l,ro~,lyl ether of propylene carbonate (RAPI-CURE PE~PC) has a molecular weight of 158 and a viscosity of 13 cps at 25~C (Intcl,~lional Specialty Products, Wayne, NJ or Charlotte, NC).
PEPC helps to solubilize the UV 6990.
SF 1188 is the trade name for the copolymer of a polyllleLllyl siloxane and a polyoxy alkene ether having a viscosity of 600-1200 cps at 25~ C, a density of 1.04 g/cc avg., and a surface tension of 25.5 dynes/cm2 (GE Silicones, WaLelrold, NY). SF 1188 is an anti-blocking agent which prevents tacking together of 5~ rlt layers of ink or matrix when the product is wound upon itself.
In Table 2, UVR~6110 is the kade name for 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate which has an epoxy equivalent weight of 131 - 143 and a viscosity at 25~C of 350 -450 cps (Union Carbide, Danbury, CT.). See Carroy, Antoine, Aspects of Photoinitiaion: Cationic UV-Curing Eff~iciency of Cycloaliphatic Epoxide-Based Systems Through Photoinitiator and UV-Wavelength Selection (1993). UVR-6128 is the kade name for bis-(3,4-epoxycyclohexyl) adipate which has an epoxide equivalent weight of 350-450 and a viscosity at 25~C 190 - 210 cps (Union Carbide, Danbury, CT.). Tone 0301 is the trade name for an ~-caprolactone kiol which has an hydroxyl equivalent weight of 98 - 103 and a viscosity of 2250 cps at 55~C (Union Carbide, Danbury, CT.). Tone 0301 is kifunctional with respect to reactivity. Tone 0201 is the trade name for a caprolactone diol having an average molecular weight of 530 and a viscosity of 65 cps at 55~C (Union Carbide, Danbury, CT.). Tone 0201 is difunctional with respect to lca.;LiviLy.
Various other components at low addition levels such as wetting and anti-blocking agents and other components known in the art, such as CA 02237393 l998-05-l2 W O 97/184g3 PCTAUS96~7800 fillers, diluents, pigm~nt.e, etc. can be added to these form~ tions as required.
Physical test data on lc;~ltscllLaliv~ form~ tions are also provided in Tables 1 and 2. Tensile data were obtained on films 2 - 3 mils in 5 thi~knP~s using a 50 % strain rate in a test procedure similar (a 3 inch gauge length was used for the test data reported herein) to ASTMD 882-91, Standard Test Methods for Tensile Properties of Thin Plastic Sheeting.
The cure dose was 500 mj/cm2 on a Fusion Systems bench top conveyor (Fusion Systems, Inc., Rockville, MD) with an H bulb under a nitrogen 10 blanket. The cure temperature was 60~C. Tensile mea~u.cl,.ents were made a "~i"i..~ of 24 hours after curing using a Thwing-Albert Intelect 500 Tensile Tester (Thwing-Albert Instrument Co., Philadelphia, PA).
Ambient laboratory conditions for tensile measurements were in the range of 23 - 35~C at a relative hllmi-lity of 45 - 55%. Modulus data reported 15 are for t_e tangent modulus at the inLcl-;c~t of the stress-strain curve.
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o ~ o o~
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CA 02237393 l998-05-l2 W O 97/18493 PCT~US96rl7800 .
MATRIX FORMULATIONS
FORMULATION
IDENTIFICATION (PARTS BY
WEIGHT) COMPONENTS: 2A 2B 2C 2D 2E 2F
ÇYCLOALIPHATIC EPOXIDES:
POLYOLS:
VINYL k;l~KS:
~T T .TFn 150B 13.5 VECTOMER 4010 4.5 VECTOMER 3010 2.0 ACRYLATES:
ADDITIVES:
IRGANOX 1076 1.0 1.0 1.0 1.0 1.0 1.0 WI 6990 4.0 4 0 4 0 4 0 4 0 3 0 IRC~ACURE 651 1.0 PROPERTIES:
MODULES (MPa): 1117 703 200 103 579 ELONGATION MAX(%): 5.3 7.0 75 36 27 BREAK STRENGTH (MPa): 37.2 25.514.5 3.4 15.2 MODULUS CHANGE, (%), -76 95C/95RH 6 DAYS) VISCOSITY 25 C (Poise) 3.9 3.0 2.6 3.8 CA 02237393 l998-0~-l2 W O 97/18493 PCTrUS96/17800 The 95~C/95% relative hnmi~lity (RH~ conditioning was done in a Blue M Power-0-Matic 60 (Blue M Electric, Blue Island, IL) L~ cldlulc/1.~....icljly oven. Samples were co~ t~ for at least 24 hours at ambient after removal from the oven before testing. Viscosity was deL~ illed using either a Brookfield model LVF or a model RVT
(Brookfield F.ngi~ .illg Laboratory, Inc., Stoughton, MA) viscometer.
Tensile data show a range of values from about 100 to 1000 MPa.
The data show the usual variation in ploL:ellies with crosslink density and the backbone flexibility. The effect of crosslink density is illustrated in Table 1 where use of the monofunctional monomer Vectomer 3010 in place of the difunctional mo~ me.r Ve~;lolllel 4010 (Formulations lA and lN) leads to decrease in modulus associated with the decrease in crosslink density. The same can be seen in Table 2 where difunctional Tone 0201 is used in place of the trifunctional Tone 0301 (Form~ til~ns 2A and 2C).
The example of backbone flexibility can be seen in Table 2 where WR-6128 is used in place of the more rigid UVR 6110 molecule (Formlll~ti-ns 2C and 2E).
Stability data, as measured by modulus change after conditioning at 95~C/95% RH for 20 and 30 days are given in Table 1 and after 6 days in Table 2. For the purposes of the present invention, the modulus should not change by more than about 20% after 30 days at 85~C/85%
RH. The precision of the modulus measurement is approximately +/-5%. Therefore, the precision of the modulus change measurement will be greater than 5%. The data ~lcsellLcd in the tables infljc~te good retention of mo(l~ ls for vinyl ether formlll~tion lA. At 20 days the vinyl ether formulations with approximately 20% acrylate nionomer are reasonably stable as is the vinyl ether formulation lB based on the vinyl ether ulcLllalle oligomer. However, at 30 days all these latter materials have m~rkeAly increased in modulus. The use of the Vectomer 2032 type oligomer may, therefore, be limited by stability requirements in the particular application of the system. Nonetheless, the basic and underlying concept of the present invention has been shown.
W O 97/18493 PCT~US96/17800 This is also a practical limitation in the amount of acrylate monomer that can be added while m~int~inin~ qll~t~ temperature and hllmi~lhy stability for many applications. Ch~mi~l kinetics would suggest that all of the above formulations would have been acceptable after 30 5 days at 85~C/85% RH. Moreover, the color stability of the vinyl ether cullly~>ullds based on the ester type oligomer (Formulations lA, lF, lG
and lH) was good, showing only a slight off color tint after the 30 day test. Matrix culll~uulld lB was ~ y off color and would not be acceptable without further stabilization in applications where color stability is an important criteria.
A matrix compound (formula 2A) based on cycloaliphatic epoxides and polyols showed poor l,clr~"lllallce in the 95~C/95% RH test in~ ting that ~is type compound is limited to applications where high temperature, high hllmi~lity stability is not critical.
~pecific formulations for the in~s tested are given in Table 3. As used in that Table, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholhlu~lopallolle-l is a free radical-type pholoilliLi~lcr which is sold under the trade name Irgacure 9û7 (Ciba-Geigy Corp., Hawthorne, NY).
TiO~ is a white pigment available from multiple sources, e.g., Tronox CR-800 from Kerr-McGee ChPmir~l Corp. Bis-~2,2,6,6-tetramethyl-4-piperidyl) sebacate is a hindered amine light stabilizer sold under the trade name Tinuvin 770 (Ciba-Geigy Corp., Hawthorne, NY). The other blend components listed in Table 3 have been previously described.
W INK FORMULATIONS:
INK IDENTIFICATION
(PARTS BY WEIGHT) COMPONENTS: UV1 ¦ W2 ¦ UV3 ¦ W4 ¦ UV5 EBECRYL 8804 68.25 68.25 68.25 68.25 68.25 TMPTA 18.9 18.9 18.9 18.9 18.9 HDODA 10.5 10.5 10.5 10.5 10.5 TRPGDA 7.35 7.3s 7.35 7.35 7.35 TIO2 5.0 5.0 5.0 5.0 5.0 IRGANOX 1076 1.0 1.0 1.0 1.0 1.0 IRGACURE 907 3.0 -- 1.5 0.75 --IRGACURE 651 -- 3 1.5 2.25 3.0 SF-1188 0.5 0.5 0.5 0.5 0 5 TINUVIN 770 -- -- -- -- 1.0 Test plaques for dele.. i~lion of T-peel Adhesion were pl~al~d as follows. An a~lvxi...~t~ 75 micron thir'~n~s~ of Desolite'9 Product Code 950-044 optical fiber coating (DSM Desotech Inc., Elgin, IL), an industry-known UV curable acrylate coating, having a viscosity of 5000 cps at 25~C and a tensile modulus upon curing of 690 MPa at 23~C, 50%
10 relative hllmitlity, is cured at a cure dose of 500 mj/cm2 using a Fusion Systems D bulb under a nitrogen blanket. The cured film is held for at least one day before procee-lin~ to the next step. After the holding period, an approximate 10 micron thickness layer of a UV curable acrylate polymer based ink is then applied and cured under a nitrogen 15 blanket with a Fusion Systems H bulb at a cure dose of 250 mj/cm2 (this step is skipped for non-color coded testing). The color coded composite is then held for at least one day before proceerling. In the final step, an approximately 75 micron thick layer of matrix compound is applied at a W O 97/18493 PCT~S96/17800 I~"lpe.aLul~ of 60~C and then cured with a Fusion Systems H bulb at a cure dose of 500 mj/cm2 under a nitrogen blanket. In some tests, a release layer is applied to the top of the composite to provide a nom-bonded layer at the top of the test composite. The fini~h~-l composite is 5 again held for at least 48 hours. Tape (Scotch'l9 3M m~iling tape, 3M, Minneapolis, MN) is then applied to both sides of the sample for support to prevent tensile failure of the composite, a 1 inch wide test strip is cut, and a separation made by hand at the interface between the ink and the matrix compound in the non-bonded region. A T-peel test is then run on 10 a Thwing-Albert tensile tester at a crosshead rate of 2 in./min. The peel level is recorded along with the failure int~ e.
Test data for the various matrix compound and ink combinations are given in Table 4. As can be seen, formulations lA and lB (which contain no acrylate components) have very low adhesion to the optic fiber 15 coating material when no ink is present. When the UVl or UV2 ink is applied, adhesion of lA (which contains a vinyl ether encapped urethane oligomer) remains low. However, adhesion of lB (which contains a vinyl ether ellcayyed oligomer) ~ aills low. However, ~t1h~osinn of lB (which COll~illS a vinyl ether encapped ester oligomer) increases signiftr~ntly.
W O 97/18493 PCT~US96/17800 MATRIX ADHESION
(T-PEEL ADHESION, pounds/inch width) FIBER COATING D950-044 13ASE lA
INK ID NONE Wl W2 UV3 UV4 UV5 NONE UV2 %
MATRIX ACRYLATE
ID:IN MATRIX
lA o 0.01o o4'o l~l' 0.01 0.03 lB 0 0.020.55 0.57 lN 0 0.010.02 0.09 0.04 lL 100d >2.04 > 1.42 0.02 0.02 lE 10a 0.06 0.09 lH 20a 0.22 0.15 lK 50~ > 3.15 0.70 lC 10 0.13 0.10 lF 20~) 0.10 0.20 lI 50~ > 1.86 > 1.83 lD 10C 0.06 0.10 lG 20C 0.07 0.09 lJ 50c 0.25 0.40 lM 50d 0.5 > 2.19 2A 0 0.040.14> 1.42 2B lOa >1.72 > 1.48 2C 0 0.34f 2D 0 0.66f 2E 0 > 1.51f 2F 0 0.07' a: TRPGDA
b: HDODA
c: TMPTA
d: MONOMER + OLIGOMER
e: Matrix layer cured at 40~C
f: Matrix layer cured at ambient UVl and UV2 both contain an urethane acrylate oligomer.
Therefore, the inks in ~hose cases contain an oligomer which is more chemically similar to the lB matrix compound than the lA matrix compound. Hence, the adhesion of lB to the ink is greater than lA to the ink.
W O 97/18493 PCT~US96/I7800 As various acrylate components are added to the lA type matrix (matrix materials lC through lM), the a&esion can be increased to obtain a desired level. The greater the acrylate content of the matrix, the greater the ch~mir~l .simil~rity be~w~en the matrix and the ink and, S therefore, the greater the adhesion. Once the matrix acrylate content has reached about 50%, the adhesion is too high to obtain a m.-~nin~fiul test.
Where the greater than ( > ) sign is shown in Table 4, the peel occurs between the back-up tape and the matrix compound in-1ic~tin~ that the peel adhesion level between the ink and the matrix compound is at a higher level than can be ~l.ot~rmin~o~ by this test co~ ul~lion. In all other test samples, the peel interface is 'v~ween the ink and tbe matrix compound or belwec;ll the matrix compound and fiber coating material where no ink is present.
It is a~alell~ from the above-data that combinations of vinyl ether ell~apped u~ e and ester oligomers can also be used to control the peel adhesion.
~ldition~lly~ the data shows that if the ink is based on a ester acrylate oligomer, that the matrix compound lB above would have lower peel adhesion to the ink than would matrix compound lA.
Moreover, in a mixed acrylate/vinyl ether or other cationic cure system, both cationic and free radical type UV activated initiators are required.
To dt;L~ e the viability of embo~ime~ t~ where the ink contains an inhibitor of the c~tionir cure matrix materials, four llifrel~llL blends of ink were ~,~al~d by adding 1.0 percent by weight of four components to forrnulation lA in Table 1. These materials were Irgacure 651, Irgacure 907 (previously described as an initiator for acrylate systems), 1-vinyl-2-pyrrolidone (NVP), and a hindered amine light stabilizer bis-(2,2,6,6-tetr~m~thyl-4-piperidyl) sebacate which is sold under the trade name Tinuvin 770 (Ciba-Geigy Corp., Hawthorne, NY). The materials were cured as previously described for matrix compounds. In these tests, the blends cont~inin~ Tinuvin 770 and Irgacure 907 did not cure but remained VVO 97/18493 PCTnUS96/17800 viscous liquids even after exposure to UV light. The blend corlt~ining NVP, upon exposure to W light, yielded a undercured, tacky film which was too fragile for tensile analysis. The blend cc ~ g Irgacure 651 was well-cured.
The viability of cure inhibition in a free-radical based polymer matrix was tested by the addition of 0.5% and 0.25% by weight of naphthaquinone to the acrylate coating Desotech19 950 44. A similar amount was added in the reverse case for matrix lN. On exposure to a 500 mj/cm2 dose of W radiation, the 950-044 with 0.5% n~phth~-luinone 10 produced a low modulus, greatly undercured product. The lN matrix was slightly undercured. At a 0.25% naphthaquinone level, the 950-044 again was undercured with a modulus of 18 MPa. The lN matrix with 0.25% naphth~ in~ ne was well-cured with a modulus of 418 MPa.
Table 4 sets forth peel adhesion data for Matrix lA from inks 15 cont~ining 3 parts by weight of Irgacure 907 (UV1) and Irgacure 651 (UV2). As can be seen, there is a decrease in adhesion when going from the Irgacure 651 to the Irgacure 907 cont~ining ink. F.Y~min~ti-)n of the molecular structure of Irgacure 907 shows it to be a hindered amine.
UV3 and UV4 inks have a combination of Irgacure 651 and ~rgacure 907 initiators. In combination with matrix lA, both of these inks also show lower adhesion relative to UV2 and Matrix lA. When the hindered amine light stabilizer Tinuvin 770 is added to the ink ~W5) and Matrix lN is used, a similar drop in peel adhesion is seen relative to the UV2/lN
combination.
Table 4 also describes peel adhesion data for cationic cure systems based on cycloaliphatic epoxide/polyol combinations. As can be seen from tests con~ t~l with Matrix m~ter~ 2A through 2E, values are somewhat higher than those obtained using formulations based on vinyl ether ch~ tty. In fact, it appears nPcess~ry to use Irgacure 907 in the ink to properly reduce the peel adhesion. Furtherrnore, use of the Llirun~;Lional polyol 0301 results in lower adhesion than does polyol 0201.
Increasing the level of 0201 also increases the adhesion. When combinations of the two chemistries are used as in formula 2F, the adhesion reading falls between the values reported for the non-mixed formlllAti~ns. These data support the finding, based upon the present disclosure, one of skill in the art could fornml~te the various components S to obtain a desired adhesion level without undue experimentation. Other properties, such as modulus and stability, will dictate which combinations are most desirable in obtaining the final ~r~ lies depending upon the desired application.
Based upon the disclosure of the present invention, if the optical 10 fiber coating is a cationic material, it would be desirable to use a C~t;oniccure ink for adhesion to the ~lber coating and an acrylate based matrix for release from the cationic ink. Table 4 also demol~LlaL~s that this is the case. For example, when Matrix lA was cured first, i.e., as the optical fiber coating, subseq~lent cure of the acrylate ink UV2 or acrylate matrix 15 lL on the vinyl ether coating surface resulted in poor adhesion. Hence the ink used where the fiber coating is ~ut~ l;Ally a cationic cure compound should also be comprised substAnti~lly of a cationic cure components and the matrix compounds should be co~ lised subst~nti~lly of free radical initi~t~l acrylate type components.
Claims (24)
1. A coated optical fiber composition comprising:
a) a coated optical fiber b) a colorant layer intimately adhered to the coated optical fiber and c) an outer coating releasably adhered to the colorant layer, wherein the colorant layer is a polymeric coating prepared by either i) polymerizing a composition comprising an ink and an acrylate monomer or oligomer using a free radical initiator, or ii) polymerizing a composition comprising a ink and a monomer or oligomer capable of being polymerized by cationic polymerization using a cationic initiator, and wherein the outer coating is a polymeric coating prepared by iii) polymerizing a composition comprising a monomer or oligomer capable of being polymerized by cationic polymerization using a cationic initiator when the colorant layer is made of acrylate monomers or oligomers, or iv) polymerizing a composition comprising an acrylate monomer or oligomer using a free radical initiator when the colorant layer is made of cationically curable monomers or oligomers.
a) a coated optical fiber b) a colorant layer intimately adhered to the coated optical fiber and c) an outer coating releasably adhered to the colorant layer, wherein the colorant layer is a polymeric coating prepared by either i) polymerizing a composition comprising an ink and an acrylate monomer or oligomer using a free radical initiator, or ii) polymerizing a composition comprising a ink and a monomer or oligomer capable of being polymerized by cationic polymerization using a cationic initiator, and wherein the outer coating is a polymeric coating prepared by iii) polymerizing a composition comprising a monomer or oligomer capable of being polymerized by cationic polymerization using a cationic initiator when the colorant layer is made of acrylate monomers or oligomers, or iv) polymerizing a composition comprising an acrylate monomer or oligomer using a free radical initiator when the colorant layer is made of cationically curable monomers or oligomers.
2. The composition of claim 1 wherein the colorant layer comprises an acrylate monomer or oligomer that is polymerized using a photoinitiator that generates a free radical upon exposure to UV light.
3. The composition of claim 1 wherein the outer coating comprises a cationically polymerizable monomer or oligomer that is polymerized using a photoinitiator that generates a cation upon exposure to UV light.
4. The composition of claim 1 wherein the colorant layer comprises a cationically polymerizable monomer or oligomer that is polymerized using a photoinitiator that generates a cation upon exposure to UV light.
5. The composition of claim 1 wherein the outer coating comprises an acrylate monomer or oligomer that is polymerized using a photoinitiator that generates a free radical upon exposure to UV light.
6. The composition of claim 1 wherein the acrylate monomer or oligomer is urethane which is end-capped with one or two acrylate groups.
7. The composition of claim 1 wherein the monomer capable of being polymerized by cationic polymerization comprises a mixture of a cycloaliphatic epoxide and a polyol.
8. The composition of claim 1 wherein the monomer or oligomer capable of being polymerized by cationic polymerization is end-capped with one or more vinyl ethers.
9. The composition of claim 8 wherein the oligomer comprises a urethane endcapped with one or two vinyl ethers.
10. The composition of claim 1 wherein the composition comprising a cationically polymerizable monomer or oligomer further comprises an acrylate monomer.
11. The composition of claim 10, wherein the amount of acrylate monomer relative to the cationically polymerized monomer is an effective amount to increase the adhesion of the outer coating to the colorant layer to a desired level of adhesion.
12. The composition of claim 1, wherein the cationically polymerizable monomer is Allied Signal 150B.
13. The composition of claim 1, wherein the cationically polymerizable monomer is Vectomer 2032.
14. The composition of claim 1, wherein the cationically polymerizable monomer is bis-(4-vinyloxybutyl)isophthalate.
15. The composition of claim 1, wherein the cationically polymerizable monomer is 4-vinyloxybutyl benzoate.
16. The composition of claim 1, wherein the composition comprising an acrylate monomer or oligomer further comprises an inhibitor of cationically initiated polymerization.
17. The composition of claim 16, wherein the inhibitor is water, a basic compound, or a mixture thereof.
18. The composition of claim 16, wherein the inhibitor is a pigment capable of interacting with the cation.
19. The composition of claim 16, wherein the inhibitor is a hindered amine light stabilizer.
20. The composition of claim 19, wherein the amine is (2,2,6, 6-tetramethyl-4-piperidyl) sebecate.
21. The composition of claim 20, wherein the amine is 1-vinyl-2-pyrrolidone.
22. The composition of claim 1, wherein the composition comprising a cationically polymerizable monomer or oligomer further comprises an inhibitor of free-radical initiated polymerization.
23. The composition of claim 22, wherein the inhibitor is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1.
24. The composition of claim 1, further comprising a plurality of coated optical fibers within the outer layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55812595A | 1995-11-13 | 1995-11-13 | |
| US08/558,125 | 1995-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2237393A1 true CA2237393A1 (en) | 1997-05-22 |
Family
ID=24228311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002237393A Abandoned CA2237393A1 (en) | 1995-11-13 | 1996-11-07 | Matrix compounds for forming optical fiber ribbons |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0861453A1 (en) |
| AU (1) | AU7554496A (en) |
| CA (1) | CA2237393A1 (en) |
| WO (1) | WO1997018493A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998050317A1 (en) * | 1997-05-06 | 1998-11-12 | Dsm N.V. | Radiation-curable ink composition |
| US6197422B1 (en) | 1997-05-06 | 2001-03-06 | Dsm, N.V. | Ribbon assemblies and radiation-curable ink compositions for use in forming the ribbon assemblies |
| EP1408017A3 (en) * | 1997-05-06 | 2006-01-11 | DSM IP Assets B.V. | Radiation curable ink compositions |
| US6130980A (en) * | 1997-05-06 | 2000-10-10 | Dsm N.V. | Ribbon assemblies and ink coating compositions for use in forming the ribbon assemblies |
| JP2002503199A (en) * | 1997-06-11 | 2002-01-29 | デー エス エム エヌ．ヴェー． | Optical glass fiber ribbon aggregate, matrix forming composition used to form ribbon aggregate, and ink coating composition |
| US6085010A (en) * | 1997-06-11 | 2000-07-04 | Dsm N.V. | Optical glass fiber ribbon assemblies and radiation-curable compositions for use in forming ribbon assemblies |
| US6301415B1 (en) | 1997-08-14 | 2001-10-09 | Dsm N.V | Optical glass fiber ribbon assemblies, matrix forming compositions radiation-curable compositions |
| US6391936B1 (en) | 1997-12-22 | 2002-05-21 | Dsm N.V. | Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies |
| US6018605A (en) * | 1997-12-31 | 2000-01-25 | Siecor Operations | Photoinitiator--tuned optical fiber and optical fiber ribbon and method of making the same |
| US6040357A (en) * | 1998-05-28 | 2000-03-21 | Dsm N.V. | Method of making a radiation-curable ink composition, radiation-curable ink composition and ribbon assembly |
| US6501890B1 (en) | 1999-08-09 | 2002-12-31 | Borden Chemical, Inc. | Heat strippable optical fiber ribbons |
| CN1204431C (en) * | 2001-03-15 | 2005-06-01 | 住友电气工业株式会社 | Split type optical fiber core |
| WO2002081396A1 (en) | 2001-04-05 | 2002-10-17 | Borden Chemical, Inc. | Optical fiber ribbon with pigmented matrix, and methods for making and using same |
| FR2847347B1 (en) * | 2002-11-18 | 2005-01-28 | Nexans | METHOD FOR MANUFACTURING OPTICAL FIBER TAPE AND OPTICAL FIBER TAPE |
| FR2851053B1 (en) * | 2003-02-07 | 2005-06-03 | Nexans | OPTICAL FIBER TAPE AND METHOD FOR MANUFACTURING OPTICAL FIBER TAPE |
| US8044110B2 (en) | 2003-05-29 | 2011-10-25 | Prysmian Cavi E Sistemi Energia S.R.L. | Optical fiber with polymeric coating crosslinked in the presence of both radical and cationic photoinitiators |
| ES2541425T3 (en) * | 2007-10-24 | 2015-07-20 | Agfa Graphics N.V. | Inkjet printing methods with radiation curable inkjet inks |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892764A (en) * | 1985-11-26 | 1990-01-09 | Loctite Corporation | Fiber/resin composites, and method of making the same |
| KR880003203A (en) * | 1986-08-05 | 1988-05-14 | 나까하라 쯔네오 | Optical fiber core |
| US4900126A (en) * | 1988-06-30 | 1990-02-13 | American Telephone & Telegraph Co. | Bonded array of transmission media |
| CA1341128C (en) * | 1989-06-27 | 2000-10-24 | Borden Chemical, Inc. | Optical fiber array |
| US5181269A (en) * | 1991-09-17 | 1993-01-19 | At&T Bell Laboratories | Optical fiber including acidic coating system |
-
1996
- 1996-11-07 EP EP96937910A patent/EP0861453A1/en not_active Withdrawn
- 1996-11-07 WO PCT/US1996/017800 patent/WO1997018493A1/en not_active Application Discontinuation
- 1996-11-07 AU AU75544/96A patent/AU7554496A/en not_active Abandoned
- 1996-11-07 CA CA002237393A patent/CA2237393A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0861453A1 (en) | 1998-09-02 |
| AU7554496A (en) | 1997-06-05 |
| WO1997018493A1 (en) | 1997-05-22 |
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