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| United States Patent |
5,881,194
|
|
Duecker
|
March 9, 1999
|
Radiation-cured matrix material; optical fiber ribbons containing same;
and process for preparing said optical fiber ribbons
Abstract
A radiation-curable matrix material for affixing coated and inked optical
fibers in a ribbon configuration is disclosed. The material comprises an
aliphatic polyether-based urethane acrylate; a monomer having a plurality
of acrylate or methacrylate moieties; an alkyl acrylate or methacrylate;
and an optional photoinitiator. Also disclosed are an optical fiber ribbon
prepared therefrom; a process for preparing such ribbon; and a
radiation-curable coating composition generally applicable for coating a
substrate.
| Inventors:
|
Duecker; David Clarke (4714 Greenlee Ave., Cincinnati, OH 45217)
|
| Appl. No.:
|
187006 |
| Filed:
|
March 17, 1994 |
| Current U.S. Class: |
385/115; 385/123; 427/500; 427/503; 427/514; 427/515; 427/517; 522/90; 522/96 |
| Intern'l Class: |
G02B 006/04; G02B 006/16; C08F 002/50 |
| Field of Search: |
385/115,145,123
522/90,93,97,96,81
427/500,503,514,515,517
|
References Cited [Referenced By]
U.S. Patent Documents
| 3411010 | Nov., 1968 | Genahr et al.
| |
| 3912516 | Oct., 1975 | Recchia et al.
| |
| 4065587 | Dec., 1977 | Ting.
| |
| 4116786 | Sep., 1978 | Hodakowski.
| |
| 4123137 | Oct., 1978 | Marcatili.
| |
| 4130708 | Dec., 1978 | Friedlander et al.
| |
| 4131602 | Dec., 1978 | Hodakowski et al.
| |
| 4133723 | Jan., 1979 | Howard.
| |
| 4139436 | Feb., 1979 | Jasani.
| |
| 4176190 | Nov., 1979 | Noethe.
| |
| 4188455 | Feb., 1980 | Howard.
| |
| 4246379 | Jan., 1981 | Howard.
| |
| 4324575 | Apr., 1982 | Levy.
| |
| 4326010 | Apr., 1982 | Bauer.
| |
| 4369300 | Jan., 1983 | Carter et al.
| |
| 4435461 | Mar., 1984 | Gray, III et al.
| |
| 4438190 | Mar., 1984 | Ishimaru et al.
| |
| 4462286 | Jul., 1984 | Kolychek et al.
| |
| 4472021 | Sep., 1984 | Ansel et al.
| |
| 4477548 | Oct., 1984 | Harasta et al.
| |
| 4496210 | Jan., 1985 | Ansel et al.
| |
| 4496686 | Jan., 1985 | Ansel.
| |
| 4512340 | Apr., 1985 | Buck.
| |
| 4533445 | Aug., 1985 | Orio.
| |
| 4567107 | Jan., 1986 | Rizk et al.
| |
| 4588787 | May., 1986 | Kordomenos.
| |
| 4600649 | Jul., 1986 | Leo.
| |
| 4608409 | Aug., 1986 | Coady et al. | 522/97.
|
| 4610746 | Sep., 1986 | Broer et al.
| |
| 4629287 | Dec., 1986 | Bishop.
| |
| 4697877 | Oct., 1987 | Hida et al.
| |
| 4701016 | Oct., 1987 | Gartside, III et al. | 350/96.
|
| 4707076 | Nov., 1987 | Skutnik et al.
| |
| 4717739 | Jan., 1988 | Chevreux et al.
| |
| 4733941 | Mar., 1988 | Broer et al.
| |
| 4733942 | Mar., 1988 | Hida et al.
| |
| 4738509 | Apr., 1988 | Broer et al.
| |
| 4744631 | May., 1988 | Eichenbaum et al.
| |
| 4762751 | Aug., 1988 | Girgis et al.
| |
| 4786586 | Nov., 1988 | Lee et al.
| |
| 4806574 | Feb., 1989 | Krajewski et al.
| |
| 4849462 | Jul., 1989 | Bishop.
| |
| 4889768 | Dec., 1989 | Yokoshima et al.
| |
| 4900126 | Feb., 1990 | Jackson et al. | 350/46.
|
| Foreign Patent Documents |
| 0114982 | Dec., 1982 | EP.
| |
| 0111280 | Jun., 1984 | EP.
| |
| 0157396 | Oct., 1985 | EP.
| |
| 0157540 | Oct., 1985 | EP.
| |
| A 194891 | Sep., 1986 | EP.
| |
| 6131330 | Jul., 1984 | JP.
| |
| A 63-275619 | Apr., 1987 | JP.
| |
| A 63-281109 | Nov., 1988 | JP.
| |
| A1-153710 | Jun., 1989 | JP.
| |
| 2170497 | Aug., 1986 | GB.
| |
Other References
Sales Records provided by Opposer for Desolite.RTM. 950-700 and
Desolite.RTM. 950-701.
Description of Desolite.RTM. 950-700 and 3036-114E.
Description of Desolite.RTM. 950-701 and 950-080.
Material Safety Data Sheet of DC 1248.
Fiber Optics Technology and Applications, pp. 26-33, Stewart D. Personick.
International Wire & Cable Symposium Proceedings, 1981, pp. 388-395, Morin
et al.
|
Primary Examiner: Berman; Susan W.
Attorney, Agent or Firm: Roylance, Abrams, Berdo & Goodman, L.L.P.
Parent Case Text
This application is a division of application Ser. No. 013,207, filed in
Feb. 1, 1993, now abandoned, which application was a continuation of Ser.
No. 915,742, filed Jul. 21, 1992, now abandoned, which was in turn a
continuation of Ser. No. 733,074, filed Jul. 18, 1991, now abandoned,
which was in turn a continuation of Ser. No. 371,833, filed Jun. 27, 1989,
now abandoned.
Claims
What is claimed is:
1. An optical fiber array comprising
(1) coated and inked optical fibers, and
(2) an ultraviolet radiation-cured matrix material for embedding and
securing therein a plurality of coated and inked optical fibers in a
desired configuration, said matrix material comprising the reaction
product of:
(a) from about 64 percent to about 80 percent by weight of a
silicone-modified wholly aliphatic polyether-based urethane acrylate;
(b) a sufficient amount of from about 15 percent to about 21 percent by
weight of a monomer having a plurality of acrylate or methacrylate
moieties per molecule to crosslink said matrix material when cured, to
impart solvent resistance thereto and to increase tensile modulus;
(c) a sufficient amount of from about 3 percent to about 8 percent by
weight of a monomer selected from the group consisting of stearyl
acrylate; stearyl methacrylate; isoctyl acrylate; isoctyl methacrylate;
lauryl acrylate; lauryl methacrylate; caprolactone acrylate; caprolactone
methacrylate; decyl acrylate; decyl methacrylate; isodecyl acrylate; and
mixtures thereof to permit the cured matrix material to remain adhered to
inked surfaces of said fibers under use conditions yet with sufficiently
low adhesive force to make said matrix material, when cured, easily
strippable, without causing substantial swelling of the matrix material;
(d) from about 2 percent to about 7 by weight of a photoinitiator; and
(e) optionally, from about 0.5 percent to about 1.5 percent by weight of a
stabilizer;
all of said percentages by weight being based on total weight of (a), (b),
(c), and (d),
wherein said cured matrix material is strippable from the coating on said
coated and inked fibers substantially without removing said coating from
said fibers,
and wherein said cured matrix material has a tensile modulus over about
1,000 psi at 23.degree..+-.0.5.degree. C.
2. An optical fiber array according to claim 1 wherein the coating on said
coated and inked fibers comprises a cured acrylate-containing or a cured
methacrylate-containing coating material.
3. An optical fiber array of claim 1 wherein said coated and inked fibers
are colored over their respective coatings by applied vinyl inks of
different colors, for individual fiber identification.
4. An optical fiber array according to claim 1 wherein said coated optical
fibers include ink coloration substantially upon their respective surfaces
and wherein said matrix composition, when cured, is strippable from said
ink coloration without removing it from said fibers.
5. An optical fiber array according to claim 1 wherein said (b) monomer
present in said matrix material (2) is selected from the group consisting
of trimethylolpropane triacrylate; trimethylolpropane trimethacrylate;
pentaerythritol triacrylate; pentaerythritol trimethacrylate;
pentaerythritol tetraacrylate; pentaerythritol tetramethacrylate;
trimethylolpropane propoxylate triacrylate; trimethylolpropane propoxylate
trimethacrylate; trimethylolpropane ethoxylate triacrylate;
trimethylolpropane ethoxylate trimethacrylate; glycerolpropoxytriacrylate;
glycerolpropoxytrimethacrylate; dipentaerythritol monohydroxy
pentaacrylate; dipentaerythritol monohydroxy pentamethacrylate; C.sub.6 to
C.sub.12 hydrocarbon diol diacrylates; C.sub.6 to C.sub.12 hydrocarbon
diol dimethacrylates, and mixtures thereof.
6. An optical fiber array according to claim 1 wherein said (b) monomer
present in said matrix material (2) comprises trimethylolpropane
triacrylate.
7. An optical fiber array according to claim 1 wherein the matrix material
(2) additionally comprises from about 1 to about 30 percent by weight of a
polyester based aliphatic urethane acrylate oligomer which is capable of
increasing adhesion of said matrix material to said coated and inked fiber
relative to the composition comprising only (a) through (e).
8. The optical fiber array of claim 1 wherein said monomer (c) in (2) is
stearyl acrylate.
9. An optical fiber ribbon assembly comprising:
a plurality of glass optical fibers disposed in a generally planar and
generally parallel arrangement,
said optical fibers being coated with a coating comprising a cured
acrylate-containing or a cured methacrylate-containing coating
composition,
said coated fibers being inked over their respective coatings with inks of
different respective colors, for individual fiber identification, and
an ultraviolet radiation-cured matrix disposed about said fibers and
bonding them in said arrangement;
said matrix comprising the reaction product of:
(a) from about 64 percent to about 80 percent by weight of a
silicone-modified aliphatic polyether-based urethane acrylate;
(b) from about 10 percent to about 25 percent by weight of
trimethylolpropane triacrylate;
(c) from about 3 percent to about 8 percent by weight of stearyl acrylate;
(d) from about 2 percent to about 7 percent by weight of a photoinitiator;
and
(e) optionally, from about 0.5 percent to about 1.5 percent by weight of a
stabilizer;
all of said percentages by weight being based on total weight of (a), (b),
(c) and (d).
10. An optical fiber ribbon assembly comprising
a plurality of glass optical fibers disposed in a generally parallel
arrangement and
an ultraviolet radiation-cured matrix bonding said fibers in said
arrangement, said matrix comprising the reaction product of:
(a) from about 64 percent to about 80 percent by weight of a
silicone-modified aliphatic polyether-based urethane acrylate;
(b) from about 15 percent to about 21 percent by weight of
trimethylolpropane triacrylate;
(c) from about 3 percent to about 8 percent by weight of stearyl acrylate;
(d) from about 2 percent to about 7 percent by weight of
hydroxycyclohexylphenyl ketone photoinitiator; and
(e) from about 0.5 percent to about 1.5 percent by weight of thiodiethylene
bis (3, 5-di-tert-butyl-4-hydroxy) hydrocinnamate;
all of said percentages by weight being based on total weight of (a), (b),
(c) and (d).
11. A process for preparing an optical fiber array comprising:
arranging optical fibers in a generally desired arrangement;
applying about said fibers the matrix composition of claim 1; and
curing said matrix composition by ultraviolet irradiation or via electron
beam, thereby securing said fibers in said arrangement.
12. A process for preparing an optical fiber array from a plurality of
coated and inked glass optical fibers, wherein said optical fibers are
covered with a coating comprising a cured acrylate-containing or a cured
methacrylate-containing coating composition, and wherein said coated
fibers are inked over their respective coatings with inks of different
respective colors, for individual fiber identification,
said process comprising:
aligning said plurality of coated, inked fibers in a generally planar,
generally parallel disposition;
disposing matrix composition comprising components (a)-(e) according to
claim 10 about said fibers; and
curing said matrix by ultraviolet irradiation or via electron beam to bond
said fibers in said disposition.
13. An optical fiber array comprising
(1) coated optical fibers, and
(2) a radiation-cured release matrix material for embedding and securing
therein a plurality of coated optical fibers in a desired configuration,
in which said coated optical fibers are disposed in a desired relationship
to each other, to form a unitary structure, said structure being produced
by arranging said coated optical fibers in said desired relationship, then
applying liquid matrix composition to said coated optical fibers to embed
them therein and then curing said liquid composition by exposure to curing
radiation, said matrix material comprising the cured reaction product of:
(a) from about 35 percent to about 98 percent by weight of a
silicone-modified wholly aliphatic polyether-based urethane acrylate;
(b) a sufficient amount of from about 0.5 percent to about 35 percent by
weight of a monomer having a plurality of acrylate or methacrylate
moieties per monomer molecule, to crosslink said matrix composition when
cured, to impart solvent resistance thereto and to increase tensile
modulus;
(c) a sufficient amount of from about 0.5 percent to about 20 percent by
weight of a monoacrylate or monomethacrylate monomer having an alkyl
moiety comprising from 7 to 18 carbon atoms to permit the cured matrix
composition to remain adhered to said inked surface under use conditions
yet with sufficiently low adhesive force to make said matrix composition
easily strippable, without causing substantial swelling of the matrix
composition; and
(d) from about 0 percent to about 10 percent by weight of a photoinitiator;
all of said percentages by weight being based on total weight of (a), (b),
(c) and (d),
wherein said matrix material is strippable from the coating on said coated
fibers substantially without removing said coating from said fibers and
wherein said matrix material has a tensile modulus over about 1,000 psi at
23.degree..+-.0.5.degree. C.
14. The optical fiber array of claim 13, wherein said composition, when
cured, has a tensile modulus over about 3,600 psi at
23.degree..+-.0.5.degree. C.
Description
BACKGROUND OF THE INVENTION
The present invention relates to radiation-curable compositions useful when
cured as matrix material for optical fiber ribbons; to optical fiber
ribbons containing such matrix material; and to processes for preparing
such matrix-containing ribbons.
Optical glass fibers have revolutionized the telecommunications industry.
The result has been a tremendous growth in demand for optical fibers which
are free of many of the inherent defects of glass fibers.
Immediately after drawing, glass fibers are exceptionally strong and have
very few intrinsic defects. However, such pristine fibers are very easily
flawed by exposure to environmental conditions including dust and
moisture. Therefore, there have been developed in the prior art numerous
coatings which are minimally capable of protecting the underlying glass
fiber from external harmful forces and which optimally possess properties
rendering them capable of obviating one or more of the various potential
problems which may deleteriously effect optical fiber performance. Such
properties include, inter alia, a glass transition temperature rendering
the fiber useful over a large potential temperature use range; a higher
refractive index than that of the fiber to refract any errant light
signals away from the fiber; rapid cure, e.g., under ultraviolet
irradiation; and high impermeability to moisture which may damage the
coating or the fiber itself and may cause delamination of the two.
Additionally, the adhesion level between the fiber and the coating must be
optimized so that the coating will remain adhered to the fiber during use
but be easily stripped therefrom, with minimal damage to the integrity of
the fiber and the coating, so that the fibers may be easily spliced in the
field. Above all, the fiber coatings should display good thermal,
oxidative and hydrolytic stability, to protect the underlying fiber over
the long term, i.e., over twenty-five years' time.
In certain applications, such as in short haul, fiber-to-the-home uses, a
single, coated optical fiber may adequately transmit a signal from one
point to the next. However, in most embodiments, a relatively large number
of fibers are necessary to transmit a large volume of signals. For
example, in the telecommunications industry, aggregates of fibers spanning
oceans or continents and containing dozens of individual fibers may be
required. Fibers are conveniently aggregated into cables, wherein large
numbers of coated optical fibers are laid in parallel and are protected by
a common sheathing material such as a layered arrangement which may
include fiberglass, steel tape and reinforced rubber cabling material.
When numerous individual coated optical fibers are aggregated into a cable,
it is necessary to be able to identify each of the individual fibers. For
example, when two cable segments are to be spliced together, it is
necessary to splice together ends of each like optical fiber in order for
a signal to convey properly. When only a few fibers are contained in a
cable, identification may be adequately made by having the coating of each
individual fiber be a characteristic color; thus, the splicer may simply
match up green fiber to green fiber, red to red, and so forth.
However, when the cable contains one hundred or more fibers, it may become
impracticable to use a sufficient number of distinctive inks as to color
each fiber distinguishably. Thus, a geometric means of distinguishing each
fiber is used. For example, arranging the fibers in a number of layers,
each layer containing perhaps twelve ink-coated fibers of different
respective colors, will greatly facilitate the task of matching up fibers
when splicing.
One practical way by which such spatial ordering of numerous fibers may be
accomplished is to create two-dimensional fiber arrays, wherein fibers are
situated in a generally planar arrangement, within a given array, with the
fibers in the array disposed in parallelism with each other. These arrays
are stacked one atop another in a three dimensional structure.
Such arrays are known in the art as ribbons. For example, it is known to
prepare a two-dimensional ribbon by forming a "sandwich" of parallel
coated optical fibers between two sheets of adhesive-coated Mylar tape,
thus affixing the fibers in that configuration. This "sandwich" provides
structural integrity and a tack free exterior surface.
However, this arrangement is less than optimal because the tape occupies a
substantial proportion of the total volume of the sandwich, so that when
several "sandwiches" are stacked to form a cable, an undesirably high
proportion of the total cable volume is taken up by tape (rather than by
optical fiber).
Thus it has been envisioned to prepare an optical fiber ribbon having a
matrix material in which the optical fibers are embedded in the desired
generally planar, parallel arrangement. This matrix material should, inter
alia, have suitable glass transition temperature; cure rapidly; be
non-yellowing; and have high thermal, oxidative and hydrolytic (moisture)
stability.
Additionally, the matrix material must be adherent enough to the coated,
colored optical fibers to prevent separation of the fibers during
processing into cables, but not so adherent as to remove the ink
coloration from the individual ink-colored fibers when the matrix material
is stripped from the fibers to permit splicing. Removal of the ink from a
coated, colored optical fiber is referred to in the industry as "breakout
failure"; it makes identification of the individual fibers impossible.
Furthermore, the matrix material must possess solvent resistance, inasmuch
as, in the field, splicers typically remove residual matrix and coating
material from stripped fibers using a solvent such as trichloroethane or
ethanol. Matrix material on an unstripped fiber should not absorb solvent
and swell and thus compromise the integrity of ribbon.
SUMMARY OF THE INVENTION
Accordingly, the invention provides, in one embodiment, a radiation-curable
matrix composition for affixing coated and ink-colored optical fibers in a
ribbon configuration. The matrix composition generally comprises:
(a) from about 35 percent to about 98 percent by weight of an aliphatic
polyether-based urethane acrylate;
(b) from about 0.5 percent to about 35 percent by weight of a monomer
having a plurality of acrylate or methacrylate moieties per monomer
molecule;
(c) from about 0.5 percent to about 20 percent by weight of an acrylate or
methacrylate monomer having an alkyl moiety comprising from 7 to 18 carbon
atoms; and
(d) from about 0 percent to about 10 percent by weight of a photoinitiator,
all of the percentages by weight being based on the total weight of (a),
(b), (c) and (d).
In preferred embodiments, the polyether-based urethane acrylate is silicone
modified; and the matrix material additionally comprises a stabilizer, is
ultraviolet curable and comprises at least about 1 percent by weight of
the photoinitiator.
In an alternate embodiment, the material includes from about 1 percent to
about 30 percent of an adhesion increasing compound such as a
polyester-based aliphatic urethane acrylate oligomer in addition to the
alkyl-containing acrylate-functional monomer (c).
In another embodiment, then, the invention is a process for adjusting the
adhesive bond of a cured matrix material to glass optical fibers which are
coated with a coating comprising a cured acrylate-or
methacrylate-containing coating composition and colored by the application
of inks of different respective colors for fiber identification, by
incorporating into an uncured matrix material as described above a
component that is capable of increasing the adhesive bond.
In another embodiment, the invention is an optical fiber ribbon assembly
comprising a plurality of coated, colored optical fibers in a fixed
relationship, e.g., a generally planar, generally parallel arrangement,
and a radiation-cured matrix material bonding said fibers in said position
within the matrix material. The matrix material has sufficient adhesion to
the fibers to remain adhered thereto during use but is easily strippable
therefrom. Specifically, the invention may be such an optical fiber ribbon
wherein the matrix material is as described above.
In yet another embodiment, the invention is a process for preparing an
optical fiber ribbon. The process comprises mechanically aligning the
optical fibers in the desired (e.g., generally parallel) arrangement;
applying about the fibers the matrix material described above; and curing
the matrix material to secure the fibers in the desired arrangement, e.g.,
preferably with ultraviolet light or an electron beam.
In a still further embodiment, the invention is a coating composition for
coating a substrate, the composition being as described above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Radiation Curable Matrix Composition
The invention relates in part to a radiation-curable matrix composition,
e.g., for affixing coated and inked optical fibers in a ribbon or other
desired configuration. The cured matrix material should have, inter alia,
the following properties: moisture resistance; solvent resistance; ease of
stripping; resistance to breakout failure; low volatiles content; fast
cure when irradiated; and long term thermal, oxidative and hydrolytic
stability. It should be non-yellowing. It should also be resistant to
failure during "cabling". Cabling is the term used to describe a process
of gathering a plurality of the ribbons together to form a cable.
The matrix composition contains at least three basic ingredients, and, if
envisioned for ultraviolet cure, at least four:
(a) a polyether-based urethane acrylate;
(b) a monomer having a plurality of acrylate or methacrylate groups;
(c) an alkyl acrylate or an alkyl methacrylate monomer; and
(d) optionally, for a U.V.-curable composition, a photoinitiator.
(A) The Polyether-Based Urethane Acrylate
The first ingredient is a specific urethane acrylate. Specifically, it is
based on an aliphatic polyether polyol, which is reacted with an aliphatic
polyisocyanate and acrylated.
In a preferred embodiment, this component is an oligomer which is
silicone-modified, e.g., it may have silicone coreacted into the polyether
portion of the backbone. The silicone-modified alternative may provide the
most desirable release characteristics vis-a-vis the ink (i.e., may
exhibit less adhesion than the non-silicone-containing urethane acrylate).
This component is chosen to possess good thermal and hydrolytic properties
and a low glass transition temperature, and to be somewhat non-yellowing.
The polyether-based urethane acrylate comprises from about 35 percent to
about 98 percent by weight of the matrix composition, based on the total
weight of the (a) through (d) ingredients. Preferably, the (a) component
comprises from about 53 percent to about 87.5 percent, and more preferably
about 64 percent to about 80 percent by weight of the composition, based
upon the total weight of the (a) through (d) ingredients. If less than
about 35 percent by weight of this component is used, the release
properties of the matrix may suffer. If more than about 98 percent by
weight is used, the viscosity of the composition may be undesirably high
and swelling may occur when the matrix is exposed to certain solvents
which may be used in the field and which may be absorbed by the matrix,
such as ethanol, trichloroethane or isopropyl alcohol.
Examples of suitable urethane acrylates (a) include but are not limited to
Ebecryl 4842 (equivalent to Chempol 19-4842), which is a silicone-modified
compound, and Ebecryl 19-6264, which is not silicone-modified, and which
contains about 15% by weight of 1,6-hexanediol diacrylate as a reactive
solvent, both from Radcure Specialties, Inc., Louisville, Ky.
(B) The Monomer Having A Plurality of Acrylate or Methacrylate Groups
The second component of the matrix composition is a monomer having a
plurality of acrylate or methacrylate moieties.
This component, which may be difunctional or higher but which is preferably
trifunctional, serves to increase the crosslink density of the cured
coating and therefore to improve solvent resistance (by preventing
absorption of solvent into the matrix) and to increase modulus. Examples
of suitable components (b) include but are not limited to
trimethylolpropane triacrylate; trimethylolpropane trimethacrylate;
pentaerythritol triacrylate; pentaerythritol trimethacrylate;
pentaerythritol tetraacrylate; pentaerythritol tetramethacrylate;
trimethylolpropane propoxylate triacrylate; trimethylolpropane propoxylate
trimethacrylate; trimethylolpropane ethoxylate triacrylate;
trimethylolpropane ethoxylate trimethacrylate; glycerol
propoxytriacrylate; glycerol propoxytrimethacrylate; dipentaerythritol
monohydroxy pentaacrylate; dipentaerythritol monohydroxy
pentamethacrylate; C.sub.6 -C.sub.12 hydrocarbon diol diacrylates; C.sub.6
-C.sub.12 hydrocarbon diol dimethacrylates; and mixtures thereof. A
preferred component (b) is trimethylolpropane triacrylate.
The monomer having a plurality of acrylate or methacrylate functionalities
comprises from about 0.5 percent to about 35 percent by weight of the
composition, based on the total weight of (a), (b), (c) and (d).
Preferably, it comprises from about 10 percent to about 25 percent, and
more preferably from about 15 percent to about 21 percent by weight of the
composition, again based on total weight of (a) through (d). If less than
about 0.5 percent by weight of component (b) is used, insufficient
crosslink density, low modulus and poor solvent resistance may result; if
more than about 35 percent is used, the cured composition may shrink to
such an extent that adhesion may suffer (i.e., the matrix material may
shrink away from the coated and inked optical fibers).
(C) The Alkyl Acrylate or Alkyl Methacrylate Monomer
The third component of the matrix composition is an acrylate or
methacrylate monomer having an alkyl moiety comprising from 7 to 18 carbon
atoms.
One of the key features of the present invention is its optimized adhesion
level, i.e., it has a high enough adhesion level to remain adhered under
virtually all use conditions yet low enough to render it easily strippable
for splicing. Further, the adhesion level of the matrix to the coated and
inked fibers is variable, as discussed in further detail hereinbelow, to
meet different use conditions.
This third component (c) is instrumental in conferring release properties
to the matrix material vis-a-vis the coated, inked optical fibers. As
discussed above, it is necessary that a field worker is able to peel away
the matrix material without removing the ink which identifies the
underlying coated optical fibers, in order to splice the fibers together
correctly. Furthermore, the inclusion of this third component increases
the hydrolytic stability of the matrix material relative to that of the
composition not including it. Thus, even in an embodiment, discussed
infra, wherein increased (rather than decreased) adhesion is required,
this adhesion decreasing component should be used in addition to a further
component that is capable of overriding this adhesion decreasing property,
the adhesion-increasing component replacing a portion of the polyether
urethane acrylate component (a).
In either embodiment, the adhesion level of matrix material to ink should
fall within the range of between about 0.02 pounds per linear inch
(lb./in.) and about 0.20 lb./in.; preferably between about 0.04 lb./in.
and about 0.15 lb./in.; and more preferably between about 0.06 lb./in. and
about 0.10 lb./in., as measured on a one-inch wide sample by a T-peel
test, using an Instron, model 1122, at 23.degree. C., with a 10 mm/min
crosshead speed.
Examples of such monomers include but are not limited to stearyl acrylate;
stearyl methacrylate; isooctyl acrylate; isooctyl methacrylate; lauryl
acrylate; lauryl methacrylate; C.sub.14 to C.sub.15 hydrocarbon diol
diacrylates; C.sub.14 to C.sub.15 hydrocarbon diol dimethacrylates;
caprolactone acrylate; caprolactone methacrylate; decyl acrylate; decyl
methacrylate; isodecyl acrylate; isodecyl methacrylate; isobornyl
acrylate; isobornyl methacrylate; and mixtures thereof. Of the above,
those having straight chain alkyl groups of from 12 to 18 carbon atoms are
preferred. Particularly preferred is stearyl acrylate, such as Sartomer
SR-257 stearyl acrylate from the Sartomer Company of West Chester, Pa.
The alkyl-functional acrylate or methacrylate monomer (c) comprises from
about 0.5 percent to about 20 percent by weight of the matrix composition,
based on the total of the weights of components (a) through (d).
Preferably, it comprises from about 1 to about 14 percent by weight and
more preferably about 3 to about 8 percent by weight of the composition,
based on the total weight at (a), (b), (c) and (d). As mentioned supra, if
less than about 0.5 percent by weight of this component is used,
hydrolytic stability may suffer. If more than 20 percent is used,
crosslink density may be undesirably low, causing swelling of the matrix
material due to solvent absorption when exposed to solvent in the field.
(D) The Photoinitiator
The fourth component of the matrix composition is a photoinitiator. The
necessity for this component depends on the envisioned mode of cure of the
matrix material: if it is to be ultraviolet cured, a photoinitiator is
needed; if it is to be cured by an electron beam, the composition may
comprise substantially no photoinitiator.
In the ultraviolet cure embodiment, the photoinitiator, when used in a
small but effective amount to promote radiation cure, must provide
reasonable cure speed without causing premature gelation of the matrix
composition. Further, it must not interfere with the optical clarity of
the cured matrix material. Still further, the photoinitiator must itself
be thermally stable, non-yellowing, and efficient.
Suitable photoinitiators include, but are not limited to, the following:
hydroxycylohexylphenyl ketone; hydroxymethylphenylpropanone;
dimethoxyphenylacetophenone; 2-methyl-1-›4-(methylthio)
phenyl!-2-morpholinopropanone-1;
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one;
1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one;
4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone;
diethoxyacetophenone; 2,2-di-sec-butoxyacetophenone; diethoxy-phenyl
acetophenone; and mixtures of these.
The photoinitiator comprises from about 0 percent to about 10 percent by
weight of the composition, based upon the weight of composition of the (a)
through (d) ingredients (0 percent representing the electron beam-curable
embodiment). In the ultraviolet curable embodiment, the photoinitiator
comprises from about 1 percent to about 10 percent by weight of the
composition, based on (a) through (d). Preferably, the amount of
photoinitiator, when used, is from about 1.5 percent to about 8.0 percent,
and more preferably from about 2.0 percent to about 7.0 percent by weight,
based upon the total weight of the (a) through (d) ingredients. A
particularly preferred photoinitiator is hydroxycylcohexylphenyl ketone,
such as is supplied by Ciba-Geigy Corp., Ardsley, N.Y., as Irgacure 184.
The photoinitiator should be chosen such that cure speed, as measured in a
dose versus modulus curve, of less than 1.0 J/cm.sup.2, and preferably
less than 0.5 J/cm.sup.2, is required, when the photoinitiator is used in
the designated amount.
Optional Ingredients
The matrix composition may also comprise one or more optional ingredients,
discussed infra.
(E) Component Capable of Increasing Adhesion
As discussed above, a controlled adhesion level is an important parameter
of the present invention. The adhesion level should again lie within the
range of between about 0.02 lb./in. and about 0.20 lb./in., preferably
between about 0.04 lb./in. and about 0.15 lb./in., and more preferably
between about 0.06 lb./in. and about 0.10 lb./in. as measured by T-peel
test, as described, supra. Functionally, this means that the matrix
material is adherent enough to the coated and inked optical fibers so as
not to separate therefrom under normal use conditions, yet releasable
enough to separate easily from the coated, inked fibers clearly and
without removing a substantial amount of ink therefrom during, for
example, splicing operations.
In order to attain this desired amount of adhesion, it may be necessary to
incorporate an agent capable of increasing the adhesion level of the
matrix material to a coated and inked optical fiber relative to the
composition not incorporating it. This higher adhesion level might be
necessary, for example, when an ink having relatively poor adhesion to the
matrix material is used. This adhesion-increasing additive may be used in
addition to or in lieu of a portion of the polyether-based urethane
acrylate component (a).
The invention thus further comprises a process for adjusting the adhesive
bond of a cured matrix material to coated and inked glass optical fibers
by incorporating such adhesion-increasing component into the uncured
matrix material.
When used, the adhesion-increasing component preferably comprises from
about 1 to about 30 percent by weight, based on the total weight of
components (a), (b), (c) and (d) only.
Suitable adhesion-increasing components include, but are not limited to,
polyester-based aliphatic urethane acrylate oligomers, commercially
available examples of which include cargill 1512 oligomer, from Cargill,
Inc., Minneapolis, Minn., and Ebecryl 284, from Radcure Specialties, Inc.,
Louisville, Ky.
(F) Stabilizers
Another optional class of components includes various stabilizers. To
improve shelf life (storage stability) of the uncured coating, as well as
to increase thermal and oxidative stability of the cured coating, one or
more stabilizers may be included in the composition. Examples of suitable
stabilizers include tertiary amines such as diethylethanolamine and
trihexylamine; hindered amines; organic phosphites; hindered phenols;
antioxidants; mixtures thereof; and the like. Some particular examples of
antioxidants which can be used include
octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate;
thiodiethylene bis (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate; and
tetrakis ›methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)! methane.
When a stabilizer is used, it may be incorporated in an amount from about
0.1 percent to about 3.0 percent, based on the weight of the (a) through
(d) ingredients. Preferably, it is included in the range from about 0.25
percent to about 2.0 percent by weight, and more preferably in the range
from about 0.5 percent to about 1.5 percent by weight, based on the total
weight of the (a) through (d) ingredients. Desirable properties of a
stabilizer include non-migration (probably enhanced by low polarity). A
preferred stabilizer is thiodiethylene bis (3,5-di-tert-butyl-4'-hydroxy)
hydrocinnamate, such as Irganox 1035, from Ciba-Geigy Corporation,
Ardsley, N.Y.
The matrix composition should have a viscosity of about 5,000 cps to 9,000
cps at 23.degree. C., and a fast cure. The cured matrix material should
have a modulus of over about 1,000 psi, a glass transition temperature of
less than about -40.degree. C. (onset), low surface tack, and high thermal
and hydrolytic stability.
The Optical Fiber Ribbon Assembly
The invention further relates to an optical fiber ribbon assembly. The
ribbon assembly generally comprises a plurality of coated, inked optical
fibers held in a fixed relationship, e.g., in a parallel and planar or
other prescribed arrangement, and a radiation curable matrix composition,
in which the fibers are embedded, the matrix bonding the fibers in the
desired arrangement. The matrix material has sufficient adhesion to the
fibers to remain adhered thereto during use but is easily strippable
therefrom without substantially damaging the integrity of an ink layer on
the coated optical fibers.
The optical fibers which are part of the ribbon are those known in the art
which are singly or dually coated before being bonded in the matrix
material and which contain an ink layer on their surface, rendering each
distinguishable from other fibers in the ribbon.
The optical fibers which are coated may comprise for example, a glass core
and a glass cladding layer. The core, for example, may comprise silica
doped with oxides of germanium or phosphorus and the cladding, a pure or
doped silicate such as a fluorosilicate. Alternately, the fibers may
comprise a polymer clad silica glass core. Examples of such polymer
claddings include organosiloxanes such as polydimethylsiloxane or a
fluorinated acrylic polymer.
The fiber coatings are of the type known in the art and preferably are
radiation, e.g., ultraviolet light, cured. The coating compositions may
comprise a single or a dual layer and often contain cured acrylate or
methacrylate components such as urethane diacrylates. A suitable secondary
coating, for example, may comprise an aromatic polyester urethane
acrylate; vinyl pyrrolidone; ethoxyethoxyethylacrylate; a photoinitiator;
and stabilizer.
As discussed hereinabove, in order for the optical fiber ribbons to be
spliced in a reasonably easy manner, it is desirable to identify the
individual fibers by color coding them. It is possible to add a coloring
agent to the outermost fiber coating layer; however, this is impractical
because the coating will impart its color to the apparatus used to apply
it, requiring numerous sets of drawing and coating apparatuses to
accommodate each color of ink used.
Thus, it is more efficacious to ink over the optical fiber coating or
coatings ink-containing layers of different colors, for individual fiber
identification, by any means known in the art. The applied ink composition
may be variable in nature but generally is vinylic and may comprise, for
example, one or more organic or inorganic pigments; a vinyl copolymer;
synthetic silica; and an organic solvent. As implied, supra, the precise
nature of the ink composition will dictate the amounts and nature of the
adhesion-affecting components in the matrix.
The matrix composition which bonds the fibers is of the type which
constitutes the present invention, i.e., one which comprises:
(a) from about 35 percent to about 98 percent by weight of an aliphatic
polyether-based urethane acrylate;
(b) from about 0.5 percent to about 35 percent by weight of a monomer
having a plurality of acrylate or methacrylate moieties;
(c) from about 0.5 percent to about 20 percent by weight of an acrylate or
methacrylate monomer having an alkyl moiety comprising from 7 to 18 carbon
atoms; and
(d) from about 0 percent to about 10 percent by weight of a photoinitiator,
all of said percentages by weight being based on total weight of (a), (b),
(c) and (d).
One kind of ribbon structure, and a cable made from such ribbon, is
described in U.S. Pat. No. 3,411,010 to Genahr et al., which is
incorporated herein by reference.
Process For Preparing an Optical Fiber Ribbon
The invention comprises, in a further aspect, a process for preparing an
optical fiber ribbon. Broadly, the process comprises mechanically
arranging coated and inked fibers in a desired (i.e., generally planar and
generally parallel) configuration; applying a matrix composition about the
fibers; and curing.
A suitable but non-limitative means for applying the matrix composition to
the fibers is as follows. Optical fibers which have been coated and inked
over in the manner described hereinabove or in any manner known in the art
may be used. The optical fibers may be mechanically arranged in the
desired configuration (e.g., in a generally parallel, generally planar
disposition relative to each other). The fibers may be held in the desired
configuration, for example, by taping or otherwise holding the ends
together. The matrix composition may be applied about the fibers by any
conventional means, i.e., by dipping the fibers into a vat of the
composition or pouring the material thereupon. Once the matrix composition
has been applied substantially uniformly about the fibers, it may be
radiation cured, preferably either by ultraviolet light irradiation or via
electron beam. Optionally, the composite may be flipped over, more matrix
composition applied thereto, and the matrix again cured as above. The
resulting ribbon contains the fibers bonded and secured in the desired
disposition (i.e., generally parallel and generally planar). The adhesive
bond of the cured matrix material to the coated and inked fibers may be
adjusted by incorporation into the uncured compositions of a component
capable of increasing the adhesive bond of the type discussed, supra,
e.g., a polyester-based aliphatic urethane acrylate oligomer.
Coatings For Substrates
Although the matrix composition has been exemplified hereinabove for use as
a matrix material for coated and inked optical fibers, it should be
understood to be useful in any embodiment where it is desired to coat or
bind a substrate (e.g., a flexible substrate) wherein the coating has an
optimized adhesion level to the substrate and particularly an ink-covered
substrate. Examples of such substrates include, but are not limited to,
glass, metal or plastic. For example, composition may be used as a release
coating for a glass or plastic substrate having a logo printed thereon, as
may be used in electronics or other industries, to identify a supplier, or
in any embodiment where it is desired to temporarily protect a printed
surface. For example, a logo may be protected during shipping with such a
release coating, which coating may be removed by the customer. Thus, the
invention, stated more broadly, is a radiation curable coating composition
for coating a substrate, the coating composition comprising:
(a) from about 35 percent to about 98 percent by weight of an aliphatic
polyether-based urethane acrylate;
(b) from about 0.5 percent to about 35 percent by weight of a monomer
having a plurality of acrylate or methacrylate moieties;
(c) from about 0.5 percent to about 20 percent by weight of an acrylate or
methacrylate monomer having an alkyl moiety comprising from 7 to 18 carbon
atoms; and
(d) from about 0 percent to about 10 percent by weight of a photoinitiator,
all of the percentages by weight being based on total weight of (a), (b),
(c) and (d).
EXAMPLES
The following Examples serve to further illustrate the invention. In these
Examples and elsewhere throughout this application, all parts and
percentages are by weight, on a dry solids basis, and all temperatures are
in degrees centigrade (.degree.C.) unless expressly stated to be
otherwise. In all of the Examples, cure speeds were measured with an
International Light IL 745-A radiometer with model A309 light bug. In the
Examples and elsewhere in this application, the terms "modulus" and
"Instron modulus" refer to tensile modulus.
Unlike the remainder of the application, where percentages by weight refer
to the total weight of the (a) through (d) components, parts by weight in
the Examples refer to the total composition described in that Example,
including all components. The optional ingredients are identified by an
asterisk (*) in the Examples. The optional components may be necessary for
use, if the exemplified coating is to meet the rigorous requirements for a
commercially acceptable matrix for optical glass fiber ribbons.
Example 1
A Coating Composition For A Flexible Substrate
A radiation-curable composition was formulated as follows:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
72.28
aliphatic ether urethane acrylate,
from Radcure Specialties, Inc.
Louisville, Kentucky (a)
Trimethylolpropane triacrylate (b)
17.82
SR-257 stearyl acrylate, from
4.95
Sartomer Company, West Chester, PA (c)
Irgacure-184 hydroxycyclohexylphenyl
3.96
ketone photoinitiator, from Ciba-Geigy,
Ardsley, NY (d)
Irganox-1035 thiodiethylene bis (3,5-
0.99
di-tert-butyl-4-hydroxy) hydrocinnamate
stabilizer, from Ciba-Geigy *
______________________________________
The viscosity of the resulting (uncured) formulation was 6520 cps (at
25.degree. C. using a Brookfield viscometer, model LVT, at 6 rpm, # 34
spindle).
Shelf life as a function of change in viscosity over time of the uncured
formulation was determined by weighing a 50 gram sample of the liquid into
a 4-ounce glass jar with a lid and heating in a 200.degree. F.
(93.3.degree. C.) oven for 16 hours. The change in viscosity was
determined to be +8.3%.
The uncured material was applied to a substrate. The substrate comprised a
flat glass sheet having taped on its surface an approximately seven-to
nine-mil thick radiation-cured coating overprinted with an ink layer. The
radiation-cured coating comprised the following:
______________________________________
Ingredient Parts by Weight
______________________________________
vinyl pyrrolidone 11.5
ethoxyethoxyethylacrylate
11.5
Retarder/Stabilizer package
0.99
aromatic polyester urethane acrylate
74.01
2,2-dimethoxy-2-phenyl-acetophenone
2.0
photoinitiator
______________________________________
The ink, which was orange in color, comprised pigment; a vinyl copolymer;
synthetic silica and an organic solvent. It conferred an orange color to
the coated, inked substrate.
The above composition was applied to the aforedescribed coated and inked
substrate as an about six-mil coating using a Bird applicator. It was
ultraviolet cured in air at 0.7 J/cm.sup.2 using a 200 watts per inch
medium pressure mercury vapor lamp.
Adhesion of the cured matrix material was determined as follows. The coated
substrate was cut into a 31/2.times.1 inch strip. A T-peel test was done
using an Instron model 1122 with a crosshead speed of 10 mm/min at
23.degree. C., range setting 100 g. An adhesion value of 0.075 (.+-.0.011)
lb./in. was measured.
The cured matrix had tensile modulus, at 23.degree. C., of 10,930 psi glass
transition temperature, as determined according to ASTM D-3418, of less
than about -40.degree. C. (onset) and good surface tack.
Water absorption of the sample was measured as follows. The cured matrix
material was equilibrated at 50% (.+-.5%) relative humidity at 23.degree.
C. (.+-.2.degree. C.) for 48 hours. The sample was weighed and a weight
"A" recorded. The sample was then soaked for 24 hours at 25.degree. C. in
distilled water, then patted dry and weighed. This weight was recorded as
"B". The sample was next placed in a vacuum oven under 10 mm Hg pressure
at 25.degree. C. for 24 hours, removed, and again equilibrated at 50%
(.+-.5%) relative humidity at 23.degree. C. (.+-.2.degree. C.) for 48
hours and weighed. This third weight was recorded as "C". Percent water
absorption measured as
##EQU1##
was about 2.6%.
Solvent absorption of the sample was measured as follows. The cured matrix
material (6-mil thickness) was cut in an approximately 2.times.2 inch
section and weighed in a tared container. The film was immersed in ethanol
for 5 minutes and then patted dry. It was returned to the tared container
and reweighed after 5 minutes. The % solvent absorption was taken as the
increase in weight divided by the initial weight.times.100. The value was
14.2%.
Percent volatiles in the cured coating was determined by subjecting a
sample cured and equilibrated as above to thermal gravimetric analysis
(TGA) at 200.degree. C. for 40 minutes in nitrogen atmosphere. A 5.12%
volatiles weight loss was measured.
Oxidative induction temperature was measured by subjecting a 10 mg sample
of the coating cured as above to differential scanning calorimetry in a
pure oxygen atmosphere. The test was commenced at 100.degree. C. and
increased by 10.degree. C. per minute until oxidation began, as evidenced
by the beginning of a temperature exotherm. This point, the oxidative
induction temperature, was measured at between about 190.degree. C. and
about 210.degree. C.
Example 2
A Composition Having Good Adhesion and Viscosity but Slight Swelling
A formulation was made having the following components:
______________________________________
Ingredients Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
1,6-hexanediol diacrylate (b)
9.0
SR-257 Stearyl acrylate (c)
5.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The uncured formulation had a viscosity of 5750 cps at 25.degree. C. using
a Brookfield viscometer, model LVT, #34 spindle at 6 rpm and a Brookfield
74R temperature controller with a Thermosel.
The formulation was coated and cured in the manner of the previous Example.
Modulus of the cured coating was determined to be 1,770 psi at
23.degree..+-.0.5.degree. C., using an Instron Model 1122 fitted with a 50
kg load cell using a cross head speed of 5 mm/min and a chart speed of 200
mm/min.
Adhesion was determined in the following manner. A composition-coated and
cured sheet substrate was cut into 0.8 inch-by-3 inch strips. Adhesion of
the coating to the substrate was measured as in Example 1, and a value of
0.079 lb./in. was determined. Solvent absorption (ethanol) was determined,
in the manner of Example 1, to be 28.8%.
Example 3
A Formulation Having Lower Adhesion Properties
The following formulation was made up:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
Chemlink 2000, mixture of C.sub.14 and
9.0
C.sub.15 hydrocarbon diol diacrylates from
Sartomer Company (b)
SR-257 Stearyl acrylate (c)
5.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
When coated onto a substrate, cured, and subjected to the modulus and
adhesion tests of the previous Examples, a modulus of 1,320 psi and
adhesion level of 0.032 lb./in. were recorded.
Example 4
A Formulation Having Somewhat High Adhesion
The following composition was formulated:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 264 aliphatic ether urethane
80.6
acrylate, from Radcure Specialties,
Inc. (a)
Radcure isobornyl acrylate (c)
15.3
Irgacure-184 photoinitiator (d)
4.1
______________________________________
The uncured composition had a viscosity at 25.degree. C. of 8,550 cps, and
the cured composition has a modulus of 50,800 psi, these properties
measured as in the previous Examples.
Breakout was determined visually by observing the amount of ink removed
from the substrate onto the cured matrix, and a value of about 1 was
assigned, on a scale of 0 to 5, with 0 signifying that no ink was removed
and 5 signifying that all the ink was removed from the substrate.
Exxample 5
A Formulation Having Somewhat High Adhesion and Higher Viscosity
The following composition was prepared:
______________________________________
Ingredients Parts by Weight
______________________________________
Ebecryl 264 aliphatic ether
78.0
urethane acrylate (a)
Photomer 4072, trimethylolpropane
18.0
propoxylate triacrylate, from
Henkel Corp., Ambler, PA (b)
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The uncured composition had a viscosity of 11,920 cps, measured as in
Example 1, and, when cured in the manner of previous Examples, the cured
composition had a modulus of 55,600 psi and a breakout value of 1, all as
measured as in the previous Examples.
Example 6
A Formulation Having Increased Adhesion
The following formulation was made:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
55.0
aliphatic ether urethane acrylate (a)
Cargill 1512, aliphatic polyester
30.0
urethane acrylate in 25% hexanediol
diacrylate solvent from Cargill, Inc.,
Minneapolis, MN*
1,6-hexanediol diacrylate (b)
11.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The formulation which resulted was coated onto an inked (orange) substrate
and cured in the manner described in earlier Examples. The adhesion level
of the formulation was shown by a spot adhesion test (performed by curing
a thin coat of the material on the inked substrate and peeling the cured
material off by hand) to be high enough to pull most of the ink off of the
substrate.
Example 7
Another Formulation Having Increased Adhesion
The following formulation was devised:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
55.0
aliphatic ether urethane acrylate (a)
Ebecryl 284 aliphatic polyester
28.0
urethane diacrylate in 1,6-hexanediol
diacrylate (88% oligomer solids), from
Radcure Specialties, Inc.* (parts by
weight based on solids plus solvent)
1,6-hexanediol diacrylate (b)
13.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The formulation was coated onto a substrate and cured and the adhesion
level tested as in the previous Example. Again, the coating proved to have
high enough adhesion to pull most of the ink off of the substrate.
Example 8
A Composition Having Low Adhesion
The following formulation was made:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
Tone M-100 caprolactone acrylate
14.0
monomer, molecular weight 344, from
Union Carbide Corporation, Danbury,
CT (c)
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The formulation was coated onto a white-inked substrate as above; adhesion
was measured, in the manner of Example 1, to be 0.023 lb./in.
Example 9
Another Composition Having Low Adhesion and Low Modulus
The following formulation was made:
______________________________________
Ingredients Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
Stearyl acrylate (c)
14.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
When cured in the manner of previous Examples, the cured compositon had a
modulus of 880 psi and an adhesion value of 0.023 lb./in., as measured in
previous Examples.
Examples 10
Another Composition Having Low Adhesion
A formulation was made from the following:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
Ageflex FA-12 lauryl acrylate,
14.0
from CPS Chemical Company, Inc.,
Old Bridge, NJ (c)
Irgacure-184 photoinitiator (d)
4.0
______________________________________
When cured and subjected to the modulus and adhesion tests of the previous
Examples, a modulus of 738 psi and adhesion level of 0.031 lb./in. were
noted.
Example 11
A Composition Having Acceptable Adhesion But Low Modulus
The following composition was prepared:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
81.0
aliphatic ether urethane acrylate (a)
Isobornyl acrylate (c)
15.0
Irgacure-184 photoinitiator (d)
4.0
______________________________________
The resulting uncured composition had a viscosity of 8,260 cps, measured as
in Example 1. When cured as above, the material had a modulus of 900 psi
and a breakout value, as described in Example 4, of 0.
Example 12
Another Composition Having Acceptable Adhesion and Good Modulus
The following composition was formulated:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
75.0
aliphatic ether urethane acrylate (a)
Photomer 4072 trimethylolpropane
21.0
propoxylate triacrylate (b)
Irgacure-184 (d) 4.0
______________________________________
The resulting uncured composition had a viscosity of 9,670 cps, measured as
in Example 1. When cured as in previous Examples, a modulus of 5,200 psi
and breakout value of 0 were recorded.
Example 13
A Formulation Having Moderately High Adhesion
The following composition was made:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl 4842 silicone modified
82.0
aliphatic ether urethane acrylate (a)
1,6-hexanediol diacrylate (b)
14.0
Irgacure-184 (d) 4.0
______________________________________
The uncured composition had a viscosity of 5,180 cps, measured as in
Example 1. When cured, a modulus of 3,672 psi was measured. After coating
onto a white-inked substrate and curing the formulation in accordance with
previous Examples, adhesion was determined to be 0.153 lb./in. according
to the procedure described in Example 1.
Comparative Example 1
A Composition Having Poor Breakout Properties
The following formulation was devised:
______________________________________
Ingredient Parts by Weight
______________________________________
Ebecryl-284 aliphatic polyester
66.0
urethane acrylate, from Radcure
Chemlink 2000 mixture of C.sub.14 -C.sub.15
15.0
hydrocarbon diol diacrylates, from
Sartomer Company
Isobornyl acrylate, from Radcure
15.0
Irgacure-184 hydroxycyclophenyl ketone
4.0
from Ciba Geigy
______________________________________
The above composition had an uncured viscosity of 2,600 cps, as measured
using a Brookfield Viscometer, model LVT, at 25.degree. C., #34 spindle,
at 12 rpm, and a Brookfield 74R temperature controller with a Thermosel.
Uncured, the composition had a slightly yellow color.
The matrix was applied to an orange substrate of the type in Example 1 and
ultraviolet cured in air at 0.7J/cm.sup.2 using a 200 watts per inch
medium pressure mercury vapor lamp. Modulus of the cured coating was
determined to be 42,400 psi, and a breakout value of 4 was assigned, in
accordance with the method of Example 4.
Comparative Example 2
A Composition Having Too High A Level of Adhesion
The following composition was formulated:
______________________________________
Ingredient Parts by Weight
______________________________________
Cargill 1512 aliphatic ester
75.76
urethane acrylate, in hexanediol
diacrylate
Chemlink 2000 mixture of C.sub.14 and
20.2
C.sub.15 diol diacrylates (b)
Irgacure-184 (d) 4.04
______________________________________
The uncured coating had a viscosity at 25.degree. C. of 2,010 cps, measured
as in Example 1.
The modulus at 23.degree. C. was determined to be 80,000 psi. When applied
to an orange substrate and cured as in previous Examples, the material was
assigned a breakout value of 4.5.
Comparative Example 3
A Coating Having Poor Breakout
A mixture of equal parts by weight of the formulations of Example 4 and
Comparative Example 2 was cured as above. A breakout value of 2 was
assigned to the coating.
Examples 14-19
Solvent Resistance of Bonded Ribbons
Formulations having Good Breakout and Marginal Solvent Resistance
Optical fiber ribbons were made from each of the formulations of Examples 2
and 13.
One-and-one-half inch strips of both kinds of ribbons were cut and placed
in small vials to which were added, for each of the two types of
matrix-containing ribbons, one of three solvents, respectively: isopropyl
alcohol, ethyl alcohol and water. The so-treated samples were examined for
appearance changes and breakout. The effects of the solvents on appearance
and breakout are summarized in the following table:
______________________________________
Ease of
Change
breakout
Example Example in relative to
Example
2 13 Solvent
Appear-
non-solvent
No. Matrix Matrix tested ance treated ribbon
______________________________________
14 X Isopropyl
NO Same
alcohol
15 X Isopropyl
NO Easier
alcohol
16 X Ethanol
NO Somewhat
easier
17 X Ethanol
NO Easier
18 X Water NO Not
significantly
easier
19 X Water NO Not
significantly
easier
______________________________________
These results show solvent-sensitivity of the tested samples. This is
believed to be related to poor crosslink density.
Examples 20-24
Solvent Sensitivity to Trichloroethane
Coated orange substrates were prepared using the coatings identified in the
following Examples. Coating and curing was performed as described in
preceding Examples:
Example 14 (for Example 20);
Example 2 (for Example 21);
Example 9 (for Example 22);
Example 3 (for Example 23); and
Example 10 (for Example 24).
One-inch wide strips of each coated substrate were soaked in
trichloroethane for five minutes. With the exception of Example 20, each
coated substrate delaminated at least partially as a result of the solvent
exposure.
Example 25
Preparation of a Coated and Inked Substrate
A flat glass sheet was coated using a Bird applicator with a 6 mil coating
of a commercially available, stabilized, UV-curable urethane acrylate
oligomer-based composition.
The coating was UV-cured in air at 0.7J/cm.sup.2 using a medium pressure
200 watts per inch mercury vapor lamp. This was in turn printed with a
proprietary blue ink from Borden Packaging and Industrial Products,
Cincinnati, Ohio, using a Meyer rod. The material of Example 1 was coated
atop the inked substrate in the manner described in Example 1. Adhesion
was measured to be 0.15 lbs/in. at 23.degree. C. in accordance with the
methods of Example 1. It was observed that some of the ink was lifted from
the substrate when the matrix material was removed therefrom.
Conclusion
A radiation-curable matrix composition has been devised to possess a number
of important qualities rendering it useful for various applications, e.g.,
for affixing coated and inked optical fibers in a ribbon configuration.
The cured matrix material has a number of properties making it
particularly suitable for such end uses, these properties including
moisture resistance; solvent resistance; thermal, oxidative and hydrolytic
stability, and so forth.
However, one property of the cured matrix material of the present
invention, which is a valuable property, is its controlled and optimized
adhesion level, which allows it to remain adhered to the (fiber) substrate
during use, yet be strippable without substantial damage to the substrate,
when required. This property is regulated by adjusting or controlling the
use of either of the adhesion-decreasing component (i.e., the alkyl
acrylate or methacrylate), or of the adhesion-increasing component (i.e.,
the polyester-based aliphatic urethane acrylate oligomer), or by a
combination of the two, at appropriate levels to achieve the desired
adhesion levels, in the range of 0.02 lb./in. to 0.20 lb./in.
While the invention has been disclosed in this patent application by
reference to the details of preferred embodiments of the invention, it is
to be understood that this disclosure is intended in an illustrative
rather than in a limiting sense, as it is contemplated that modifications
will readily occur to those skilled in the art, within the spirit of the
invention and the scope of the appended claims.
* * * * *
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