JPH0421546A - Ultraviolet hardenable coating for optical fiber and optical fiber coated by its coating method - Google Patents

Abstract

PURPOSE: To improve the stability to temp., oxidation and hydrolysis by coating an optical fiber with a specific radiation curable primary coating.

CONSTITUTION: A radiation curable compsn. is obtd. by compounding (A) 20 to 80 wt.% (hereafter %) acrylated urethane oligomer obtd. by reaction of a hydrocarbon polyol with an aliphat. isocyanate and a terminal capping monomer consisting of a hydroxylalkyl (meth)acrylate, (B), 5 to 50% 6-18C alkyl (meth)acrylate, (C) 5 to 60% monomer or oligomer having an arom. part, a contg. (meth)acrylic unsaturation and a hydrocarbon part and capable of making the refractive index of the compsn. larger than the refractive index of the compsn. contg. A, B, D, E, (D) 0.1 to 30% org. functional silane fixer and (E) 1.0 to 10% photoreaction initiator. Next, the optical fiber is coated with this compsn. and the coating is cured by irradiation with UV rays by which the primary coating is formed.

COPYRIGHT: (C)1992,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to radiation curable primary and secondary coatings for optical fibers and optical fibers containing such coatings.

Until recently, the fiber optic industry concentrated on so-called "long haul" applications. In such applications, optical fibers are used to traverse and connect long distances, such as transoceanic or transcontinental cables. In that case, the optical fiber had to be sealed with bulky protective cable material in a protected underground or undersea environment.Therefore, the optical fiber was not directly exposed to environmental hazards. Ta.

A recent trend in the fiber optic market is very localized networks used to connect homes. The fibers in such applications are directly exposed to much harsher conditions (including severe extremes and extreme temperatures) than in traditional applications of glass fibers. As a result, previously used coatings do not perform well under such adverse conditions; there was therefore a need (IIeed) to develop coatings with higher functionality.

Such a coating meets the above conditions, i.e.
There was a need to have temperature, oxidative, and hydrolytic stability and be able to protect the fiber over long periods of time, ie, over 25 years.

Immediately after compression, it is possible to prepare optical fibers for light transmission that are exceptionally strong and exhibit few inherent drawbacks. However, this sturdy prototype fiber easily cracks when exposed to environmental conditions that include dust and moisture. When small cracks occur, depending on their size, the strength of the fiber decreases, making it brittle and easily broken by external forces. Therefore, optical gas fibers in the prior art were coated with at least one resin immediately after preparation. The minimum requirement of the coating is to protect the underlying master fiber from external forces.

Generally, at least two coatings are used: a primary or buffer coating and a secondary coating. The internal or primary coating is applied directly to the glass fiber. When cured, it forms a soft, rubbery, resilient material that serves as a buffer to protect the fibers by relieving the stresses that occur when the fibers are bent, cabled, or coiled. Otherwise, such stress would induce micro-bending in the fiber, attenuating the light passing through the fiber and reducing the efficiency of signal transmission. A secondary coating is applied over the primary coating. And the secondary coating is applied during processing and actual use.
It must act as a hard, durable protective outer layer that prevents damage to the glass fibers.

Certain properties are desirable for the primary coating and other properties for the secondary coating. For example, the primary coating must maintain sufficient adhesion to the glass fibers during thermal and hydrolytic aging, but must not be able to be stripped away from the glass fibers when splicing. It won't happen.

The modulus of the primary coating should be a small value, because it can easily absorb stress and reduce the stress on the fiber, which induces micro-bending and consequent poor efficiency of signal transmission. This is because it must be protected.

This absorption effect must be maintained over the temperature range to which it may be exposed throughout the lifetime of the fiber.

Therefore, the primary coating has a low glass transition temperature (I
g). This low glass transition temperature is
This will ensure that the coating remains rubber-like over the temperature range in which it may be used.

However, simply having a low Tg does not guarantee good optical loss characteristics at low temperatures. Because the coefficients of thermal expansion of the secondary coating and the glass are significantly different, the secondary coating will shrink more severely than the glass when exposed to lower temperatures. Therefore, the primary coating should be chosen to alleviate this stress. Therefore, it is desirable that the Tg of the primary coating is still lower than the minimum temperature of use, but that the Tg is high enough such that the modulus increases with decreasing temperature. This property compensates for the difference in coefficient of thermal expansion between the secondary coating and the glass, thereby minimizing microscopic flaws and resulting signal attenuation. To obtain this property, the shape of the modulus versus temperature curve (ie, the modulus of the primary coating at low temperatures) is critical.

The primary coating should also have a relatively high refractive index, ie, greater than that of the cladding material of the coated fiber. This high refractive index allows the refractive index of the glass cladding and the primary coating to be different.

This difference in refractive index allows undirected optical signals to be refracted away from the glass core.

Another essential property of the primary (buffer) coating is moisture resistance. Moisture quickly degrades the strength of the coating itself, as well as the underlying glass fibers under stress. The reaction is one of hydrolysis and stress corrosion. Moisture also adversely affects the adhesion of the primary (II) coating to the glass, causing delamination. Therefore, it is desirable that the coating be as hydrophobic as possible. Preferably the primary coating is 5
It should have a water absorption value of less than 2.5% by weight, more preferably less than 2.5% by weight.

Similarly, the secondary coating must have a number of essential and optimal properties. The secondary coating is
This secondary coating must act as a hard protective layer to prevent damage to the fiber during processing and utilization; therefore, this secondary coating has a relatively high glass transition temperature (Ig
), i.e. tg of about 50°C, and a high modulus, i.e. about 1
It should have a modulus of 00,000 psi.

The secondary coating has a Tg higher than the maximum temperature of use.
It is desirable to have This is because at or near the Tg of a polymer, many physical properties such as modulus, tensile strength, coefficient of thermal expansion, hygroscopicity, etc. change dramatically with small temperature changes. This significantly changes the properties of the fiber.

Additionally, like the primary coating, the secondary coating should exhibit minimal changes in its physical properties when exposed to moisture. Many polymeric coating materials undergo significant hydrolysis, plasticization, and
Experience softening and loss of protective function. Therefore, it is desirable that the secondary coating also be as hydrophobic as possible. The hydrophobic secondary coating also enhances the performance of the primary coating by keeping water away from the glass fiber itself, thereby inhibiting moisture that can induce hydrolysis and stress corrosion of the glass fiber.

The secondary coating also has a high refractive index, preferably higher than that of the glass fiber substrate, so that it can strip out undirected light like the primary coating. You must do so.

This is especially necessary in embodiments where the primary coating is removed.

Another important property of the secondary coating is the coefficient of friction (
coF), a low COF makes it easier to wind and unwind fibers from a spool; a low COF also makes it easier for fibers to slide past each other in a cable structure. This makes it possible to reduce stress. However, if C
If the OF is too low, it will not line up properly on the spool. The COF is determined in large part by the cure characteristics of the secondary coating; if the coating has a reasonably hard cured surface, the COF tends to be low. Various slip agents can be added to achieve even lower COFs; however, adverse effects such as surface tension problems, contamination, volatilization, and blooming can occur with the use of slip agents. .

There are still other desirable properties that apply to primary and secondary coatings for coating. For example, fiber manufacturers can obtain economical faster cure rates by coating fibers as quickly as possible. and higher line (l
ine) have a desire to increase speed. The cure rate of a coating material can be determined by plotting a UV dose versus modulus curve. The lowest UV dose at which the coating modulus is dose independent is considered when considering the cure rate of the coating material. Fiber manufacturers have a demand for coatings that cure faster; for example, higher line speeds allow wet-on-wet applications;
Obtained by primary and secondary coatings that can be simultaneously UV cured. One way to do this is by Carl
No. 4,474,830 issued October 2, 1984 by R. Taylor.

In accordance with this patent, an optical fiber is passed through a coating apparatus that includes first and second dies. The first die confines the initial coating liquid over a portion of the length of the fiber. A second coating liquid is applied onto the fiber through the gap between the first and second dies. The gap is small enough so that substantially no recirculation of the second coating liquid occurs near the point of application of the first coating liquid to the fiber. The second coating liquid is preferably applied to a free surface, i.e. that surface is applied to the fiber at either the first or second die in the immediate vicinity of the point at which the coating liquid is applied. Not in contact. Additional coatings can be applied in a similar manner.

Another desirable objective of applying primary and secondary UV curable coatings is to minimize the amount of unbound material present in the coating after curing. Even when the cured coating is considered to be a 100x solid, there may still be small amounts of material that is not chemically bonded to the polymeric framework during curing. Examples of materials used in coatings include unreacted monomers, unreacted photoinitiators, and certain non-functional additives. It is undesirable to use excessive amounts of such materials. This is because, over time, the physical properties of the coating can change due to volatilization of its useful components.

For example, volatile materials of the primary coating tend to permeate into the secondary coating, rendering it visible and causing a loss of strength. Volatile materials also generate unpleasant odors.

Still other important properties of an optical fiber coating are viscosity and shelf life. Satisfactory shelf life is considered a coating stability of at least 6 to 12 months. The viscosity can be adjusted somewhat by controlling the temperature at which the coating is applied. However, a high viscosity is advantageous because it maintains rheology and ease of handling during coating, whereas a low viscosity facilitates foam release and minimizes the amount of heat required during preparation. It is convenient because it can be used to prevent overheating.
This is undesirable since it may cause premature gelation or increase in viscosity due to thermal initiation of polymerization.

Various single or double layer fiber coatings are in the prior art. They are epoxy or urethane based resins. However, many of these resins cure slowly; or have poor hydrophobicity;
and poor oxidative stability; and undesirable yellowing.

Primary (buffer) coatings have also been developed that are cured by ultraviolet radiation. However, such prior art primary coatings are inherently not very moisture resistant and suffer from some of the drawbacks mentioned above.

To eliminate these drawbacks, prior art primary coated optical fibers have been surface treated with tough, flexible protective coatings that have excellent resistance to moisture and abrasion. Prior art coatings include extruded nylon [
Jacket J coating is also available.

However, it is more expensive and difficult to apply than UV-cured coatings.

Accordingly, the present invention seeks to provide primary and secondary coatings with the highest thermal, oxidative, and hydrolytic stability. and the primary coating adheres well to the glass fiber but is also removable therefrom; provides a sufficient cushioning effect to the fiber; has a relatively low glass transition temperature; and
The stress applied to the fiber can be reduced. The secondary coating must act as a hard protective layer; have a relatively high glass transition temperature and high modulus; be hydrophobic and resistant to moisture; have a high refractive index; and have a suitable It must have a coefficient of friction value. Additionally, the two coatings can be wet cured by simultaneous radiation curing at commercially acceptable cure rates.
It can be formulated for use on-wet.

Accordingly, in a preferred embodiment of the present invention, radiation curable primary and secondary coatings for optical fibers have been provided. The primary coating has a refractive index greater than that of the fiber support and a relatively low glass transition temperature and modulus (ie, less than about -20° C. and less than about 500 psi, respectively). The secondary coating is
With a relatively high glass transition temperature (i.e., about 50°C) and about 10
It has a modulus of 0,000 psi. The secondary coating also has a higher index of refraction than the optical fiber's coating material to strip undirected light when coated alone. We have also developed optical fibers coated with only secondary coatings, or optical fibers coated with primary and secondary coatings of the present invention. Radiation curable primary coatings for optical fibers of the present invention can be applied in one preferred LIi manner: (A ) (i) a hydrocarbon polyol; (ii) an aliphatic polyisocyanate; and (ii) an end-ca selected from hydroxyalkyl acrylate and hydroxyalkyl methacrylate.
(B) about 5% to about 80% by weight of an acrylated urethane oligomer, which is the reaction product of the monomer;
% overlap to about 50% overlap: (c) A monomer or oligomer having (1) an aromatic group, (2) an acrylic or methacrylic unsaturated group, and (3) a hydrocarbon group (the monomer or oligomer is about 5% by weight (which can increase the refractive index of the composition)
~60% by weight: (D) Organofunctional silane fixing agent in an amount of about 0.1% to about 3% by weight.
0% by weight: and (E) from about 1.0% to about 10% by weight of a photoinitiator, [all weight% listed above are for (A), (B), (C)
.

(D), and (E) for the primary coating based on the total weight.

The primary coating may optimally include other materials such as at least one chain transfer agent, preferably a mercapto-functional chain transfer agent, and at least one stabilizer.

The present invention also provides, in one preferred embodiment: (,1) from about 20% to about 80% by weight of polyester-based aliphatic urethane acrylate oligomers; (It) isobornyl acrylate; isobonyl methacrylate; CM-C
16 saturated hydrocarbon diol diacrylate: C4-C1
from about 20% to about 60% by weight of an acrylated or methacrylated compound selected from the group consisting of: 6-saturated hydrocarbon diol dimethacrylate; %, [all weight % above are (1), (II), and (I
[I) is based on the total weight of the secondary coating] Includes a radiation curable secondary coating for an optical fiber comprising:

The secondary coating may optionally include at least one stabilizer.

Coated optical fibers have also been developed. One BlH
In , the optical fiber includes an optical fiber coated only with the secondary coating layer described above. In another preferred embodiment, a coated optical fiber has been developed comprising an optical fiber, an applied primary coating layer as described above, and an applied secondary coating layer as described above.

A method for preparing coated optical fibers was also developed. In one embodiment, the method comprises: applying a primary coating as described above to an optical fiber; applying a secondary coating layer as described above over the primary coating layer; and preferably simultaneously irradiating the two coating layers. including hardening.

The coating composition of the present invention is also useful for coating and protective purposes on other objects.
It can be formulated for use on ceramic, granite, marble surfaces, and the like.

DETAILED DESCRIPTION OF THE INVENTION This invention relates, in part, to radiation curable primary and secondary coatings for optical fibers. The coated optical fiber can include a glass core and a glass adhesion layer. The core can include, for example, silicates such as silica doped with germanium or phosphorus oxides and deposited, pure or doped fluorosilicates. Alternatively, the fiber can include a polymer-coated silica glass core. Such polymeric deposits include organosiloxanes such as polydimethylsiloxane or fluorinated acrylic polymers. The primary coating should have, inter alia, the following properties: moisture resistance; ease of coating and removal: low volatile content; low modulus over the life of the fiber; low glass transition temperature and service life. The secondary coating should form a hard protective layer; it should also have a relatively high modulus and glass transition temperature; and moisture resistance. The two coatings should be clear: odorless: cure quickly, and should remain adhesive even when aged in hot and humid environments.

-° Coating The primary coating composition of the present invention contains five components (A) to (E).

A-based oligomers - The first component is a unique hydrocarbon-based oligomer (
A). This ingredient is added to about 20% of the weight of the composition based on the total weight of all components A-E of the composition.
% to about 80% by weight. Preferably, the oligomer comprises from about 30% to about 70%, more preferably from about 45% to about 65% by weight, based on the weight of the composition based on the total weight of components A-H.

The specific hydrocarbon-based oligomers used in the present invention were chosen to provide the tissue with excellent thermal, oxidative, and hydrolytic stability.

It is known in the art that there are various types of UV-curable oligomers that can produce coatings of the type that are soft, resilient, and have low glass transition temperatures. One system known in the art is an acrylate end-capped polybutadiene rubber as a base resin or a rubber-modified acrylated monomer. These structures have excellent low temperature properties and are suitably hydrophobic, but are susceptible to oxidation over long periods of time due to the presence of carbon-carbon double bonds (unsaturation) in the structure.

The use of acrylated silicones as base resins in such compositions is also known in the art.

Acrylated silicones have excellent low temperature properties and hydrophobicity, but are difficult to formulate with suitably high refractive indices and tend to have poor thermal stability. And in fibers coated in this way, hydrogen gas is generated that attenuates the signal.

Yet another system known in the art involves the use of acrylated fluorocarbons. While suitably hydrophobic and thermally stable, acrylated fluorocarbons are incompatible with most non-halogenated organic compounds. Furthermore, acrylated fluorocarbons are very expensive compared to other tissues.

To overcome many of the drawbacks of prior art systems, the present invention employs a urethane acrylate system based in whole or in part on a hydrogenated polybutadiene backbone. Generally, urethane acrylate systems based on polyether or polyester are known and can be formulated to be soft and
A buffer coating with low modulus and low Tg could be formed. However, polyether or polyester based systems usually have poor water resistance and are thermally unstable. Additionally, known aromatic isocyanate-based urethane oligomers exhibited thermal instability and a tendency to yellow. While polyether-based urethane acrylates have excellent low Tg properties, they are generally not sufficiently hydrophobic and susceptible to oxidation for use in optical fibers; Urethane acrylates have excellent thermal stability but are cheap to hydrolyze.

Therefore, the present invention uses oligomers that eliminate many of the problems mentioned above.

The oligomer (A) used in the present invention is (iii) a hydrocarbon polyol; (ii) an aliphatic polyisocyanate; and (iii) an endca
ppping) is a reaction product of monomers. The hydrocarbon polyol (iii) is provided by a flocculent or branched hydrocarbon containing a large number of hydroxyl end groups and providing a hydrocarbon backbone to the oligomer. The hydrocarbon group has a molecular weight of about 600 to about 4000. The molecular weight in this case is determined by gel permeation chromatography (GPC), which uses methylene chloride as a cutting tool and measures the molecular weight of polystyrene as a standard.

"Hydrocarbon" refers to the majority of methylene groups (-CH,-)
containing internal unsaturation and/or pendant (pe
ndent) refers to non-aromatic compounds that can contain unsaturation. Fully saturated (ie, hydrogenated) hydrocarbons are preferred because the long-term stability of the cured optical fiber coating increases as the degree of unsaturation decreases. Suitable hydrocarbon polyols include fully or partially hydrogenated 1,2-polybutadiene terminated with hydroxyl groups; 1,2-polybutadiene polyols hydrogenated to an iodine number of 9 to 21; and mixtures thereof. It is preferred that the hydrocarbon polyol is substantially completely hydrogenated; therefore, preferred polyols are hydrogenated 1
．． 2-polybutadiene.

Polyisocyanate component (ii) is non-aromatic.

Oligomers based on aromatic polyisocyanates yellow in the cured coating. Suitable saturated aliphatic polyisocyanates include isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate;
l, 4-tetramethylene diisocyanate; 1,5-pentamethylene diisocyanate; 1,6-hexamethylene diisocyanate); il, 7-hebutamethylene diisocyanate; 1, B-octamethylene diisocyanate);
1,9-nonamethylene diisocyanate; 1.10-
Decamethylene diisocyanate; 2+2+4-trimethyl-L5-pentamethylene diisocyanate i2,7-
Dimethyl-1,5-pentamethylene diisocyanate;
3-methoxy-1,6-hexamethylene diisocyanate; 3-butoxy-1,6-hexamethylene diisocyanate; omega, omega'-dipropyl ether diisocyanate; 1,4-cyclohexyl diisocyanate; 1,3-cyclohexyl diisocyanate ; trimethylhexamethylene diisocyanate; and mixtures thereof. Isophorone diisocyanate is a preferred aliphatic polyisocyanate.

The reaction rate of diisocyanates with hydroxyl-terminated hydrocarbons can be increased by using catalyst in amounts of 100 to zoopp-. Suitable catalysts include dibutyltin dilaurate, dibutyltin oxide,
Diptylic acid di-2-hexoate, stannous oleate,
stannous octoate, lead octoate, ferrous acetoacetate, and triethylamine, diethylmethylamine,
Amines such as triethylenediamine, dimethylethylamine, morpholine, N-ethylmorpholine, piperazine, N,N-dimethylbenzylamine, N,N-dimethylbenzylamine, N,N-dimethyllaurylamine, and mixtures thereof, preferred catalysts are , dibutyltin dilaurate.

The end-capped monomer (ii) has the following formula (wherein R3, R4, and e are hydrogen, methyl, ethyl,
or propyl, where m is 1 to
an integer of 10, and p is 0 or 1). Suitable hydroxyl-terminated monoacrylates that can be used as end-capping monomers include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Among them, hydroxyethyl acrylate is preferred. The reason is that the curing speed of the polyurethane oligomer is further increased. polyol,
The molar ratio of diisocyanate and end-capping monomer is preferably approximately 1:2:2.

Preferred oligomers have the following formula: % where R1 is a fully or partially hydrogenated 1°2
- polybutadiene; 1,2-polybutadiene hydrogenated to an iodine number of 9 to 21; and linear or branched carbonized with a molecular weight of 600 to 4000 selected from the group comprising polyisobutylene, fully or partially hydrogenated. is a hydrogen polymer; R2 is a linear, branched, or cyclic alkylene having 6 to 12 carbon atoms; and X and Q are independently of the formula: (a) where R3, R4 and R5 are independently hydrogen, methyl, ethyl, or propyl, m is an integer from 1 to 10, and p is either O or 1. b) a saturated alkyl radical having from 9 to 21 carbon atoms] and must have at least one acrylate or methacrylate end group.

The oligomers described above are described in US Pat. No. 4,786,586 to Lee et al., which is incorporated herein by reference.

The oligomers mentioned above are particularly suitable. The reason is that the saturated hydrocarbon backbone in the oligomer provides suitable hydrophobicity and thermal stability. The glass transition temperature of the present oligomer is about -20°C and can be lowered further by incorporating additives discussed below.

The primary coating comprising the present oligomer has a water absorption value of less than 5% by weight, preferably less than 2.5% by weight.

B Acrylic Monomer The second essential component of the primary coating composition is:
The monomer (B) is based on alkyl acrylate or methacrylate. The alkyl group of the monomer is 6 to 1
having 8, preferably 8 to 15 carbon atoms,
It is hydrocarbon in character. This monomer (B) is either linear or branched.
This monomer (B) is about 5% by weight based on the weight of the composition based on the total weight of components A-H of the composition.
~50% by weight, preferably from about 7.5% to about 30%, more preferably from about 10% to about 20%.

Homosumers are selected because they are compatible with the highly hydrophobic oligomers discussed above.
This monomer is selected because of its soft curing properties and its low Tg, which lowers the Tg of the composition containing the monomer. Examples of suitable C4 to C11 furkyl acrylate or methacrylate based monomers include hexyl acrylate; hexyl methacrylate;
2-ethylhexyl methacrylate; 2-ethylhexyl methacrylate; isooctyl acrylate; isooctyl methacrylate; octyl acrylate; octyl methacrylate; decyl acrylate; decyl methacrylate;
Stearyl acrylate; Stearyl methacrylate;
C14~cps hydrocarbon diol diacrylate; C1
4- to C15 hydrocarbon diol dimethacrylate; and mixtures of the above materials, preferred alkyl acrylate monomers include stearyl acrylate, lauryl acrylate, and isodecyl acrylate.

Particularly preferred is lauryl acrylate. The alkyl acrylate- or methacrylate-based 7-mers are prepared by applying a spindle using an LVT type B-type viscosity needle at 25°C, such that the viscosity of the entire primary coating composition is
dle) Sufficient amount should be used to give a viscosity in the range of about 2,000 centipoises to 10,000 cps as measured by spindle number 34 at a speed of 6 rpm.

The next component is a monomer or oligomer (C) that can adjust the refractive index of the composition.

The monomer or oligomer (C) contains at least (1) an aromatic group, (2) an acrylic or methacrylic unsaturated group, and (3) a hydrocarbon group.
Based on the weight of the composition based on the total weight of components (A) to (E), about 60
-For boat fishing, an amount not exceeding % by weight should be used.
From about 5% to about 60% by weight, preferably from about 10% by weight
About 40% by weight, more preferably about 15% to about 30% by weight
It should contain the amount of % by weight.

Using monomers or oligomers (C) can increase the refractive index for the reasons mentioned above. Aromatic groups of the monomer or oligomer can in turn increase the refractive index; however, hydrocarbon groups are necessary to increase the compatibility of the hydrocarbon-based oligomer (A) with the present monomer. . The acrylic or methacrylic unsaturated group has effective reactive acrylic unsaturation that can crosslink with other components of the composition during UV curing, thus making the monomer or oligomer compatible with the entire system. Therefore, ice cubes or oligomers minimize the volatile content of the cured tissue. hydrocarbon trait (hydrocarbon trait)
Examples of aromatic monomers or oligomers additionally containing a vinyl group and a vinyl group include polyalkylene glycol nonylphenyl ether acrylates such as polyethylene glycol nonylphenyl ether acrylate or polypropylene glycol nonylphenyl ether acrylate; polyethylene glycol nonylphenyl ether acrylate; methacrylate or polyalkylene glycol nonylphenyl ether methacrylate, such as polypropylene glycol nonylphenyl ether methacrylate; and mixtures thereof. In each case, the phenyl group serves to increase the refractive index of the coating, and the nonyl component makes the composition slightly more hydrophobic, making it compatible with hydrophobic oligomers (A).

The refractive index of the composition containing the heptamers or oligomers is at least about 0.005 higher than that of the composition containing only (A), (B), (D), and (E). The primary coating composition, for example, has a refractive index of 1.48 or greater.

The refractive index of the primary coating must be even higher than that of the fiber cladding, if the fiber coated with the coating composition of the present invention is doped with a solution of poor purity (d
If it is own-doped, that is, it contains a chemical dopant that lowers the refractive index of the fiber itself, then the refractive index of the coating is such that it refracts the transmitted signal even without this component. , will be sufficiently different from the refractive index of the fiber; therefore, in such embodiments, monomer or oligomer (C) is not essential to the composition.

Dan-ashi! The fourth component is a fixing agent (D). Adhesion is a particularly immediate problem in hot, humid environments where the risk of delamination is even greater.

It is known in the industry to enhance the adhesion of resins to glass using either acid-functional materials or organo-functional silanes. Acid-functional materials would be effective here, but
Organofunctional silanes are preferred.

Acid-functional materials are less preferred because they are corrosive to other materials and tend to lose adhesive properties when exposed to moisture. Silanes are chosen as adhesion promoters because they have much better propensities with respect to these factors. Additionally, it is beneficial to use adhesion promoters that have functionality that binds to the main tissue during curing, and also to minimize the amount of unbound volatility. Suitable organo-functional silanes (but not limited to amino-functional silanes) include mercapto-functional silanes; methacrylate-functional silanes; acrylamide-functional silanes; allyl-functional silanes: vinyl-functional silanes; and acrylate-functional silanes. The adhesion promoter is preferably a methoxy or ethoxy substituted silane. Preferred organofunctional silanes (not limited to mercaptoalkyltrialkoxysilanes) include methacryloxyalkyltrialkoxysilanes, aminoalkyltrialkoxysilanes, and mixtures thereof. Methacrylated silanes are desirable because they bond well with the cured structure, but they tend to slow down the rate of cure of this structure with the amount used.

Mercapto-functional fixatives also bind chemically during curing, but do not measurably slow down the curing rate of the tissue.

Some preferred organofunctional silanes that enhance adhesion in the wet state include 3-aminopropyltriethoxy silane,
3-methacryloxypropyltrimethoxy silane,
3-mercaptopropyltrimethoxy silane, and 3
-mercaptopropyl (gammamercaptopropyl)triethoxysilane, and mixtures thereof.

A particularly preferred fixing agent is 3-mercaptopropyltrimethoxy silane.

The silane component is present in the present composition in a small but effective amount to enhance the adhesion of the composition to the inorganic support surface, in this embodiment glass, and in other embodiments glass, enamel, marble, granite, etc. should be mixed into the product.

The silane component is from about 0.1% to about 3.0% by weight, based on the weight of the composition based on the total weight of the five components A-E.

Preferably, the silane is about 0.2% to about 2.0% by weight, more preferably about 0.2% by weight, based on the total weight of oligomer, alkyl acrylate or methacrylate, multifunctional monomer photoinitiator, and silane. 3% by weight to about 1.
It is 0% by weight.

The fifth component of the primary coating composition is a photoinitiator (E), when used in a small but effective amount to promote radiation curing. The composition should provide a reasonable rate of cure without causing premature gelation of the composition.

Furthermore, the optical clarity of the cured optical coating must not be compromised. Still further, the photoinitiator itself must be thermally stable, non-yellowing, and efficient.

Suitable photoinitiators include: hydroxycyclohexylphenylketone; hydroxymethylphenylpropanone; dimethoxyphenylacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; -(4-
isopropylphenyl)2-hydroxy-2-methylpropan-I-non;1-(4-dodecylphenyl)-2
-Hydroxy-2-methylpropan-1-one 14-(
2-hydroxyethoxy)phenyl-(2-hydroxy-
2-propyl) ketone; jetoxyacetophenone; 2
, 2-di-sec-butoxyacetophenone: jetoxy-phenylacetophenone; and mixtures thereof.

The photoinitiator preferably ranges from about 1.0% to about 10% by weight, based on the total weight of the composition of components A-H.
．． It is 0% by weight. Preferably the amount of photoinitiator is A-H
from about 1.5% to about 8.0% by weight, more preferably about 2.0% by weight, based on the total weight of the components of
~7.0% by weight. A particularly preferred photoinitiator is hydroxycyclohexyl phenyl ketone. When using the specified amount of photoinitiator, the cure rate measured in the dose vs. modulus curve is 1. The photoinitiator should be chosen so that it is less than 0.5 J/cm', preferably 0.5 J/cm'.

Various optional components, other than the five components A-H, can be used in the primary coating. For example, optional chain transfer agents can be used to control the modulus and glass transition temperature of the coating. can do. Curing of acrylate-containing monomers or oligomers involves free radical (fr)
ee radical). One method known in the industry for controlling the modulus and glass transition temperature of free radical polymerization products by controlling their molecular weight is to use one or more chain transfer agents. be. When a chain transfer agent is added to the formulation,
The resulting polymer has a lower molecular weight, resulting in a coating with a lower modulus and lower glass transition temperature.
Assume that.

Preferred chain transfer agents are mercapto compounds optionally having a hydrocarbon chain of at least 8 carbon atoms. Examples of suitable mercapto chain transfer agents include methylthioglycol; methyl-3-mercaptopropionate; ethylthioglycolate; butylthioglycolate; butyl-3-mercaptopropionate; isooctylthioglycolate; 3-Mercaptopropionate; Isodecylthioglycolate; Isodecyl-3-
Mercaptopropionate; dodecylthioglycolate; dodecyl-3-mercaptopropionate; octadecylthioglycolate; and octadecyl-3-mercaptopropionate. Parathiocresol; thioglycolic acid; and 3-mercaptopropionic acid can also be used, but are somewhat incompatible with the resin and can create odor problems.

A particularly preferred chain transfer agent is octadecyl-3 mercaptopropionate (COMP).

A chain transfer agent, if used, is from about 0.1% to about 10.0% by weight, based on the total weight of components A-E, based on the weight of the composition. Preferably a chain transfer agent is about 0.25% by weight on a weight basis based on the total weight of components A-H.
~5.0% by weight, more preferably about 0.5% by weight~4.0% by weight. Approx. 1 of a suitable chain transfer agent
．． 0 wt % adhesion lowers the glass transition temperature of the composition by about 3° C. and also lowers the modulus by about Loops i, clearly increasing the adhesion of the coating to glass fibers. Incorporating more than about 2.0% by weight of a chain transfer agent into the mixture desirably lowers the modulus and glass transition temperature of the composition, but somewhat shortens the shelf life.

One or more stabilizers may be included in the composition to increase the thermal and oxidative stability of the cured coating as well as to improve the shelf life (storage stability) of the uncured coating. I can do it. Examples of suitable stabilizers include tertiary amines such as diethylethanolamine and trihexylamine; hindered amines; organic phosphites; hindered phenols; and mixtures thereof. Some specific examples of antioxidants that can be used include octadecyl-3-(
3', 5'-di-tert-butyl-4'-hydroxyphenyl)propionate: thiodiethylene bis3
, 5-di-tert-butyl-4-hydroxy)hydrocinnamate; and tetrakis[methylene(3,5-
(tert-butyl-4-hydroxyhydrocinnamate)]methane.

When using a stabilizer, based on the weight of components A-H,
Amounts from about 0.1% to about 3.0% by weight can be mixed. Preferably in the range of about 0.25% to about 2.0% by weight, more preferably in the range of about 0.5% to about 1.5% by weight, based on the total weight of components A-E. may contain stabilizers. Desirable properties of stabilizers include:
These include (1) non-migration (probably enhanced by low polarity) and (2) basicity (helps neutralize residual acids that can prematurely initiate polymerization). Preferred stabilizers are octadecyl-5-(3',5'-di-tert-butyl 4'-hydroxyphenyl)propionate and trihexylamine.

A preferred primary composition for coating an optical fiber then comprises: (A) from about 45% by weight to an aliphatic urethane acrylate oligomer having a hydrogenated 1,2-polybutadiene polymer as the backbone; 65% by weight; (B) about 10% to about 20% by weight of lauryl acrylate; (C) about 15% to about 30% by weight of polypropylene glycol nonylphenyl ether acrylate: (D)
from about 0.3% to about 1.0% by weight of a gamma mercaptopropyltrimethoxysilane adhesion promoter; (E) from about 2.0% to about 7.0% by weight of a hydroxyl chlorohexyl phenyl ketone photoinitiator; (F) about 0.5% to about 4.0% by weight of an octadecyl-3-mercaptopropionate chain transfer agent; and (G) octadecyl 3-(3', 5'-diter)
from about 0.5% to about 1.5% by weight of t-butyl-4'-hydroxyphenyl)propionate; all weight percentages above are based on the total weight including (A) through (E).

The most important properties of secondary uniminiy & secondary optical fiber coatings are also impeccable thermal, oxidative and hydrolytic stability; hardness; high modulus; high glass transition temperature; and high refractive index. Accordingly, the secondary coatings of the present invention are formulated to have these and other properties.

The secondary coating of the present invention also comprises (1) about 20% to about 80% by weight of a polyester-based aliphatic urethane acrylate oligomer; (II)
20% by weight of an acrylated or methacrylated compound selected from the group consisting of: hexanediol diacrylate; hexanediol dimethacrylate; isobornyl acrylate; % to 60% by weight; and (I) from about 1.0% to 10% by weight of photoinitiator.
II) is based on the total weight.

■Urenaku! The first essential component (1) of the Lato I Gomer secondary coating composition is a polyester-based aliphatic urethane acrylate oligomer.

Oligomers commonly used in UV cure systems include acrylated polyesters, epoxies, and urethanes.

Acrylated polyesters are undesirable because they are easily hydrolyzed during high temperature hydrolytic aging.

Acrylated epoxies have unacceptable thermal and oxidative stability problems and are prone to yellowing. Regarding acrylated urethanes, urethanes based on aromatic and aliphatic isocyanates can be used. Aromatic urethanes have poor thermal and oxidative stability, whereas aliphatic urethanes do not have these drawbacks.

The main chains of the most commercially used urethane acrylates are of polyether or polyester nature. These two backbones have inherent drawbacks. Polyethers are - hydrolytically stable, but easily oxidized, whereas polyesters are oxidatively stable, but easily hydrolyzed. Polyesters can be protected from hydrolysis by maximizing formulation hydrophobicity by selecting hydrophobic monomers, initiators, additives, etc. and/or inherently hydrophobic polyesters.

Compound hydrophobicity can be similarly improved when polyether-based urethanes are used. However, for polyether-based urethanes, it is necessary to add various heat stabilizers and antioxidants.

Therefore, a preferred approach is to use a hydrophobic polyester-based urethane that is protected from hydrolysis by selecting other formulation ingredients to maximize the hydrophobicity of the total formulation. This is important because the overall physical properties of the coating decrease dramatically upon absorption of water.

Suitable base oligomers are aliphatic urethane oligomers with a polyester backbone.

A particularly desirable example is an acrylated aliphatic urethane oligomer containing 75% oligomer solids in hexanediol diacrylate solvent. A suitable oligomer is
Cargill Inc, +Minneapolis
, Carg, containing 75% by weight polyester-based acrylic aliphatic urethane oligomer in 25% hexanediol diacrylate, commercially available from MMN.
ill 1512, the zero oligomer component is based on the essential composition, i.e., the total weight of the dry base material:
About 20% to about 80% by weight, more preferably 30% to 80% by weight, even more preferably about 40% to about 80% by weight. Note that the above percentages are based on the weight of oligomer only.

(2) Acrylate Functional Compound Component The second component of the secondary coating is an acrylated or methacrylated compound (II).

The function of this compound is to adjust the viscosity of the coating so that it is inexpensive to apply to buffer coated fibers.

The compound is hydrocarbon in nature to make the secondary coating hydrophobic and compatible with other components of the tissue, and preferably contains a bicyclic structure to have low shrinkage. It is.

Suitable monomers include isobornyl acrylate;
Isobornyl methacrylate: a mixture of C14 and CtS diol diacrylates or dimethacrylates, or hexanediol diacrylates or hexanediol dimethacrylates, or mixtures thereof.
Mention may be made of C16 saturated hydrocarbon diol acrylates or methacrylates.

A mixture of isobornyl acrylate and hexanediol diacrylate (hexanediol diacrylate is a reactive solvent for the oligomer) is a preferred component. Acrylated or methacrylated components (
II) is about 20% by weight to about 60% by weight, more preferably about It can contain from 25% to about 50%, more preferably from about 30% to about 40% by weight.

m-L dish koji M As in the case of the primary coating, the photoinitiator (II[)
is a desirable component of the secondary coating. Any of the acceptable photoinitiators described as suitable for the primary coating are also suitable: and also a preferred photoinitiator is hydroxycyclohexyl phenyl ketone. The photoinitiator is used in an amount effective to initiate radiation curing of the composition. m, about 1.0% to about 10% by weight based on the total weight of (1), (II), and (m), and preferably used (1), (II), and (III). )
from about 1.5% to about 8% by weight based on the weight of the ingredients;
More preferably, it is about 2.0% by weight to about 7.0% by weight.

- For boat fishing, lower amounts of photoinitiator are acceptable and desirable in the secondary coating relative to the primary coating. First of all, the secondary coating has greater acrylate functionality than the primary coating and also cures substantially faster than the primary coating. Alternatively, the coating can be applied wet-on-wet,
If then simultaneously cured, it is important not to use too much photoinitiator during the secondary coating to minimize the effective dose to cure the primary coating through the secondary coating. .

As in the case of the primary coating, various stabilizers can be mixed, including one or more of organic phosphites, hindered phenols, hindered amines, and mixtures thereof. A particularly preferred stabilizer is thiodiethylene bis(3,5 di-tert-butyl-4-hydroxy)hydrocinnamate. When used, stabilizers include (1) oligomers (It) hetamine-2 and (I
II) on a weight basis based on the total weight of photoinitiator, about 0.1
% to about 3% by weight, more preferably 0.25% by weight
~about 2% by weight, more preferably 0.5% by weight~
An amount of about 1.5% by weight can be added.

A preferred secondary coating composition for coating an optical fiber is therefore: (1) a polyester-based aliphatic urethane acrylate oligomer containing about 4
0% to about 80% by weight; (II) a mixture of isobornyl acrylate and hexanediol diacrylate;
0% to about 40% by weight; and (DI) hydroxycyclohexylphenyl ketone photoinitiator from about 2.0% to about 7.0% by weight; all of the above weight% are: (1), (II), and (III) based on the total weight.

More preferably, the secondary coating composition also comprises:
Based on the weight of the composition, thiodiethylene bis(3
, 5-di-tert-butyl-4-hydroxy)hydrocinnamate, from about 0.5% to about 1% by weight.
．． Contains 5% overlay.

The modulus of the secondary coating is at least about 40.
000ρsi. The relatively higher modulus of the secondary coating than the primary coating results in desirable physical properties such as cut resistance and microbending resistance and the formation of smooth, slippery fibers that are easy to wind and unwind. In preferred embodiments, the secondary coating of the present invention can be used over the primary coating. However, in another embodiment, the primary coating layer can be omitted and the optical fiber can be coated directly with the secondary coating. Conditions where a secondary coating is sufficient include fibers, extremes, and high humidity.

Or a state where it is not exposed to large bending.

Such applications may include long-distance transmission applications such as transoceanic or transcontinental cables, where the fibers are encapsulated within the cable material.This invention relates to a method for making coated optical fibers. There is also.

(iii) end-capping the optical glass fiber with (A) a hydrocarbon polyol, (ii) an aliphatic polyisocyanate, and (iii) a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate; The acrylated urethane oligomer that is the reaction product with the monomers is about 20 to 80 wt. %, (B) an alkyl acrylate or methacrylate monomer whose alkyl moiety has 6 to 18 carbon atoms, (A), (B),
Approximately 5-50% based on the total weight of (C), (D) and (E)
wt. %, (C) A monomer or oligomer having (1) an aromatic moiety, (2) a moiety with acrylic or methacrylic unsaturation, and (3) a carbon-hydrogen moiety, the composition of which has a refractive index of (A), (A) which may be larger than that of a composition containing only (B), (D), and (F).
Based on the total weight of (B), (C), (D) and (E), approximately 5-6°wt. %, (D) silane fixing agent with organic functional groups (A).

Based on the total weight of (B), (C), (D) and (E), approximately o, i approximately 3. Qwt,! , and (E) a photoreaction initiator (A), (B), (C),
Based on the total weight of (D) and (E), approximately 1.0-10wt.
(ii) applying (1) a polyester-based aliphatic urethane acrylate oligomer onto said primary coating layer, the total weight of (1), (II) and (III) Based on about 20 80i+t. %, (It) Isobonyl acrylate, Isobonyl methacrylate, Cb
Cab Saturated Hydrocarbon Diol No Acrylate, CA
An acrylate or methacrylate compound selected from the group consisting of C16 saturated hydrocarbon diol dimethacrylate and mixtures thereof (1), (It) and (I
II) based on the total weight of approximately 260wt. %, and (III) photoinitiator (1), (It) and (I
II) based on the total weight of approximately 110wt. In another embodiment, the method includes applying a secondary coating layer comprising: This method includes applying only the secondary coating layer of the present invention to an optical fiber and curing the secondary coating layer in situ with radiation.

The primary and/or secondary coating layers can be applied and cured by known methods. A good method for overcoating two coating layers is reported in US Pat. No. 4,474, B: C. Tiller of AT&T Bell Laboratories. Furthermore, the coating or coating layer can be cured, preferably by UV radiation, to obtain a cured polymeric coating.

It is also possible to apply and cure the primary coating and then apply and cure the secondary coating.

Furthermore, the present invention relates to optical fibers, especially glass optical fibers, coated with only the secondary coating of the present invention, or coated with both the primary and secondary coatings. The primary coating surrounding the fibers has a glass transition temperature Tg of at least -2
Desirably lower than 0°C results in a cured polymeric material, such as about -30°C or even lower.

The Tg of the cured primary coating must be lower than the minimum service temperature, but high enough that its modulus increases as the temperature is lowered; this property makes it possible for the secondary coating to The differences in coefficient of thermal expansion between the fibers are compensated for and in this way slight bowing and resultant signs of fragility are minimized.

The Tg of the cured secondary coating is generally relatively high at about 50°C;
The modulus must be high, for example about 100,000 psi. For the secondary coating, it is desirable that its Tg be higher than the maximum service temperature. This is because at or near the Tg of the polymer, a small change in temperature can dramatically change its physical properties.

The two coating layers, when cured, provide the fiber with exceptional thermal, hydrolytic and oxidative stability;
It reduced the stress on it. Optical Mli fibers coated with both the primary and secondary coating layers of the present invention are highly moisture resistant or otherwise protected from environmental damage.

Coating compositions of the present invention have been reported above for use as optical fiber coatings. However, it is to be understood that these coatings can be used in any embodiment where a stable, moisture-resistant coating is desired, particularly in coating the surface of a product useful in prior art. They can be used for a wide variety of end purposes, from (for example in the production of safety glass) to vinyl coatings (in the production of waxless floors). There are countless other optically useful products that can be manufactured, including optical switches, optical relay devices, microelectronic devices, optical combing devices, etc.

1 [This is a further correction of Shita Tomei. In these examples, and elsewhere throughout this application, all parts and percentages refer to dry solid ingredients and all temperatures are in degrees Celsius, unless otherwise indicated. In all examples, the curing temperature was A
Measurements were made using an International Light IL745A radiometer equipped with a Model 309 Light Hack.

Unlike other parts of the application where the weight percentages correspond to the total weight of components A-E for the primary coating layer and components A-1 for the secondary coating layer,
The parts by weight in this example correspond to the total weight of the composition including all ingredients described in this example. In the examples, optional ingredients can be identified by marking them with an asterisk (*). If the coatings illustrated herein meet the absolute requirements for commercially available coatings for optical glass fibers,
Other ingredients must also be used.

Is Takagoi a carp? Hard Nol/i function tζ-n C Sakaki tuyekujuku day hsu-A-jil lower n) was generated in the beat.

Lauryl acrylate (B) 14.50 Hydroxycyclohexyl phenyl ketone photoinitiator (E) 6.00 Nate stabilizer* 1.50 Viscosity of uncured coating is 4005 cps (225
(using a Type B viscometer LVT type, 6 rρm, #34 spindle).

Coat 6 mils of this composition on a flat glass sheet using a Bird applicator at 20 W/in.

It was cured in air using a medium pressure mercury lamp at 0.7 J/C11z.

The glass transition temperature of the resulting cured primary coating is approximately -39.6°C.
The refractive index of the cured film was 1.492.

The temperature hardening for the modulus was 225
℃: 153.0ρsi; 0℃: 167, Bpsi;
20℃: 864.7psi; -40℃: 49, B
07psi; -60°C: 199.018psi, and the curing rate was approximately 0.3 J/cm2 when the modulus was measured against the irradiation dose curve.

The water absorption of the sample was measured as follows. The cured film was equilibrated at 50% relative humidity (±5χ) and 23°C (±2°C) for 4 hours. Measure the weight of the sample and find the weight “A”
was recorded. Further, the sample was placed in distilled water at 25℃ for 24 hours.
After soaking for a period of time, it was patted dry and the weight was measured. This weight was recorded as "B".

Next, the sample was placed in a vacuum furnace at a pressure of 10 Hg and 25°C for 24 hours, and then taken out again at a relative humidity of 50% (±5χ) at 23°C.
℃ (±2℃) for 48 hours, and the weight was measured. This third weight was recorded as "C".

Percentage of water absorption B-CX 100χ When measured as follows, it was approximately 1.48%.

Other samples coated with this 6 mil thickness were tested as follows to determine the effects of accelerated aging on various properties. Samples were heated at 48°C at 50% relative humidity (±5χ) and 23°C (±2°C).
After time equilibration, they were attached to clips and hung in a room under the following accelerated aging conditions: (1) 125°C for 7 days (2) 93.3°C for 110 days (3193°C) , 3℃, 30 days (4) 93.3℃, 95% relative humidity, 10 days (5
] 93.3°C 3 relative humidity 95% for 30 days.

After the set time had elapsed, the samples were removed and allowed to equilibrate again for 48 hours. The following characteristics were recorded: These data suggest excellent stability to thermal and hydrolytic stress.

93.3℃9 93.3℃1 1g Center point A -34,6℃-34,6℃-36,6℃35
,5℃ 36,6℃ ) +33.1χ +39.4χ +37,9χ+2
7.9χ +19.5χ The following UV curable coatings were produced as follows: Nonylphenyl ether acrylate (C) 25.00 Isodenyl acrylate (B) 11.75 Hydroxymethylphenylpropanone photoinitiation Agent (E) 6.00 The above formulation used several different ingredients and somewhat different proportions than those used in Example I.

The viscosity of this formulation was measured using a B-type viscometer LVT type, 6 rpm,
5 at 25°C as measured using #34 spindle.
650 cps, refractive index 21, 1.4849 at B°C. Coated on a glass plate in the same manner as in Example I,
00 W/in, in air using a medium pressure mercury lamp, 0.7
The resulting 6 mil thick coating when cured at J/cm2 is:
Modulus is 295, Bpsi, Tg -28,7℃
It had excellent adhesion to glass and low water absorption (2
．． 02χ), this coating performed well in the high humidity and dry accelerated aging tests.

The following primary coatings were formulated: Weidian 1'' (C) 25.00 Octyl/decyl acrylate (B) 11.75 Hydroxymethylphenylpropanone photoinitiator (E) 6.
00 Namate stabilizer rate 0
．． 50T-mercaptopropyltrimethoxysilane fixative (D) 0.
75 This formulation shows that materials (B) and (C) were selected and used. The viscosity of this formulation was measured using a Type B viscometer LVT model, #34 spindle, 5 rpm at 25°C.
It was 3890 cps. When applied to a glass plate as in Example I and cured in air under a 200-W/in medium-pressure mercury lamp at 0.7 J/cm2, its modulus was 276.0 psi and its adhesion to glass was It had excellent properties and low moisture absorption (1, B9χ).

The following primary coatings were formulated: (Same as Example) (C) 8.00 Isodecyl acrylate (B) 20.50 Hydroxymethylphenylpropanone photoinitiator (E) ) 6.00 Mate stable opening 0.50 Nate chain transfer agent* 0.6
5 This formulation uses components with different ratios, the chain transfer side may or may not be used, and the concentration of component (C) was lowered to adjust the refractive index. The viscosity of the formulation was measured using a B-type viscometer LVT type, 5rps, #3.
59 at 25°C when measured using a 4 spindle.
50 cps, and the refractive index was 1.4796 at 21.5°C. When a glass sheet was coated with 6 mm in the same manner as in Example I and cured at 0.7 J/cm'' in air under a 200 W/in medium pressure mercury lamp, its modulus was 280 psi and Tg was - At 31.2°C, the fixing properties on glass were excellent and the water absorption was low (1.41).

The radiation curable primary coating was formulated as follows.

Lauryl acrylate (B) 14.00 Toxysilane fixative (D) 1, Uυ The viscosity of the uncured coating was 3750 cps (
(at 25°C using a Type B viscosity needle LVT type, 6 rpm, #34 spindle).

6 on the glass sheet in the same manner as in the previous example.
When coated to mil thickness and cured, the coating adhered well under high humidity conditions, but cured more slowly than the Example I coating. By substituting an acrylate silane for the methacrylate silane used in this example, a similar formulation with a much faster cure rate can be produced.

The resulting cured primary coating had a glass transition temperature of approximately -39,
At 4°C, the modulus was 155.5 psi, and the refractive index of the cured film was 1.492. Curing speed is 0.5 J
/Cl1z and water absorption of 1.40%, both of which were measured in a manner similar to that of Example I.

Weight change, glass transition temperature and Instron modulus change were measured under similar conditions as in Example I and recorded as follows. Again, excellent hydrolytic and thermal stability was observed.

7g Midpoint -35,9°C -36,1°C 35,5°C 35,7°C 36,4°C A radiation curable secondary coating composition was produced as follows.

Mate Stabilizer* ■, υO A 6 mil coat of the above composition was applied onto a glass plate using a bird applicator. The coating power is 200W/in.

It was cured in air at 0.7 J/cmz using a medium pressure mercury lamp. The film with the secondary coating has a modulus of approximately 10.
At 3.700 psi, the water absorption was about 1.68% and the cured film had a refractive index of about 1.506. Curing rate measured by modulus versus irradiation dose curve is approximately 0.3 J
/c++''.The UV transmittance of the uncured coating is the ratio of the light transmittance of a lI quartz slide coated with 1 mil of the uncured composition to the light transmittance of the uncoated slide. By calculation, it was determined to be about 73%.

Weight change and Instron modulus change (here 8
(measured at 5° C.) was measured under the same conditions as in Example ① and recorded as follows. Again, excellent hydrolytic and thermal stability was observed.

93.3 ℃.

93.3 ℃.

) +17.2χ +18.3χ +34.32 -4.
A secondary coating was formulated that was the same as the coating of Example 2, except that it contained 3.times.-23.9.times.14.00% isobornyl acrylate and did not contain any stabilizers. The coating, when applied to glass and cured as described above, has excellent tensile properties, cure speed, water absorption, UV transmission and stability. Yellowed in dry aging test.

The coating composition was formulated as follows: III) 4.
It is believed that the 00 aliphatic urethane acrylate oligomer (1) provides favorable properties. Formulations as described above performed well in thermal, oxidative and hydrolytic aging tests without exhibiting any yellowing properties. When commercially available oligomer (1) is cured, it has a lower modulus than the oligomer used in solution in Example 2.

A mixture of CI4 and cps diol diacrylates was used as a viscosity modifier along with isobornyl acrylate.

The above formulation was coated on glass using the coating technique of Example 1 at 6 mils and UV cured. It had a higher Tg and a higher crosslink density compared to the coating of Example 1.

A 50:50 mixture of bis(2,4-di-t-butylphenyl)pentaerythritol phosphite and thiodiethylene bis(3,5-di-t-butyl-4hydroxy)hydrocinnamate in about 0.5 parts by weight. Similar formulations were prepared, except that the stabilizer was contained as a stabilizer cage. During the measurements, the hydrolytic stability decreased, probably due to the use of phosphite. Although this is undesirable for optical fiber coatings, it is not a problem for many other applications. When about 1% of the hindered phenol used above is used as a stabilizer, the hydrolytic stability becomes once again usable for coating optical fibers.

The following coating composition was prepared: Pentaacrylate 14.50 Isobonyl acrylate (It') 11.00 Photoinitiator (III) 4.00 Agent* 1.00 This coating composition was Based on the data, the curing speed was slightly slower than that of the formulation of Example (1).

This data may have given a false impression as this coating has a high tg and high cross-link density; however, the hydrolytic aging properties of this coating, although good, It's hard to say that it's that good. Its viscosity and modulus at room temperature were the same as those of the formulation of Example II. All properties are within acceptable ranges for secondary coatings on optical fibers.

The optical fibers with the primary and secondary coatings of the present invention have several properties that make the coated fibers useful in many applications and suitable for each in local networks ranging from textiles to domestic use. It is designed to have these important properties:

After curing the primary coating, the refractive index is greater than that of the original fiber (i.e., about 1.48), the modulus is less than about 500 ρsi, and the glass transition temperature is about -20'C2.
Preferably it will be below about -30°C. The primary coating is sufficiently hydrophobic to prevent infiltration and subsequent hydrolysis of the underlying fibers, has a low enough modulus to cushion and protect the underlying fibers, and The glass transition temperature is low enough to maintain a rubbery state throughout the usable temperature range, thereby acting as a silica for its glass fibers.

After curing, the secondary coating is a hard protective layer with a glass transition temperature of about 50° C. and a modulus of about 100,000 psi.

Additionally, the secondary coatings are moisture resistant and have a coefficient of friction suitable for the application requiring them. The Wl friction coefficient of the secondary coating is such that the coated fibers remain straight and slide easily along the respective spoon.

Both the primary and secondary coatings have suitable viscosities for coating, and when cured they contain few unbound reactants (volatiles) and have excellent shelf life properties.

The present invention enables the production of coating formulations that meet these criteria and the production of coated optical fibers that are well suited for use in everything from fiber to domestic applications.

Although there are many uses for the coatings produced by the invention,
They do not necessarily have to meet the strict requirements placed on optical fiber coatings. Such versatile coatings can be formulated from (A) (iii) hydrocarbon polyols, (ii) aliphatic polyisocyanates, and (ij) hydroxyalkyl acrylates and hydroxyalkyl methacrylates. About 20 to 80 wt. %, (B) a low Tg, soft-curing hydrocarbon-functionalized acrylate monomer, (C) a chain transfer agent comprising a hydrocarbon chain having 8 or more carbons in the hydrocarbon chain, and (D) the coating composition thereof. (B) stabilizers or antioxidants that further impart shelf life and storage stability to the product;
The combination of C) and (D) with (A) influences the production of radiation-curable coatings in which these components coexist. Desirably, component (B) has 6 in its alkyl moiety.
- about 5-50 iet. of alkyl acrylate or methacrylate monomer containing 18 carbon atoms. %((A
) and (B)), and the glass transition temperature of the coating is in the range of -20°C or lower. In certain embodiments, the composition can be used as a primary coating for optical fibers, where the coating has an uncured liquid viscosity of about 4,000-1 at 25°C.
0, 500cps, tensile modulus is 500psi
(based on a 6 mil thick film at room temperature).

In other embodiments, compositions of this type can be used as interlayer films in laminated glass, such as photovoltaic cells and light switches.
It can also be formulated to be useful as a coating for electronic devices such as chips.

In yet other embodiments, the composition comprises (C) (1
) an aromatic moiety, (2) a moiety containing acrylic or methacrylic unsaturation, and (3) a hydrocarbon moiety that changes the refractive index of the composition to (A
) and about 5-60 wt of monomer or oligomer, which can be increased compared to that of a composition containing only (B).
．． %, and/or (D) an effective amount of a silane having an organic functional group to promote adhesion to the surface of the glass material, and/or (E) an effective amount of photoinitiator to promote radiation curing of said coating. (C)
and/or (D) and/or (E), the glass transition temperature, uncured liquid viscosity, and cured tensile modulus preferably remain in the same range as in compositions without them. .

While this patent application has described the invention by setting forth details of preferred embodiments thereof, this specification is intended by way of example rather than in a limiting sense, and is intended to explain the true nature of the invention and the scope of the appended claims. It is to be understood that the foregoing is intended to include modifications that may readily be made by one skilled in the art.

teenager Reason Man

Claims (1)

[Claims] 1. Reaction product of (A) with an end-capping monomer selected from the group consisting of (i) a hydrocarbon polyol, (ii) an aliphatic polyisocyanate, and (iii) a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate. About 20-80 wt. %, (B) about 5-50 wt. %, (C) A monomer or oligomer having (1) an aromatic moiety, (2) a moiety containing acrylic or methacrylic unsaturation, and (3) a hydrocarbon moiety that increases the refractive index of the composition by ( About 5-60 wt. %, (D) organofunctional silane fixing agent at about 0.1-3.0 wt. %, and (E) photoinitiator at about 1.0-10 wt. %, and all percentages specified therein are (A), (B), (C)
, (D) and (E) as a weight percentage based on the total amount of radiation curable primary coatings for optical fibers. 2. The hydrocarbon polyol (i) is a 1,2-polybutadiene polyol that is wholly or partially hydrogenated, a 1,2-polybutadiene polyol that is hydrogenated to an iodine value of 9-21, or a 1,2-polybutadiene polyol that is wholly or partially hydrogenated. A radiation curable primary coating for an optical fiber according to claim 1 selected from the group consisting of partially hydrogenated polyisobutylene polyols and mixtures thereof. 3. The organic polyisocyanate (ii) is isophorone diisocyanate, dicyclohexylmethane-4,4'
- diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. 4. The radiation-curable primary coating for optical fibers according to claim 1, wherein the oligomer (A) is end-capped with hydroxyethyl acrylate. 5. The oligomer (A) is represented by the structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 1, hydrogenated to -21,
Molecular weight 600 selected from the group consisting of 2-polybutadiene and wholly or partially hydrogenated polyisobutylene
-4000 is a straight chain or branched hydrocarbon polymer, R^2 is a straight chain, branched or cyclic alkylene having 6-20 carbon atoms, and X and Q are independently (a) the structural formula is ▲mathematical formula, There are chemical formulas, tables, etc. ▼ where R^3, R^4 and R^5 are independently hydrogen, methyl, ethyl or propyl, m is an integer from 1 to 10, and p is 0 or 1. (b) a saturated alkyl group of 9 to 20 carbon atoms, provided that said oligomer has one or more acrylate or methacrylate end groups. Radiation-curable primary coating for optical fibers according to item 1. 6, the monomer (B) is hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, Claim 1 selected from the group consisting of isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, C_1_4-C_1_5 hydrocarbon diol diacrylate, C_1_4-C_1_5 hydrocarbon diol dimethacrylate, and mixtures thereof. Radiation-capable primary coatings as described in Section. 7. Claim 1, wherein the monomer (B) is selected from the group consisting of lauryl acrylate, stearyl acrylate, isodecyl acrylate, and mixtures thereof.
Radiation curable primary coatings as described in Section. 8. Radiation curable according to claim 1, wherein the monomer or oligomer (C) is selected from the group consisting of polyalkylene glycol nonylphenyl ether acrylate, polyalkylene glycol nonylphenyl ether methacrylate, and mixtures thereof. primary coating. 9. The monomer or oligomer (C) is polyethylene glycol nonylphenyl ether acrylate,
A radiation curable primary coating according to claim 1 selected from the group consisting of polypropylerane glycol nonylphenyl ether acrylate and mixtures thereof. 10. The silane fixing agent (D) is a silane with an amino function, a silane with a mercapto function, a silane with a methacrylate function, a silane with an acrylamide function, a silane with an allyl function, a silane with a vinyl function, or a silane with an acrylate function. Radiation curable primary coating according to claim 1, selected from the group consisting of silanes and mixtures thereof. 11. The silane fixing agent (D) is selected from the group consisting of mercaptoalkyltrialkoxysilane, methacryloxyalkyltrialkoxysilane, aminoalkyltrialkoxysilane, and mixtures thereof. Radiation curable primary coating. 12. The radiation curable primary coating according to claim 1, wherein the silane fixing agent (D) is γ-mercaptopropyltrimethoxylan. 13. The photoreaction initiator (E) is hydroxycyclohexyl phenyl 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(2-hydroxy-2-propylketone, diethoxyacetophenone, 2,2-di -sec-butoxyacetophenone, diethoxyphenylacetophenone, and mixtures thereof. 14. The radiation-curable primary coating for optical fibers according to claim 1, which is selected from the group consisting of ) is hydroxycyclohexyl phenyl ketone, the radiation-curable primary coating for optical fibers according to claim 1. 15. The chain transfer agent (F) having a mercapto function is
), (B), (C), (D) and (E), about 0.1-10wt. %Claim 1 further includes:
Radiation-curable primary coating for optical fibers as described in Section 1. 16. The chain transfer agent (F) is methylthioglycolate, methyl-3-mercaptopropionate, ethylthioglycolate, butylthioglycolate, butyl-3
-Mercaptopropionate, isooctylthioglycolate, isooctyl-3-mercaptopropionate, isodecylthioglycolate, isodecyl-3-mercaptopropionate, dodecylthioglycolate, dodecyl-3-mercaptopropionate, 16. The radiation curable primary coating for optical fibers of claim 15 selected from the group consisting of octadecylthioglycolate, octadecyl-3-mercaptopropionate and mixtures thereof. 17. The radiation-curable primary coating for optical fibers according to claim 15, wherein the chain transfer agent is octadecyl-3-mercaptopropionate. 18, a stabilizer (G) selected from the group consisting of organic phosphites, hindered phenols, amines and mixtures thereof; (A), (B), (C), (D) and (E);
Based on the total amount of about 0.1-3.0wt. %. A radiation curable primary coating for optical fibers as claimed in claim 1 further comprising %. 19. The radiation curable primary coating of claim 18, wherein said stabilizer is trihexylamine. 20. The optical fiber according to claim 1, further comprising a stabilizer (G) which is octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate. Radiation curable primary coating for use. 21, (A) About 45-65 wt. %, (B) about 10-20 wt. %,
(C) about 15-30 wt. polypropylene glycol nonylphenyl ether acrylate. %, (D) γ-mercaptopropyltrimethoxysilane fixative about 0.3
-1.0wt. %, and about 2.0-7.0 wt of (E) hydroxycyclohexyl phenyl ketone photoinitiator.
．． %, and all percentages herein specified are (A), (B
), (C), (D) and (E) in weight percent based on the total amount of radiation curable primary coatings for optical fibers. 22, octadecyl-3-mercaptopropionate at about 0.5-4.0 wt. based on the total amount of (A), (B), (C), (D) and (E). 22. A radiation curable primary coating for optical fibers according to claim 21, further comprising %. 23. Octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate (A
), (B), (C), (D) and (E), about 0.5-1.5wt. 23. A radiation curable primary coating for optical fibers according to claim 22, further comprising %. 24, (I) About 20-80 wt. %, (
II) an acrylated or methacrylated compound selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, C_6-C_1_6 saturated hydrocarbon diol diacrylate, C_6-C_1_6 saturated hydrocarbon diol dimethacrylate and mixtures thereof. about 20-60wt. %, and (III) photoinitiator about 1-10 wt. %, and all percentages herein are weight percentages based on the total amount of (I), (II) and (III). 25. The radiation-curable secondary coating for optical fibers according to claim 24, wherein the compound (II) is a mixture of isobornyl acrylate and hexanediol diacrylate. 25. The radiation curable secondary coating for optical fibers according to claim 24, further comprising a stabilizer selected from the group consisting of: 26, amines, hindered phenols, organic phosphites, and mixtures thereof. 27, the stabilizer is thiodiethylene bis(3,5-di-
27. The radiation curable secondary coating for optical fibers according to claim 26, which is t-butyl-4-hydroxy)hydrocinnamate. 28. The radiation-curable secondary coating for optical fibers according to claim 24, wherein the reaction initiator is hydroxycyclohexylphenyl ketone. 29, (I) about 40-80 wt. %, (
II) About 30-40 wt. %, and (III) hydroxycyclohexyl phenyl ketone photoinitiator from about 2.0 to 7.0 wt. %, and all percentages herein are percentages by weight based on the total amount of (I), (II) and (III). 30, an optical fiber, a coated optical fiber comprising a primary coating layer and a secondary coating layer, wherein the primary coating layer comprises (A) (i) a hydrocarbon polyol, (ii) an aliphatic polyisocyanate, and (iii) a hydroxyl (A), (B
), (C), (D) and (E), approximately 20-8
0wt. %, (B) the carbon atoms of the alkyl moiety are 6-18
of alkyl acrylate or methacrylate monomer at about 5-50 wt. %, (C) a monomer or oligomer having (1) an aromatic moiety, (2) a moiety containing available acrylic or methacrylic unsaturation, and (3) a hydrocarbon moiety that has a refractive index of the composition. (A), (B), (D) and (E)
The amount of monomer or oligomer can be increased from about 5-60 wt. %, (D) organofunctional silane fixing agent at about 0.1-3.0 wt.
%, and (E) photoinitiator about 1.0-10 wt. including %,
All percentages specified therein are (A), (B), (C
), (D) and (E), and wherein said secondary coating layer contains (I) about 20-80 wt. %, (II) Isobonyl acrylate, isobornyl methacrylate, C
about 2 acrylated or methacrylated compounds selected from the group consisting of _6-C_1_6 saturated hydrocarbon diol diacrylate, C_6-C_1_6 saturated hydrocarbon diol dimethacrylate, and mixtures thereof.
0-60wt. %, and (III) photoinitiator about 1-10 wt. %, and all percentages specified therein are (I), (II
) and (III) as a weight percentage based on the total amount of coated optical fiber. 31. The coated optical fiber of claim 30, wherein the primary and secondary coating layers are radiation cured after being applied to the glass fiber. 32, (I) about 20-80 wt. %, (
II) an acrylated or methacrylated compound selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, C_6-C_1_6 saturated hydrocarbon diol diacrylate, C_6-C_1_6 saturated hydrocarbon diol dimethacrylate and mixtures thereof; About 20-60 wt. %, and (III) photoinitiator about 1-10 wt. %, including all percentages specified therein (I), (II) and (
III) Coated optical fiber, which is an optical fiber coated with a coating layer that is a percentage by weight based on the total amount of. 33. (I) About 30-80 wt. %, (
II) About 25-80 wt. %, and (III) the hydroxycyclohexyl phenyl ketone photoinitiator at about 1.5-8 wt. % and the percentages specified therein are weight percentages based on the total amount of (I), (II) and (III). 34. A coated optical fiber comprising a glass optical fiber and a continuous coating applied to and around the fiber resulting in a cured polymeric material having a Tg of -20°C or less. 35. The coated optical fiber of claim 34, wherein said coating comprises a primary coating layer and a secondary coating layer, both of which are cured polymeric materials. 36. The coated optical fiber of claim 35, wherein said coating layers are both formed from radiation-curable unsaturated materials, and both are radiation-cured in situ. 37, (i) (A) (i) hydrocarbon polyol, (ii)
) aliphatic polyisocyanates, and (iii) hydroxyalkyl acrylates and hydroxyalkyl methgrades. %, (B) about 5-50 wt. %, (C) a monomer or oligomer containing (1) an aromatic moiety, (2) a moiety containing acrylic or methacrylic unsaturation, and (3) a hydrocarbon moiety, which increases the refractive index of the composition by (A ), (B), (D), and (E), the monomer or oligomer can be increased to about 5-60 wt. %, (D) organofunctional silane fixing agent at about 0.1-3.0 wt.
%, and (E) photoinitiator at about 1.0-10 wt. (ii) applying a primary coating layer to the optical fiber comprising (I) a polyester-based aliphatic urethane acrylate oligomer of about 20-% based on the total amount of (I), (II) and (III); 80wt. %, (II) isobornyl acrylate,
(I) an acrylated or methacrylated compound selected from the group consisting of isobornyl methacrylate, C_6-C_1_6 saturated hydrocarbon diol acrylate, C_6-C_1_6 saturated hydrocarbon diol dimethacrylate, and mixtures thereof; Based on the total amount of II) and (III), approximately 20-60wt. %, and (III) photoinitiator to about 1-10% based on the total amount of (I), (II) and (III).
wt. % over the primary coating layer. 38. The method of claim 37, wherein said primary and secondary coating layers are radiation cured by ultraviolet radiation. 39. Endcapping on the surface of an optically useful article (A) selected from the group consisting of (i) hydrocarbon polyols, (ii) aliphatic polyisocyanates, and (iii) hydroxyalkyl acrylates and hydroxyalkyl methacrylates. About 20-80 wt. acrylated urethane oligomer, which is the reaction product with monomer. %, (B) the number of carbon atoms in the alkyl moiety is 6
-18 alkyl acrylate or methacrylate monomer at about 5-50 wt. %, (C) A monomer or oligomer containing acrylic or methacrylic unsaturation that increases the refractive index of the composition by (A
), (B), (D) and (E) in an effective amount not to exceed about 60% of a controllable monomer or oligomer relative to that of a composition containing only (D), and (D) a small amount of an organofunctional silane adhesion promoter. and (E) a small but effective amount of a photoinitiator, all percentages specified therein of (A), (B).
, (C), (D) and (E). 40. 1,2-polybutadiene in which the hydrocarbon polyol (i) is wholly or partially hydrogenated; 1,2-polybutadiene polyol hydrogenated to an iovalence of 9-21; or partially hydrogenated 1,2-polyisobutylene polyols, and mixtures thereof.
Radiation curable coatings as described in Section. 41, the organic polyisocyanate (ii) is isophorone diisocyanate, dicyclohexylmethane-4,
40. The radiation curable coating of claim 39 selected from the group consisting of 4'-diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. 42. Claim 3, wherein the oligomer (A) is end-capped with hydroxyethyl acrylate.
Radiation curable coating according to clause 9. 43. The oligomer is represented by the structural formula ▲Mathematical formula, chemical formula, table, etc.▼, where R^1 is wholly or partially hydrogenated 1,2
- polybutadiene, 1,2-polybutadiene hydrogenated to an iodine value of 9-21 and polyisobutylene wholly or partially hydrogenated, with a molecular weight of 600-4,000; is a straight chain or branched hydrocarbon polymer, R^2 is a straight chain, branched or cyclic alkylene having 6-20 carbon atoms, and X and Q are each independently represented by (a) structural formula ▲ mathematical formula, chemical formula, table etc. ▼ where R^3, R^4 and R^5 are each independently hydrogen, methyl, ethyl and propyl, m
is an integer from 1 to 10, p is a group of 0 or 1, or (b) a saturated alkyl group having 9 to 20 carbon atoms, provided that the oligomer has one or more acrylate or methacrylate end groups. 40. A radiation curable coating according to claim 39. 44, the monomer (B) is hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, iso Decyl methacrylate, lauryl acrylate,
Radiation curable according to claim 39 selected from the group consisting of lauryl methacrylate, stearyl acrylate, stearyl methacrylate, C_1_4-C_1_5 hydrocarbon diol acrylate, C_1_4-C_1_5 hydrocarbon diol dimethacrylate and mixtures thereof. Coating. 45. The radiation curable coating of claim 39, wherein said monomer (B) is selected from the group consisting of lauryl acrylate, stearyl acrylate, isodecyl acrylate and mixtures thereof. 46. The radiation curable coating according to claim 39, wherein the monomer or oligomer (C) is selected from the group consisting of polyalkylene glycol nonylphenyl ether acrylate, polyalkylene glycol nonylphenyl methacrylate, and mixtures thereof. . 47, the monomer or oligomer (C) is polyethylene glycol nonylphenyl ether acrylate,
40. The radiation curable coating of claim 39 selected from the group consisting of polypropylene glycol nonylphenyl ether acrylate and mixtures thereof. 48, (A) acrylation product of the reaction with an end-capping monomer selected from the group consisting of (i) a hydrocarbon polyol, (ii) an aliphatic polyisocyanate, and (iii) hydroxyalkyl acrylate and hydroxyalkyl methacrylate. About 20-80 wt. %, (B) a low Tg, soft-curing hydrocarbon-functionalized acrylate monomer, (F) a chain transfer agent containing a hydrocarbon chain having 8 or more carbon atoms in the hydrocarbon chain, and (G) a coating composition. The combination of (A) with (B), (C) and (D) is radiation curable, and (A) contains a stabilizer or antioxidant that further increases the shelf life and storage stability of the product; Radiation curable coatings that affect the production of compatible component coatings with lower Tg and modulus than only (A), (B) and (C) alone and improved storage stability compared to compositions of (A), (B) and (C) alone. . 49, (A) an acrylated polyol, which is the reaction product of an end-capping monomer selected from the group consisting of (i) a hydrocarbon polyol, (ii) an aliphatic polyisocyanate, and (iii) hydroxyalkyl acrylate and hydroxyalkyl methacrylate. The composition of urethane oligomers is about 20-80 wt. %, (B) one or more low Tg, soft-curing hydrocarbon-functionalized acrylate monomers, (F) a chain transfer agent, (G) a stabilizer to further increase the shelf life and storage stability of the coating composition. or a radiation curable composition containing an antioxidant, in which the combination of (B), (F) and (G) with (A) produces a coating composition of compatible radiation curable components. Coating composition. 50, the monomer (B) has 6 carbon atoms in the alkyl moiety
-18 alkyl acrylate or methacrylate monomer at 5-50 wt. 49. A composition according to claim 48, wherein the percentages defined above are weight percentages based on the total amount of (A) and (B). 51. The composition according to claim 48, wherein the chain transfer agent (F) has a hydrocarbon chain having 8 or more carbon atoms and has a mercapto function. 52. The composition according to claim 49, wherein the chain transfer agent (F) has a hydrocarbon chain having 8 or more carbon atoms and has a mercapto function. 53. A silane having an effective amount of organic functional groups to promote the adhesion of said composition to the surface of inorganic materials such as glass, marble, granite or vitreous or mineral-like surface materials, or to the surface of optical fibers. 50. The composition of claim 49 further comprising a fixing agent. 54. The coating composition of claim 48 further comprising an effective amount of a photoinitiator to promote radiation curing of the coating. 55. The coating composition of claim 53 further comprising an effective amount of a photoinitiator to promote radiation curing of the coating. 56, Tg and modulus when cured are lower than when only oligomer (A) is cured, (A), (B)
51. The composition of claim 50, which has improved storage stability compared to a composition containing only (F) and (F). 57. The composition according to claim 56, wherein the cured coating has a Tg of -20°C or less. 58. Can be used as a primary or buffer coating for optical fibers, and has an uncured liquid viscosity of approximately 4. 58. The coating composition of claim 57, wherein the coating composition is 0.000-10,500 cps. 59. The composition was cast as a 6 mil thick film and when cured had a tensile modulus of 50 at room temperature.
59. A coating composition according to claim 58 having a psi of less than 0 psi. 60, (C) A monomer or oligomer having (1) an aromatic moiety, (2) a moiety containing acrylic or methacryl unsaturation, and (3) a hydrocarbon moiety, which increases the refractive index of the composition by (A ) and (B) in a composition containing only about 5-60 wt. Claim 5 further includes:
Coating composition according to item 2. 61. The coating composition of claim 60, further comprising (D) a silane adhesion agent having an organic functional group in an amount effective to promote adhesion of the composition to an optical fiber surface. 62. The coating composition of claim 61 further comprising an effective amount of a photoinitiator to promote radiation curing of the coating. 63, (B), (C), (D), (F), and combinations of (G) and (A) are radiation curable and (A), (
Tg and modulus are lower than only B) and (C), and (
62. The coating composition of claim 61, which affects the production of coatings of compatible components with improved storage stability compared to compositions of only A), (B), and (C). 64. The coating composition according to claim 64, which has a cured Tg of -20°C or less. 65. The uncured liquid viscosity at 25°C is about 4,000-10,000 cps when measured at 25°C using a Type B viscometer LVT type at 6 rpm and a #34 spindle. Coating composition according to item 63. 66. The coating composition of claim 64 having a room temperature tensile modulus of less than about 500 psi. 67. An optical fiber coated with the cured composition according to claim 60. 68, (I) about 20-80 wt. %, (I
I) an acrylated or methacrylated compound selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, C_6-C_1_6 saturated hydrocarbon diol diacrylate, C_6-C_1_6 saturated hydrocarbon diol dimethacrylate, and mixtures thereof. About 20-60 wt. %, and (III) an amount of a photoinitiator effective to initiate radiation curing of said coating, and all percentages defined above are (I), (II).
) and (III) as a weight percent based on the total amount of radiation curable coating compositions. 69. The radiation curable coating of claim 67, wherein said compound (II) is a mixture of isobornyl acrylate and hexanediol diacrylate. 68. The radiation curable coating of claim 67, further comprising a stabilizer selected from the group consisting of: 70, amines, hindered phenols, organophosphites, and mixtures thereof. 71, the stabilizer is thiodiethylene bis(3,5-di-
70. The radiation curable coating of claim 69 which is t-butyl-4-hydroxy)hydrocinnamate. 72. The radiation curable coating of claim 67, wherein said photoinitiator is hydroxycyclohexylphenyl ketone. 73. An optical fiber coated with the cured composition according to claim 67.