JPS6090304A - Covered optical fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies 12j to a coupled optical fiber. In particular, the present invention
The present invention relates to a method of coating an optical fiber with an ultraviolet curable silicone composition to form a flexible, low-stick coating on the optical fiber that prevents attenuation of light impulses passing through the fiber.

BACKGROUND OF THE INVENTION The currently evolving field of optical telecommunications uses light to transmit information through transparent media in a manner similar to electricity passing through copper or aluminum wire.

Because the information-carrying capacity of electromagnetic radiation increases with frequency, the amount of communication that can be handled in the visible radiation (light) band is potentially thousands of times that of wireless communication.

Since the discovery of suitable light sources for lasers around 1960, the only technical obstacle to remote optical communications has been the development of suitable transmission media. For example, air can transmit light, but rain, fog, and other atmospheric conditions can weaken the optical signal (
In other words, it "attenuated"), so it was inappropriate. The development of glass fiber light guides, or optical fibers, has provided an excellent transmission medium that is relatively inexpensive.

Modern optical fibers typically consist of a light-transmitting core of highly transparent silica glass surrounded by a transparent coating with a lower index of refraction than the core. The coating acts as an internal mirror, reflecting light back into the core, thus preventing optical signals from being lost out of the optical path.

Although the theory of low refractive index coatings has led to practical light guides for relatively short distance communications (e.g. building-to-building or intra-school), long-distance communications (such as bundling a large number of light guides together) have been achieved. (e.g. transcontinental), the problem of signal "noise" becomes more important than signal attenuation. For a particular information-carrying light wave, an incidental or incidental light wave (carrying other information) that disturbs this first light wave.
Or the signal is all "noise" from which the desired information must be extracted. It has been discovered that a coating with a higher refractive index than the core fiber can minimize signal noise in light wave transmission.

Therefore, is the sheathing material a higher or lower refractive index than the core fiber material? Research continues.

In the case of silica glass optical fiber, the reference point It! 1.4
7, that is, the refractive index of the silica glass fiber. Materials with a refractive index lower than this, preferably lower than 1.45, or materials with a refractive index higher than this, preferably higher than 1.50, are suitable.

When manufacturing fiber optic cables for telecommunications, the material used for the wrapping is very flexible and does not adhere too tightly to the glass fiber core (to permit splicing or other manipulations). ) and must maintain its integrity and optical properties under varying environments, including temperature cycling from -60°C to +80°C.

A number of optical fiber manufacturers have employed thermosetting polydimethylsiloxane coating compositions as their primary optical conductor coatings. Typically, the uncoated optical fiber is pulled through the silicone composition and then passed through an 8 inch curing oven at 800°C. The time required to fully cure a silicone composition is a limiting factor in increasing line speeds in producing optical fibers. If you raise the furnace temperature further or increase the length of the furnace, the silicone will oxidize and the fiber being pulled will begin to be affected, so for commercially available thermoset silicone coatings, increase the line speed to about 30 m/min or higher. I can't.

In the desire to increase production speeds, optical fiber manufacturers have begun researching ultraviolet (UV) curable materials. However, a coated composition with a combination of properties comparable to the silicone materials described above has not yet been found.

The inventors have discovered that certain UV-curable polysiloxane compositions provide new coating materials for optical fibers that exhibit a desirable combination of properties for optical fiber coatings. Both low and high refractive index compositions have been found, all of which cure quickly with short exposure to ultraviolet light and are thus safer and safer than thermoset silicone materials.
Significant advantages in cure speed and cost are obtained.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a fast curing composition to replace thermosetting polydimethylsiloxane compositions for the primary coating layer of optical fibers.

Another object of the invention is to provide a coating material for optical fibers that can be easily and safely coated and cured by short exposure to ultraviolet light.

Another object of the invention is to provide new low and high refractive index coating compositions.

Still another object of the present invention is that it can be manufactured efficiently and at low cost;
An object of the present invention is to provide a coated optical fiber applicable to various light wave telecommunication applications.

A further object of the present invention is to form a cured coating that is flexible, does not adhere tightly to the core fiber, can withstand large changes in environmental conditions, and allows for increased production line speeds. An object of the present invention is to provide a method for coating an optical fiber core with a primary coating.

An ultraviolet curable coating composition that achieves the above object and other objects has the formula (A) RR'EIiO, where R is hydrogen or a monovalent hydrocarbon group having 1 to 8 carbon atoms; is hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group having 2 to 20 carbon atoms having epoxy or vinyl functionality; Contains a photoinitiator.

In the present invention, a core of high-transparency silica glass; and R'
is hydrogen, a monovalent hydrocarbon radical of 1 to 2 carbon atoms or 2 to 20 carbon atoms with epoxy or vinyl functionality.
A UV-curable silicone coating composition containing a diorganopolysiloxane containing units of monovalent organic groups (11) and a catalytic amount of a photoinitiator has a refractive index higher than that of the silica glass described above. Coated optical fibers consisting of low coatings and are also considered.

According to still another aspect of the present invention, (1) (i) Formula RR'SiO (wherein R is hydrogen or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and r'' is hydrogen, carbon (11) a catalytic amount of photoinitiation; (2) exposing the coated core fiber to ultraviolet light of sufficient intensity for a sufficient period of time to coat a high transparency silica glass core fiber with a UV-curable silicone coating composition containing a UV-curing agent; A fast method of manufacturing a coated optical fiber is provided which comprises curing a coating composition to form a flexible, less adhesive, environmentally stable coating on the core fiber with a refractive index higher or lower than that of the core fiber. Ru.

Methods are also contemplated to effectively control the refractive index and viscosity of the polysiloxane coating materials disclosed herein.

For purposes of the present invention, the term "low adhesion" refers to the desirable properties of the primary coating layer over the glass optical fiber, such that the coating layer is not strong enough to interfere with normal mechanical operations applied to the optical fiber, such as bonding. does not adhere to the core fiber. This term does not relate to the optical relationship between the core and the coating (sub-coating) layer. The term "environmental stability" also refers to
The coating material of the present invention can be used to protect against environmental changes to which the fiber is normally subjected.
It particularly concerns its ability to maintain its integrity and optical properties through temperature changes between the upper and lower limits of about -60°C to +80°C.

DETAILED DESCRIPTION OF THE INVENTION To produce a fast-curing optical fiber T-
coating a transparent silica glass fiber with a V-curable epoxy- or vinyl-functional silicone coating composition;
This is then briefly exposed to UV light. The cured optical fibers of the present invention possess all of the desirable properties found in thermoset polydimethylsiloxane coated fibers, while increasing manufacturing capacity, reducing energy consumption, and improving UV curing safety. Guarantee.

Ultraviolet radiation (TRV) is one of the most widely used radiations because it is low cost, easy to manage, and poses little potential harm to industrial users. UV curable compositions exhibit extremely short cure times and avoid all of the high energy costs, environmental constraints and safety hazards associated with the use of thermoset materials.

The UV-curable compositions used in the present invention essentially consist of two components: (i) an epoxy- or vinyl-functional organopolysiloxane-based polymer and (11) rapid curing of the composition upon exposure to ultraviolet light. in combination with a photoinitiator that can promote

The epoxy-functional organopolysiloxane-based polymers contemplated in this invention consist of units having the general formula RR'SiOi. where R1j hydrogen or carbon atom number 1-
B is a monovalent hydrocarbon group, and R' is the same as R or a monovalent organic group having 2 to 20 carbon atoms and having epoxy functionality. The epoxy silicone polymer can have up to about 20% by weight epoxy functionality and must be capable of curing or crosslinking when exposed to ultraviolet light in combination with a suitable photoinitiator. The cured polymer composition must be of a lower or higher refractive index than the optical fiber core and must exhibit flexibility, low adhesion to the core fiber, and environmental stability.

Suitable epoxy-functional polydiorganosiloxanes contemplated by the present invention are more particularly dialkyl epoxy chain-terminated polydialkyl alkyl epoxy siloxane copolymers in which the polysiloxane units contain lower alkyl substituents, especially methyl groups. . To obtain the epoxy functionality, some of the hydrogen atoms on the polysiloxane chains of the polydimethyl-methylhydrogen siloxane copolymer are removed in a hydrosilation addition reaction containing both ethylenically unsaturation and epoxide functionality. react with organic molecules. The ethylenically unsaturated species is added to the polyhydroalkylsiloxane to form a functionalized conjugate in the presence of a catalytic amount of a noble metal catalyst. While such reactions are the crosslinking mechanism for other silicone compositions, in the present invention a controlled amount of crosslinking occurs in the silicone precursor or intermediate fluid.

This is called "pre-crosslinking." Precrosslinking of the silicone precursor fluid means that partial crosslinking or curing of the composition has occurred, and this results in rapid UV-initiated curing with little energy expenditure and no need for solvents. The present invention has the advantage of enabling.

The UV-curable epoxy-functional silicone intermediate fluid comprises a precrosslinked epoxy-functional dialkyl epoxy chain-terminated polydialkyl-alkyl epoxy silicone copolymer fluid, which is a vinyl or allyl functional epoxide and a viscosity of 25°C. Approximately 1 to 1 o o, o o
o centipoise vinyl functional siloxane crosslinking fluid having a viscosity of about 1 to 10 centipoise at 25°C. A hydrogen-functional siloxane precursor fluid that is OOO centipoise is reacted in the presence of an effective amount of a noble metal catalyst to promote an addition cure hydrosilation reaction between a vinyl-functional crosslinking fluid, a vinyl-functional epoxide, and a hydrogen-functional siloxane precursor fluid. let me,
It is a reaction product.

The unsaturated epoxides contemplated herein may be any of a number of aliphatic or cycloaliphatic epoxy compounds having olefinic moieties that readily undergo addition reactions to the =81H functionality. Examples of such compounds include 1-methyl-4-isopropenylcyclohexene oxide (limonene oxide; manufactured by 80MCorp), 2,6-cymethyl-243
-Epoxy-7-octene (manufactured by EICM Corp)
and 1,4-dimethyl-4-vinylcyclohexene oxide (manufactured by Viking (3hemical Co.). Limonene oxide is preferred.

The noble metal catalyst for the hydrosilation reaction related to the present invention is:
It may be selected from the group of platinum group metal complexes including complexes of ruthenium, rhodium, palladium, osmium, iridium and platinum.

Specific examples of hydrosilation catalysts suitable for purposes herein include U.S. Pat. No. '5.220.972 (Lamoreaux
), No. 3.715.334 (Karstedt
), No. 3.775°452 (Karstedt)
and No. 3.814°730 (Karstedt
) It is described in.

In the present invention, the vinyl-functional siloxane crosslinking fluids include dimethylvinyl chain-terminated linear polydimethylsiloxane, dimethylvinyl chain-terminated polydimethyl-methylvinylsiloxane copolymer, tetravinyltetramethylcyclotetrasiloxane, and tetramethyldivinyl divinylsiloxane. It can be selected from the group consisting of siloxanes. hydrogen-functional siloxane front fluid, tetrahydrotetramethylcyclotetrasiloxane, dimethylhydrogen chain-terminated linear polydimethylsiloxane, dimethylhydrogen chain-terminated polydimethyl-methylhydrogensiloxane copolymer, and tetramethyldihydrodisiloxane. can do.

Suitable photoinitiators for the epoxy-functional base polymers of the present invention include iodonium salts having the general formula: Here X is 8bF
6, AθF6, PF', and BF4, R
' is a monovalent alkyl or haloalkyl group having 4 to 20 carbon atoms, and n is an integer equal to 1 to 5. These compounds are disclosed in U.S. Pat. No. 4.279.717 (Eck
berg et al.) is extremely efficient in promoting a UV-initiated cationic ring-opening curing mechanism for epoxy-functional polysiloxanes. I confirmed it.

Among the iodonium salt photoinitiators for use with the epoxy-functional silicones of this invention are "linear alkylates".
Diaryliodonium salts derived from dodecylbenzene are preferred. Such salts have the general formula: (where x is SbF, AsF4, PF6 or FiB
B"n). These bis(4-dodecylphenyl)iodonium salts are highly effective initiators for the UV curing of a wide range of epoxy-functional silicones.

"Linear Alkylate" Dodecylbenzene is well known in the industry and is produced by the Friedel-Crafts alkylation reaction of benzene with an O(II-%3) alpha-olefin fraction. As a result, although the alkylate predominately contains branched chain dodecylbenzene, it actually contains other isomers of dodecylbenzene, such as ethyldecylbenzene and isomers such as uredecylbenzene and tridecylbenzene. are also present in large quantities. However, such mixtures contribute to the dispersive nature of the linear alkylate-derived catalyst and help keep the sides fluid. These catalysts are free-flowing viscous fluids at room temperature.

Preferred nabis(dodecylphenyl)iodonium salts are alkane soluble and water insoluble and disperse well in the preferred epoxy functional polysiloxanes used in the compositions of the present invention. Bis(4-n-tritecylphenyl)iodonium hexafluoroantimonate and bis(4-n-
Dodecylphenyl)iodonium hexafluoroantimonate is also preferred.

Vinyl functional base polymers contemplated in this invention include:
It is actually a photoreactive terpolymer that can be cured when exposed to UV radiation in the presence of certain radical photoinitiators. The terpolymer is a dimethylvinyl chain-terminated and trimethyl chain-terminated linear polydimethyl-methylvinyl-methylhydrogen-oxane terpolymer mixed fluid, polymethylhydrogen siloxane fluid, tetramethyltetravinylcyclotetra-70xane (methylvinyltetramer)
These vinyl functional terpolymers can be synthesized by acid equilibration reactions of octamethylcyclotetrasiloxane (dimethyltetramer) and octamethylcyclotetrasiloxane (dimethyltetramer). Two or more benzene terms that can be crosslinked? have Curable in the presence of polyaromatic photosensitizers. Among these photosensitizers, benzophenone and t-butylanthraquinone are preferred.

The terpolymer can also be cured in the presence of certain benzoate esters (J benzoate esters) having the following general formula:

Here, R3 is a -valent alkyl or aryl group, and z
is hydrogen, alkoxy, alkyl, halogen, nitro, amino, primary and secondary amino, amido, and the like. The nature of 2 influences the stability of the peroxy bond, with electron-deficient substituents stabilizing the peroxy bond, while electron-rich substituents make the peroxy bond more reactive. Suitable benzoate esters include t-butylperbenzoate and its para-substituted derivatives, such as t-butylperu-nitrobenzoate, t-butylperu-p-methoxybenzoate, t-butylperu-p-methylbenzoate and t-butylperu-p- There is chlorobenzoate.

The photoreactive polysiloxane terpolymers of the present invention and the photoinitiators useful therewith are disclosed in U.S. Patent Application No. 527, filed on the same date as the corresponding U.S. application.
299.

The amount of photoinitiator used is not critical as long as proper curing occurs. As with all catalysts, it is preferred to use one minimum effective amount. However, for purposes of illustration, catalyst levels of about 1-5% by weight have been found to be suitable for the compounds described above. Combinations of photoinitiators can also be used.

The epoxy- and vinyl-functional polysiloxanes described above typically have a low refractive index, i.e., less than 1.47, when the non-epoxy or non-vinyl substituent on the siloxane polymer chain is hydrogen or lower alkyl. It has a refractive index. The refractive index of polysiloxanes can be increased by incorporating polymers that also contain diphenylsiloxy units.

As mentioned above, epoxy-functional polydiorganosiloxanes can be obtained by reacting vinyl-functional epoxides with SiH-containing polydiorganosiloxanes, such as polydimethyl-methylhydrogen siloxane copolymers. Relatively high refractive index? To obtain diphenylsiloxy-containing and S1H-containing polysiloxanes, diphenylsiloxy-containing and S1H-containing polysiloxanes can be synthesized by cohydrolysis of diphenyldichlorosilane, dimethyldichlorosilane and methylhydrogendichlorosilane, and theoretically this polymer can be reacted with a vinyl-functional epoxide. This can impart epoxy functionality to the polymer. However, is it possible that a small amount of acid residue that accompanies such a linear high phenyl SiH polymer and is difficult to remove cleaves the oxirane ring of the epoxide? None, this results in a polysiloxane society that is not photoreactive. Another drawback of this method is that in order to increase the refractive index i to 1.50 or more, the polymer must contain 30 molti or more (50 molts upwind) of diphenylsiloxy units; Makes siloxane very expensive.

An important feature of the present invention is the discovery of an economical method for producing UV-curable epoxy-functional silicones with a refractive index greater than 1.47, which allows the compositions of the present invention to be used in a wide range of applications. Suitable for optical fiber coating applications. In a preferred embodiment of the invention, SiH-containing polysiloxanes having 1 carbon atom are used to prepare high refractive index compositions.
~20 is reacted with both a vinyl-functional aromatic compound (to obtain an aromatic substituent on the chain) and a vinyl-functional epoxide (to obtain an epoxy-functional substituent).

The vinyl-functional aromatic compound has at least one aromatic W
e gold-containing as well as 8 through hydrosilation addition reaction.
Contains at least one aliphatic unsaturation site capable of reacting with a 1H group to form a carbon-silicon bond. Ethynylbenzene (i.e. tystyrene) is also suitable, but
Numerous other vinyl aromatic compounds will be apparent to those skilled in the art and are intended to be included in the above compounds.

In the reaction of the EliH-containing polysilocane 7, the vinyl aromatic compound and the unsaturated epoxide can be introduced simultaneously (competing for the hydride reaction site) or preferably sequentially, with the latter resulting in a higher final The epoxy functionality and refractive index of the product can be well controlled. Since increasing the refractive index of the composition is the primary purpose of using such vinyl aromatic compounds, it is also preferred to react the vinyl aromatic compound first and add the epoxy functionality second. The exact relative amounts of vinyl aromatic compound and vinyl functional epoxide used can vary over a wide range depending on the desired refractive index and desired degree of reactivity. By appropriate selection of reactants, their amounts, and reaction conditions, high refractive index epoxy-functional silicones can be produced tailored to specific requirements.

From this point of view, it is good to conduct simple experiments regarding reaction parameters.

Combinations of iodonium salt photoinitiators and other known photoinitiators are also contemplated. Among such catalyst blends, combinations of iodonium salts and free radical photoinitiators, such as acetophenone derivatives, are preferred. Equivalent amounts of diaryliodonium salt and jetoxyacetophenone<
1:1) blend is also suitable.

The UV curable silicone coating composition of the present invention is coated onto optical fibers by methods well known in the art. For example, typically an uncoated optical fiber is passed through a coating solution and then placed in a curing chamber. Pull it through. As previously mentioned, the curing process has traditionally been the limiting factor in the speed at which coating operations can be performed. Providing a flexible, low-adhesion, environmentally stable primary coating on a silica glass core fiber by using an epoxy-functional silicone coating composition that can be cured by short-term exposure to ultraviolet light in accordance with the present invention The coating can be applied at high line speeds and without exposing the coating material or fiber to the high temperatures of the furnace.

As the compositions of the present invention allow increased line speeds, it has been found that the viscosity of the coating composition becomes an additional property that optical fiber manufacturers must consider (Examples 1- (See 3).

Generally, it is found that at high manufacturing speeds, one wetting (ie, coating) of the fiber is not possible at viscosities below about 1000 cps. At viscosities higher than about 10,000 cps, air bubbles will be entrained in the coating, creating defects in the -order coating that cause signal attenuation.

In the case of epoxy-functional silico-/ produced via the hydrosilation addition reaction of vinyl-functional epoxides to SiH-containing polysiloxanes, the viscosity of the final product depends not only on the viscosity of the SiH-containing precursor but also on the epoxy-functional It is difficult to predict as it depends on the severity. For example, a 90 cps precursor fluid containing 10% by weight of methylhydrogensiloxy units is 18% by weight of limonene oxide? Viscosity approximately 400 cps when converted to introduced epoxy functional silicone
So, 10 units of methyl hydrogen by weight? The containing 200 cps precursor fluid is converted to an epoxy functional silicone with a viscosity of 1000 ape. and 200 cps containing 6 weight i% methylhydrogensiloxy units.
Introducing 117% by weight of limonene oxide into the precursor fluid results in a viscosity of 1000 ape.

It has been found that co-addition of vinyl MQ silicone resin and vinyl functional epoxide to certain 131H-containing polysiloxanes results in products whose viscosity is dependent on resin content. The vinyl MQ resins considered here are polysiloxanes having primarily monofunctional (M) or tetrafunctional CQ) units. The vinyl groups of this resin compete with the vinyl functional epoxide for available hydride positions in the polysiloxane. The resin is thus incorporated into the epoxy-functional polysiloxane product.

Vinyl MQ, the resin is composed of M units with 2 Ys8i0H and Q units with 25ill 'i, with a ratio of M to Q units of approximately C1,5 to 1.0, preferably about [1L65
It is. Each Y group independently represents the same or different monovalent hydrocarbon radicals having up to 2 carbon atoms, and at least one Y group must be vinyl. Such groups include, for example, methyl, ethyl, vinyl or ethynyl. Methyl and vinyl are preferred. A general description of these resins is given by IJoll [Chemistry and Te
found in chapters 1 and 6 of Chnology of 5iliconee J (2nd edition, 1968).

In an embodiment of the present invention that takes advantage of the above findings, the final υV curable polysiloxane product contains pendant siloxy groups that correspond to the incorporated MQ resin. In the case of these polysiloxanes, the definition of the R' group in the above formula is 20iO% of 1 to 200 Q siloxy units and 2
It is extended to include branched organosiloxane groups with M siloxy units of zero (where Y is a monovalent hydrocarbon group having 1 to 2 carbon atoms). The terms "diorganopolysiloxane" and "organopolysiloxane-based polymer" used herein to describe the epoxy and vinyl functional polymer products of the present invention include such branched polysiloxanes. It is a sufficiently broad term to include groups.

If a high refractive index material is desired, an alternative method of altering the viscosity of the coating composition, which also introduces index-increasing aromatic groups into the system, is to use aromatic glycidyl ethers as reactive diluents. Aromatic glycidyl ether reactive diluents also add epoxy functionality, thus improving the curing properties of the coating compositions of the present invention. This is a common finding for silicone paper release compositions with added epoxy polymers in US Pat.

The following examples are presented by way of illustration and not by way of limitation, so that those skilled in the art may better understand the practice of the invention.

Examples 1-3 Three epoxy-functional silicone coating compositions were prepared as follows for optical fiber coating experiments.

Sample 1 5 parts by weight of 250 cps dimethylvinyl chain-stopped polydimethylsiloxane fluid, 320 parts by weight of limonene oxide, and 1 part by weight of platinum catalyst (platinum-octyl alcohol hexafluoride) 11. ooo was added to 31 parts of toluene. Add to this mixture +, 000 while stirring at room temperature.
150 cps dimethylhydrogen chain-terminated polydimethyl-methylhydrogen siloxane copolymer fluid (containing about a7 parts by weight of SiH) was slowly added over a period of 1 hour. Then the reaction mixture? The mixture was refluxed at 120° C. for 21 hours, 30 parts by weight of n-hexene was added at the 21st hour, and reflux was continued for an additional 4 hours. Stripping of the solvent at 130° C. under vacuum yielded a t 000 Qpθ limonene oxide functional, functional polysiloxane fluid reservoir containing about 17.2% by weight of limonene oxide groups.

It was manufactured following the same procedure as in case of 1. Sample 2 contains approximately 14.0% by weight of limonene oxide groups.
At 80 cps of fluid, sample 3ij was a 700 cp theta fluid containing approximately 11.7% by weight limonene oxide groups.

All three compositions were combined with 1.5% by weight of bis(dodecylphenyl)iodonium hexafluoroantimonate cationic photoinitiator.

Each coating composition was coated onto a 10 mil diameter pure silica glass fiber immediately after it was drawn. The coating device was a small cup fitted with a 0.025 inch orifice at the bottom. Coating was performed by pulling the drawn optical fiber downward into the test composition and then through an orifice to control the coating thickness. The coated fiber was immediately passed through a nitrogen-inert curing chamber where one focused 300 watt, 10 inch long FusionSy
stems rE J UV lamp exposure. The coated fiber was finally wound onto a take-up roll.

The coated fiber was observed to see if the coating was completely trap cured. The line speed was gradually increased to determine the line speed at which the coating on the fiber was not completely cured, ie, to find the point at which the line speed exceeded the cure rate.

For each sample examined, the coating composition cured completely even at line speeds that exceeded the coating speed. In other words, the "wetting" (ie, coating) of the optical fiber with the silicone fluid was complete at line speeds where complete curing was still observed. Complete curing was observed for the 3 gl sample composition under the following conditions.

Sample 1 50 125 Sample 2 30 120 Sample 5 33120 These results compare favorably to the maximum line speed of 30 m/min observed with commercially available thermosetting silicone systems.

60 containing 10% by weight of methylhydrogensiloxy units
600 parts by weight of cps linear dimethylhydrogen chain-terminated polydimethyl-methylhydrogen siloxane fluid was mixed with 600 parts by weight of hexane.
Parts by weight were dissolved. This solution (1,0 mol active SiH
containing 152 parts by weight of limonene oxide (
1 mole), approximately 25 ppm platinum in the form of a soluble complex catalyst, and various levels of vinyl MQ silicone resin. The reaction mixture was refluxed for 4 hours, after which unreacted EliHf was removed by reaction with hexene. Stripping of the solvent, unreacted limonene oxide and hexane under vacuum gave the epoxy functional polymer shown below.

Sample 4 19.6 0.0 340 Sample 5 1
a5 6900 sample 6 14,3 11.5 1976 sample 7
1 & 1 12.8 3800 tatami Weight % of limonene oxide introduced into the polymer ■ 100 parts by weight of each sample as the weight % of resin solids after solvent stripping (rl, stM part of jetoxyacetophenone and 1.5 Weight part (Os2'H!
5 Ph) 2 Engineering 5bF6 (U.S. Patent Application No. 375
The cure was evaluated in combination with a free radical/cationic cocatalyst system for curing epoxy-functional silicones disclosed in US Pat. 2. Apply the complete coating composition onto polyethylene kraft paper using an adhesive coater.
It was applied by hand as a mill coating and exposed to two focused medium pressure mercury vapor ultraviolet lamps attached to a PPG 1202 ultraviolet processor.

Curing was qualitatively evaluated by varying conveyor speed (exposure time), UV intensity, and curing environment. The following results were obtained.

4 300 1 N, 2.0 p 5400 Air 2.0 5 400 N, 2.5 tt As compared to the control composition (Sample 4), the set of epoxy-functional silicone compositions g'i Specific target viscosity It can be seen that the introduction of vinyl MQ resin does not result in a significant qualitative difference in curing, provided that it is kept within the range.

Example 8 10, in which limonene oxide of 11.3 weight ratio was introduced.
000 cps epoxy-functional polysiloxane 90 parts by weight f+, 2-xboxydodeca:y (Viko
lox■12, Viking Chemical Co.
A blend of 4200 cps was obtained. The co-catalysts of Examples 4-7 were added and the complete composition was exposed to 10 mils of light, 7 eyeglasses, in the same manner as Examples 1-3 above.
Coating was carried out at a pulling speed of up to 0'm/min. At a speed of 60 m/min the coating was extremely thin (less than 80 microns) and thermal decomposition (smoking) of the coating composition was evident as the fiber entering the coating bath was very hot.

However, the coating cured even at this speed upon exposure to a 300 watt Uv lamp. These results show that by using the composition of the present invention, the production line speed for optical fibers can be doubled with an appropriate formulation. Furthermore, ω-epoxy c(s
-tt) It is clear from this example that aliphatic hydrocarbons are useful as viscosity modifiers for the optical fiber nuclide compositions of the present invention.

Examples 9-12 75 cps Linear Trimethyl Chain-Terminated Polydimethyl-Methylhydrogen Siloxane Fluid 2 Having 44.9 Weight Parts of Methylhydrogensiloxy Units (t5 Moles of Active SiH Groups)
00 parts by weight were dispersed together with 126 parts by weight (1.27 moles) of styrene in 400 parts by weight of hexene. 0.35 parts by weight of platinum catalyst was added, and the reaction mixture was stirred and heated slowly to 0°C. At this point, an exothermic reaction occurred, and the temperature was raised to 75°C, then lowered to around 65°C, and then The reaction mixture was maintained at for 1 hour. Infrared analysis determined 123 moles of unreacted SiH, indicating that styrene addition was complete. Then 60 parts by weight (0.4 mol) of limonene oxide were added and the reaction mixture was brought back to 69° C. and kept at this temperature [64 hours] with stirring. The product is only CL007L007
Mol s, tn L are not shown and were removed by a brief reaction with hexene. Stripping of solvent and unreacted monomers yields a viscous fluid product with a refractive index of 1.492 (1
1,680 cps). This fluid, designated Sample 9, had 33,030 parts by weight of tyrene and 13.1 parts by weight of limonene oxide introduced. Three other compositions were prepared in a similar manner and the following results were obtained.

Styrene limonene oxide Viscosity composition (r, t'J) (wt%) (cps') Refractive index sample 9 33.0 151 11,680 1
．． 4920 sample 10 32.9 14.4 &10
0 1.4902 samples 11 29,1 29.1
88.00 [J 1.4930 Sample 12 31.8
22.1 21,000 t4970 Above polymer and cresyl glycidyl ether (DY 023, Giba
(manufactured by Geigy) to obtain the following composition.

Sample 9A 20.0 1,200 1.4990 Sample 10A 25.0 2.500 1.4992 Sample 11A 25.0 5600 1.5080 Sample 12A 25.0 1,680 1.5030 The above β-phenethyl and limonene oxide .

The UV hardening properties of substituted polysiloxane fluids were determined using jetoxyacetophenone (CHE15Ph 'h Engineering 8bF,
The catalyst-containing mixture was coated onto a polyethylene kraft substrate, and the coated substrate was then qualitatively investigated by exposing the coated substrate to ultraviolet light as described above.

The following results were obtained.

It was observed that the diaryl salt catalyst was much better soluble in the β-7 ethyl epoxy functional silicone than in the lower refractive index epoxy functional silicone described in the previous example. This means that if necessary catalyst concentration? It means that it can be made faster if it is made higher and hardens. Moreover, it is clear that the presence of the β-phenethyl substituent results in fast curing at low epoxy loadings, and that the ether blends described above cure equally well in air or an inert atmosphere. This makes the high refractive index composition a very efficient coating composition.

The presence of high amounts of talesyl glycidyl ether, such as 25%, keeps the curing rate high. It is expected that other aromatic monomers, such as bisphenol A diglycidyl ether and epoxy novolac resins, will be compatible with epoxy-functional silicones as well.

Example 13 Polysiloxane composition with low refractive index (below 1.43)?
Manufactured on the following day.

60 parts by weight trimethyl chain-terminated polydimethylmethylhydrogen siloxane fluid (25 cps), 84 parts by weight sym
-tetramethyltetravinylcyclotetrasiloxane and 1056 parts by weight of octamethylcyclotetrasiloxane were stirred in the presence of 6 parts by weight of IFiltrol 20 acid equilibration reaction catalyst at 100 DEG C. for 17 hours in a nitrogen atmosphere. The acid was neutralized by adding 6 parts by weight of MgO, and the mixture was held at 1100°C for another hour, after which the neutralized reaction product was stripped for 2 hours at 165°C under a vacuum of 48 kg Hg. 829 parts by weight of the fluid product were treated with 20.8 parts by weight of benzophenone, stirred at 70°C for 75 minutes, and then cooled to below 50°C. 4° parts by weight of t-butyl perbenzoate were added and the entire mixture was stirred for 210 minutes and then filtered to remove the solids FiltrO1 and MgOf, yielding a fluid product at 180° cps.

The composition was coated on polyethylene kraft paper to a thickness of 2 mils and then exposed to an ultraviolet lamp with a total power of 400 watts fitted to a PPG 1202 processor. The following results were obtained by curing at various line speeds.

Line speed Curing atmosphere Curing 50 ft/min Air Slightly dirty outside cures well2
00 ft/min N2 Slight dirt detection, otherwise satisfactory 400 ft/min N2 Surface hardening only (“skin”
(Production) The same composition was coated onto a 10 mil diameter optical fiber as described above and then coated with one 300 mil diameter optical fiber in an inert atmosphere.
Watsuto [HJ lamp (Fusion Bystema)
hardened by exposure to The fibers were well wetted by the coating material up to a pulling speed of about 35 m/min.

A well cured coating 140 microns thick was obtained.

At higher speeds, the coating material appeared to be fully cured even at speeds above 40 m/min, but the coating thickness decreased rapidly.

In accordance with the disclosure herein, UV-curable high refractive index vinyl-functional polymers in the presence of a benzoate catalyst are prepared with four different units, such as methylvinyl-, diphenyl-, dimethyl- and methylhydrogen-siloxy. It is expected that it can be manufactured in units.

Example 14 300 parts by weight (2.88 moles) of styrene were combined with 800 parts by weight of toluene and a platinum complex catalyst (25 p in the total mixture).
pm of platinum). The solution was heated to 80 °C, at which point it had a viscosity of 21 with 69 Tjl@% methylhydrogensiloxy units (total 4.61 mol 5LTl).
400 parts ft of cps trimethyl chain-terminated linear polydimethyl-methylhydrogen siloxane fluid was slowly heated over 4 hours, during which time reaction mixture 1 was heated to 81-84°C.
The temperature was maintained at . After stirring for 15 minutes, 289 parts (1.9 moles) of limonene oxide were added and the reaction mixture was refluxed at 82°C for 17 hours and then at 90°C for 22 hours. At this point, the number of unreacted 81H units is approximately 2.4.
I was assigned to Shigekata 1st Division. Unreacted 81H was removed by reaction with hexene and the product was stripped under vacuum at 140° C. for 40 minutes to give 880 parts by weight of 1111,800Q.
pB fluid was obtained. Assuming quantitative addition of styrene, this product, designated Sample 14, contained 31.9 weight percent styrene and 25.4 ffi weight percent norimonene oxide. The refractive index of this material was 1.503.

Coating compositions of appropriate viscosity were prepared by blending Sample 14 with various epoxy-functional reactive diluents selected from below.

DYO23 (Oiba Geigy) -〇Talesyl glycidyl ether 0Y179 (C1ba Geigy) -〇BPOBI■825 (She engineering□.hemica□6
) = each composition contains jetoxyacetophenone and (012H
t6Ph) On the 1st day, the catalyst was added at a ratio of 1 = 1 fluoride 5@ of bF6. The outline of the composition is as follows.

14A 10 10 - 1.506 14B 10 - 10 1.513 140 20 - 20 1.518 The composition was coated onto a polyethylene kraft substrate to a coating thickness of 1 mil and then coated with PPGQQ 1202 as previously described.
Cured with AN processor. The record of curing performance is as follows.

UV Power Line Speed - Sample 14 Air 600 2. Or skin hardening sample 14A Air 400 1.5 Excellent hardening sample 14A Air 400 2.0 Surface hardening only sample 14A 112400 2.0 Surface hardening only sample 14A Air 60 (12,5 Excellent hardening sample 14B Air 400 2. 0 Evidence of surface hardening Sample 14B Air 600 2.0 Excellent hardening sample 140 Air 400 2.0 Surface hardening only sample 140 Air 600 2.5 Excellent hardening Various changes and modifications of the present invention in light of the above disclosure. For example, in light of the examples, it is clear that limonene dioxide ('-spanning other polyepoxide monomers) is an effective epoxy-functional polysiloxane composition for high refractive index epoxy-functional polysiloxane compositions. The epoxy- or vinyl-functional polysiloxane compositions described herein may also be described, for example, in commonly assigned U.S. Patent Application No. 375.676 (May 1982). 6) and a U.S. patent application filed on the same date as the U.S. patent application of this application.
Modification with caloric additives to improve curing properties may also be advantageous in certain circumstances, as disclosed in US Pat. However, it is understood that these additional incidental modifications to the particular embodiments of the invention also fall within the scope of the invention.
It should.

Claims (1)

[Scope of Claims] 1. France) Highly transparent silica glass core, (B) Above: +71C coating, (i) Formula RR's1° (R in the formula is hydrogen or has 1 to 1 carbon atoms) 8 monovalent hydrocarbon group, "is hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group having 2 to 20 carbon atoms having epoxy or vinyl functionality" unit. and (11) a UV-curable silicone coating composition containing a catalytic amount of a photoinitiator, a coating having a refractive index higher or lower than that of the silica glass. l The diorganoboria xane is epoxy-functional and the photoinitiator has the following formula: (wherein X is SbF6, A
selected from the group consisting of sF3, PF6 and BF4, R' is a monovalent alkyl or haloalkyl group having 4 to 20 carbon atoms, and n is an integer equal to 1 to 5, alone or in combination. and a free radical photoinitiator.
Coated optical fiber as described in Section 2. 5. The coated light 7 eyer according to claim 2, wherein the diaryliodonium salt is a bis(dodecylphenyl)iodonium salt. 4. The photoinitiator is 7z from a combination of bis(dodecylphenyl)iodonium salt and jetoxyacetophenone.
A subject optical fiber according to claim 2. 5. The coated optical fiber of claim 2, wherein said diorganopolysiloxane has up to about 20% by weight epoxy functionality. The coated optical fiber according to claim 5, wherein the epoxy functional group is a limonene oxide group. Z The above diaryliodonium salt selected from cahis(4-n-to!Jdecylphenyl)iodonium hexafluoroantimonate and bahis(4-n-dodecylphenyl)iodonium hexafluoroantemonate. Coated optical fiber as described. &R' group of the above diorganopolysiloxane is vinyl M
The coated optical fiber according to claim 2, which is free from monovalent branched organosiloxanes derived from Q resins. 9. Claim 2, wherein said composition I also contains as component (iii) an amount of a reactive diluent selected from polyepoxylic acid monomers and aromatic glycidyl ethers in an amount sufficient to lower the viscosity. Coated optical fiber as described in Section 2. 11. The coated optical fiber of claim 9, wherein said reactive diluent is selected from the group consisting of limonene dioxide. 11. The coating has a higher refractive index than silica glass,
The above diorganopolysiloxane is mainly a polymer unit of the following formula: The coated optical fiber according to claim 2. 12. The coated optical 7-eyeper according to claim 1, wherein the diorganopolysiloxane is a terpolymer consisting of dimethylsiloxy, methylhydrogen, siloxy, and methylvinylsiloxy units. ” The photoinitiator is selected from the group consisting of benzoate esters, and polyaromatic photosensitizers having up to 20 carbon atoms having two or more benzene rings that can be fused or crosslinked with organic or heterogroups. Claim 1
The coated optical fiber according to item 2. 14. The coated optical fiber of claim 13, wherein said coating has a refractive index greater than 1.5 and said diorganopolysiloxane also contains diphenylsiloxy units. 15 (1) (+) Formula RR'SiO (RFi in the formula hydrogen or a monovalent hydrocarbon group having 1 to 8 carbon atoms h,
” is hydrogen, a monovalent hydrocarbon group of 1 to 20 carbon atoms or 2 to 2 carbon atoms with epoxy or vinyl functionality
coating a high transparency silica glass core fiber with a UV-curable silicone coating composition containing a diorganopolysiloxane containing units of (0 monovalent organic groups) and (11) a catalytic amount of a photoinitiator; 2) Expose this coated core fiber to ultraviolet light of sufficient intensity for a sufficient time to cure the coating composition on the core fiber so that the refractive index on the core fiber is higher or less flexible than the core fiber. A method for the rapid production of coated optical fibers that involves the process of forming an adhesive, environmentally stable coating. 16 The diorganopolysiloxane is epoxy-functional and the photoinitiator has the following formula: (wherein x is 81) F6
, AsF6, PF6 and BF4, R' is a monovalent alkyl or haloalkyl group having from 4 to 20 carbon atoms, and n is an integer equal to 1 to 5).
16. The method of claim 15 comprising a diaryliodonium salt of , alone or in combination with a free radical photoinitiator. 17. Claim 1, wherein the diaryliodonium salt is a bis(dodecylphenyl)iodonium salt.
The method described in Section 6. 1a. The method of claim 16, wherein said photoinitiator comprises a combination of bis(dodecylphenyl)iodonium salt and jetoxyacetophenone. 19, the diorganopolysiloxane is about 20i-1a
Epoxy functional groups up to %? Claim No. 16
The method described in section. 20. The method of claim 19, wherein the epoxy functional group is a limonene oxide group. 21. The above diaryliodonium salt is bis(4-n
-tritecylphenyl)iodonium hexafluoroantimonate and bis(4-n-dotesylphenyl)
20. The method of claim 19, wherein the method is selected from iodonium hexafluoroantimonate. 2Z Is the coating process (1) core fiber? The exposure step (
16. The method of claim 15, wherein step 2) is carried out consecutively with step (]) by drawing the coated fiber through a curing chamber equipped with a UV light source immediately after coating step (1). 25. The method of claim 16, wherein the R' group of said diorganopolysiloxane can also be combined with a monovalent branched organosiloxane derived from vinyl MQ resin. 24. Claim 16, wherein the coating composition also contains as component (iii) an amount of a reactive diluent selected from polyepoxide monomers and aromatic glycidyl ethers sufficient to reduce the viscosity. the method of. 25. The method of claim 24, wherein said reactive diluent is selected from the group consisting of limonene dioxide. 26 The coating has a refractive index higher than 7 Licas,
17. The method of claim 16, wherein said diorganopolysiloxane is comprised primarily of polymeric units of formula 2. 2z The method of claim 15, wherein said diorganopolysiloxane is a turborib comprising dimethylsiloxy, methylhydrogensiloxy and methylvinylsiloxy units. 2a The photoinitiator is a benzoate ester and a polyaromatic photosensitizer having up to 20 carbon atoms and having two or more be/zene rings which can be fused or crosslinked with an organic group or a hetero group. 28. The method of claim 27, wherein the method is selected from the group. 29. The method of claim 28, wherein said coating has a refractive index greater than 1.5 and said diorganopolysiloxane also contains diphenyl 7 units.