Connect public, paid and private patent data with Google Patents Public Datasets

Optical fiber coated with an organopolysiloxane curable actinic rays

Download PDF

Info

Publication number
USRE33737E
USRE33737E US07492779 US49277990A USRE33737E US RE33737 E USRE33737 E US RE33737E US 07492779 US07492779 US 07492779 US 49277990 A US49277990 A US 49277990A US RE33737 E USRE33737 E US RE33737E
Authority
US
Grant status
Grant
Patent type
Prior art keywords
sub
ch
organopolysiloxane
sime
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07492779
Inventor
Yoshinori Hida
Shohei Kozakai
Seiji Katayama
Noriyuki Meguriya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin-Etsu Chemical Co Ltd
Original Assignee
Shin-Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B6/00Light guides
    • G02B6/44Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401Optical cables
    • G02B6/4429Strengthening and protecting features
    • G02B6/443Protective covering
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments from glass, minerals, or slags
    • C03C25/10Surface treatment of fibres or filaments from glass, minerals, or slags by coating
    • C03C25/104Surface treatment of fibres or filaments from glass, minerals, or slags by coating to obtain optical fibres
    • C03C25/1045Surface treatment of fibres or filaments from glass, minerals, or slags by coating to obtain optical fibres with organic coatings or claddings
    • C03C25/1055Organic coatings
    • C03C25/106Single coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2962Silane, silicone or siloxane in coating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31551Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609Particulate metal or metal compound-containing
    • Y10T428/31612As silicone, silane or siloxane

Abstract

The coated optical fiber of the invention is prepared by providing a coating layer of an ultraviolet-curable organopolysiloxane or a composition comprising the same and irradiating the coating layer with ultraviolet. Specifically, each of the terminal silicon atoms of the organopolysiloxane, which preferably has a linear molecular structure, has two or more ethylenically unsaturated polymerizable groups bonded thereto through an oxygen atom, such as CH2 ═CHCOOCH2 CH2 --, [CH2 ═C(CH3)COOCH2 ]3 C--CH2 -- and (CH2 ═CHCOOCH2)2 C(C2 H5)CH2 --. By virtue of this unique molecular structure of the organopolysiloxane, the coating layer is rapidly cured by ultraviolet irradiation to give a cured coating layer exhibiting very low water absorption and small temperature dependency of the Young's modulus at low temperatures.

Description

BACKGROUND OF THE INVENTION

The present invention relates to a coated optical fiber or, more particularly, to an optical fiber coated with a layer of a cured organopolysiloxane curable by irradiation with actinic rays and having low water absorption as well as small temperature dependency of the Young's modulus as well as a method for the preparation of such a coated optical fiber.

As is known, various materials are used for optical fibers in service of the optical communication including fused quartz glass, multi-component glass and plastics. In view of the lightweight, low transmission loss, absence of induction, heat resistance and weatherability as well as large transmission capacity, however, most of the optical fibers in practical services are made of fused quartz glass. It is usual that quartz glass-made optical fibers are provided with a coating layer of a certain protecting material since quartz glass fibers are usually very small in diameter and subject to changes of the performance in the lapse of time.

Various materials have been proposed for the coating layer on quartz glass-made optical fibers including so-called silicones and organic polymers. For example, a typical silicone material for optical fiber coating is an organopolysiloxane composition comprising an organopolysiloxane having vinyl groups bonded to the silicon atoms and an organohydrogenpolysiloxane having hydrogen atoms directly bonded to the silicon atoms, of which a cured coating layer is formed by the addition reaction or so-called hydrosilation between the silicon-bonded vinyl groups and silicon-bonded hydrogen atoms in the presence of a platinum catalyst. Another curable silicone material for optical fiber coating is an organopolysiloxane composition comprising a vinyl-containing organopolysiloxane and a mercaptoalkyl-containing organopolysiloxane to effect an addition reaction between the vinyl and mercapto groups. Organic polymers include those by use of a polyether urethane acrylate or polybutadiene urethane acrylate.

These prior art coating materials for optical fibers have their respective problems and disadvantages. For example, the organopolysiloxane compositions by the hydrosilation reaction have a problem that the organohydrogenpolysiloxane is susceptible to the reaction with atmospheric moisture to evolve hydrogen gas which causes increase in the transmission loss through the optical fiber coated therewith. The organopolysiloxane compositions by the mercapto-vinyl addition reaction are sometimes unacceptable due to the very unpleasant odor ascribable to the mercapto groups emitted in the course of the curing reaction. The coating materials based on a polyether urethane acrylate have disadvantages of large water absorption and unduly high rigidity at low temperatures to increase the transmission loss of the coated optical fibers while those based on a polybutadiene urethane acrylate are disadvantageous in respect of the low curability. Accordingly, it is eagerly desired to develop a novel optical fiber coated with a coating material free from the above described problems and disadvantages in the prior art.

SUMMARY OF THE INVENTION

Accordingly, the present invention has an object to provide a novel coated optical fiber of which the above described problems and disadvantages are dissolved by use of a specific organopolysiloxane as the coating material.

Thus, the coated optical fiber of the present invention comprises:

(a) a quartz glass-made optical fiber base; and

(b) a coating layer, on the quartz glass-made optical fiber base, of an -organopolysiloxane which is represented by the average unit formula

(R.sup.1).sub.a [(R.sup.3 O).sub.n (R.sup.4).sub.3--n--m (R.sup.5 O).sub.m Si--R.sup.2 --].sub.b SiO.sub.(4--a--b)/2,                (I)

in which the groups denoted by R1 and R4 are each, independently from the others, a substituted or unsubstituted monovalent hydrocarbon group, R2 is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, R3 is a monovalent organic group having 4 to 25 carbon atoms and 1 to 3 ethylenically unsaturated groups, R5 is a monovalent hydrocarbon group free from aliphatic unsaturation having 1 to 18 carbon atoms or an organosilyl group of the general formula

--SiR.sup.6.sub.2 --O).sub.p SiR.sup.6.sub.3,              (II)

R6 being a monovalent hydrocarbon group having 1 to 9 carbon atoms and p being zero or a positive integer, a is a positive number in the range from 1.6 to 2.2, b is a positive number in the range from .[.0.02.]. .Iadd.0.002 .Iaddend.to 0.5 with the proviso that a+b is in the range from 1.8 to 2.2, n is 1, 2 or 3, m is zero, 1 or 2 with the proviso that n+m is 1, 2 or 3 and R3 has at least two ethylenically unsaturated groups when n is 1.

The present invention also provides a method for the preparation of an optical fiber coated with a layer of a cured organopolysiloxane which comprises coating a quartz glass-made optical fiber base with an organopolysiloxane represented by the above given average unit formula (I) and irradiating the organopolysiloxane with actinic rays such as ultraviolet light.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As is understood from the above given summary of the invention, the most characteristic feature of the inventive coated optical fiber is that the coating layer on the quartz glass-made optical fiber base is formed by curing a specific organopolysiloxane curable by irradiation with actinic rays and represented by the average unit formula (I) given above. The organopolysiloxane is readily cured by irradiation with actinic rays such as ultraviolet so that the process of forming the coating layer on the optical fiber base can be performed with a high efficiency and the thus radiationcured coating layer of the organopolysiloxane has outstandingly low water absorption and temperature dependency of the Young's modulus at low temperatures of, for example -10° to -30° C. Needless to say, the coating material is free from the problem of any unpleasant odor.

The coating material used for forming the coating layer of the inventive coated optical fiber is the above described organopolysiloxane represented by the average unit formula (I) or a composition comprising the same as the principal ingredient. In the formula (I), the groups denoted by the symbols R1 and R4 are each, independently from the others, a monovalent hydrocarbon group having 1 to 9 carbon atoms exemplified by alkyl groups, e.g. methyl, ethyl, propyl, butyl and octyl groups, cycloalkyl groups, e.g. cyclohexyl group, alkenyl groups, e.g. vinyl and allyl groups, aryl groups, e.g. phenyl and tolyl groups, and aralkyl groups, e.g. 3-phenylpropyl group, as well as those substituted groups obtained by the replacement of a part or all of the hydrogen atoms in the above named hydrocarbon groups with substituent atoms and/or groups such as halogen atoms and cyano groups including chloromethyl, 3,3,3-trifluoropropyl and 2-cyanoethyl groups. It is preferable that at least 50% by moles of the group denoted by the symbols R1 and R4 should be methyl groups and the molar content of phenyl groups, if any, should not exceed 35% of the groups of R1 and R4. When at least a part of R1 and R4 are phenyl groups, the group Rz should preferably be an ethylene group.

The group denoted by the symbol R2 is, when it is a divalent hydrocarbon group having 2 to 4 carbon atoms, exemplified by ethylene, propylene and butylene groups. The group R2 may optionally be an oxygen atom although an oxygen atom as R2 is less preferably in respect of the relatively low resistance of the coating layer against water. The group denoted by the symbol R3 is a monovalent hydrocarbon group having 4 to 25 carbon atoms and having, in a molecule, 1 to 3 ethylenically unsaturated functional groups such as CH2 ═CHCOO--, CH2 ═C(CH3)COO-- and CH2 ═CHCO-- exemplified by CH2 ═CHCOOCH2 CH2 --, [CH2 ═C(CH3)COOCH2 ]3 C--CH2 -- and (CH2 ═CHCOOCH2)2 C(C2 H5)CH2 --. The group denoted by the symbol R5 is, when it is a monovalent hydrocarbon group free from aliphatic unsaturation having 1 to 18 carbon atoms, exemplified by alkyl groups, e.g. methyl, ethyl, propyl, butyl, pentyl and neopentyl groups. Alternatively, the group denoted by R5 may be an organosilyl group represented by the general formula (II) given above, in which R6 has the same meaning as R1 defined above and the subscript p is zero or a positive integer. Examples of such organosilyl groups include methyl ethyl phenyl silyl, trimethyl silyl, dimethyl phenyl silyl and vinyl dimethyl silyl groups with p equal to zero and organosiloxy-substituted silyl groups. The meaning of each of the subscripts a, b, m nad n is defined already. When n is equal to 1, the group R3 should preferably have more than one ethylenically unsaturated functional groups.

Since the group R3 O necessarily contained in the organopolysiloxane is sensitive to actinic rays, the organopolysiloxane can be readily cured by irradiating with actinic rays such as ultraviolet light. The organopolysiloxane should preferably have a viscosity in the range from 1,000 to 20,000 centipoise at 25° C. When the viscosity of the organopolysiloxane is too low, the quartz glass-made optical fiber base is poorly wettable with the organopolysiloxane in addition to the difficulty in obtaining a coating layer thereof having an adequate thickness. When the viscosity of the organopolysiloxane is too high, on the other hand, disadvantages are caused in the removal of air bubbles from the coating layer as well as in respect of the difficulties in obtaining an adequate thickness of the coating layer and decreased workability.

The organopolysiloxane represented by the average unit formula (I) can be prepared by the dehydrochlorination reaction between an organopolysiloxane of a corresponding molecular structure having chlorine atoms directly bonded to the silicon atoms and an ethylenically unsaturated compound having an active hydroxy group in the molecule. The above mentioned chlorine-containing organopolysiloxane is exemplified by those compounds expressed by the following structural formulas, denoting methyl and phenyl groups by the symbols Me and Ph, respectively:

Cl2 MeSi--CH2 CH2 --SiMe2 --O--SiMe2 --O)100 --SiMe2 --CH2 CH2 --SiMeCl2 ;

Cl3 Si--CH2 CH2 --SiMe2 --O--SiMe2 O)68 (SiPh2 --O)30 --SiMe(CH2 CH2 SiCl3)--O]2 SiMe2 --CH2 CH2 --SiCl3 ;

ClMe2 Si--O--SiMe2 --O)150 SiMe2 Cl;

ClMe2 Si--O--SiMe2 --O)50 [SiMe(CH2 CHMePh)--O]50 --SiMe2 Cl; and

Cl2 MeSi--CH2 CH2 --SiMe2 --O--SiMe2 --O)130 --SiMe(CH2 CH2 CF3)--O]20 SiMe2 --CH2 CH2 --SiMeCl2.

The hydroxy-containing ethylenically unsaturated compound to be reacted with the above described chlorine-containing organopolysiloxane is exemplified by 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerithritol tri(meth)acrylate and the like, of which the last mentioned pentaerithritol derivatives are advantageous since the resultant organopolysiloxane of the average unit formula (I) should preferably have two or more of the ethylenically unsaturated groups bonded to the same silicon atom.

In the above described dehydrochlorination reaction, not all of the chlorine atoms in the chlorine-containing organopolysiloxane must be reacted with the ethylenically unsaturated hydroxy-containing compound. Namely, it is optional with an object to adequately control the viscosity of the organopolysiloxane or hardness of the cured product thereof that a part of the functional groups may be alkoxy groups or organosiloxy groups introduced by the reaction with an alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-methylpropan-1-ol, 2-methylpropan-2-ol, 2,2-dimethylpropan-1-ol and the like or organosilanol compound such as vinyl dimethyl silanol and the like.

Although the coated optical fiber of the invention can be obtained by coating a quartz glass-made optical fiber base with the above described organopolysiloxane alone followed by irradiation with actinic rays to effect curing thereof, it is optional that the organopolysiloxane is admixed with various kinds of additives. For example, physical properties of the cured coating layer can be modified by admixing the organopolysiloxane with an acrylic monomer or an oligomer thereof.

Various kinds of actinic rays are effective to cure the coating layer of the organopolysiloxane or a composition comprising the same as the principal ingredient including ultraviolet light, far-ultraviolet light, electron beams, X-rays, γ-rays and the like, of which ultraviolet is preferred in respect to the simplicity and hadiness of the apparatus. The ultraviolet lamp suitable as the irradiation source includes high- and low-pressure mercury lamps, xenon lamps, hydrogen discharge tubes and the like. The irradiation with the actinic rays can be performed in any desired gaseous atmosphere such as air and inert gases.

It is sometimes advantageous depending on the type of the actinic rays for the irradiation of the coating layer that the organopolysiloxane is admixed with a photosensitizer or photopolymerization initiator such as benzophenone compounds, e.g. benzophenone, benzoin ether compounds, e.g. benzoin isobutyl ether, ketal compounds, e.g. acetophenone diethyl ketal, thioxanthone compounds, acetophenone compounds and the like in an amount not exceeding 20% by weight or, preferably, in the range from 1 to 5% by weight based on the organopolysiloxane.

The coated optical fiber of the invention has excellent resistance against heat and water and low water absorption of the coating layer in comparison with conventional coated optical fibers in addition to the outstandingly low temperature dependency of the Young's modulus. Accordingly, the inventive coated optical fiber is serviceable over a long period of time under any severest environmental conditions.

In the following, the coated optical fiber of the invention is described in more detail with reference to the examples preceded by the description of the preparation procedure of the organopolysiloxanes as the coating material on the optical fiber base.

PREPARATION 1

Into a flask of 1 liter capacity equipped with a stirrer, reflux condenser, dropping funnel, thermometer and gas inlet tube were introduced 452 g of a chlorine-containing organopolysiloxane 1 expressed by an average structural formula

Cl.sub.2 MeSi--CH.sub.2 CH.sub.2 --SiMe.sub.2 --O--SiMe.sub.2).sub.198 O--SiMe.sub.2 --CH.sub.2 CH.sub.2 --SiMeCl.sub.2

and 300 g of diisopropyl ether followed by the addition of 14.6 g of triethyl amine and 54 g of pentaerithritol triacrylate having a hydroxy value of 130.5 and containing 0.2% of dibutyl hydroxytoluene as a polymerization inhibitor to form a reaction mixture.

The reaction mixture was heated under agitation at 70° C. for 7 hours and then cooled to room temperature followed by filtration to remove the precipitated salt and distillation of the filtrate at 65° C. under a reduced pressure to remove the solvent. The filtrate freed from the solvent was filtered again under pressurization. The thus obtained product was a clear and oily organopolysiloxane expressed by the formula

[(CH2 ═CHCOOCH2)3 CCH2 O]2 MeSi--CH2 CH2 --SiMe2 --O--SiM2)198 --O--SiMe2 --CH2 CH2 --SiMe]OCH2 C(CH2 OCOCH═CH2)3 ]2.

This product is referred to as Organopolysiloxane I hereinbelow.

PREPARATION 2

Into the same reaction vessel as used in Preparation 1 were introduced 350 g of the chlorine-containing organopolysiloxane 2 shown by the formula given below and 300 g of toluene followed by the addition of 32 g of triethyl amine and 22 g of 2-hydroxyacrylate containing 0.2% by weight of dibutyl hydroxytoluene and the mixture was heated at 70° C. under agitation. After 2 hours of agitation at the same temperature, the reaction mixture was admixed with 8.5 g of trimethyl silanol and further agitated for additional 3 hours to complete the reaction. The reaction mixture cooled to room temperature was filtered and the filtrate was freed from the solvent by distillation under reduced pressure at 100° C. followed by further filtration to give a product, which is shown by the formula given below and referred to as Organopolysiloxane II hereinbelow.

Chlorine-containing organopolysiloxane 2:

Cl.sub.3 Si--CH.sub.2).sub.2 SiMe.sub.2 --O).sub.69 (SiPh.sub.2 O).sub.30 --SiMe(CH.sub.2 CH.sub.2 SiCl.sub.3)--O--SiMe.sub.2 --CH.sub.2).sub.2 SiCl.sub.3

Organopolysiloxane II:

(CH.sub.2 ═CHCOOCH.sub.2 CH.sub.2 O).sub.2 Si(OSiMe.sub.3)--CH.sub.2).sub.2 --SiMe.sub.2 --O).sub.69 (SiPh.sub.2 --O).sub.30 --SiMe[CH.sub.2 CH.sub.2 Si(OSiMe.sub.3)(OCH.sub.2 CH.sub.2 OCOCH═CH.sub.2).sub.2 ]--O--SiMe.sub.2 (CH.sub.2).sub.2 Si(OSiMe.sub.3)(OCH.sub.2 CH.sub.2 OCOCH═CH.sub.2).sub.2
PREPARATION 3 to 6

The synthetic procedure in each of these Preparations was substantially the same as in Preparation 2 described above except that the starting chlorine containing organopolysiloxane 3, 4, 5 or 6, amount thereof, the ethylenically unsaturated compound and amount thereof, the amount of triethyl amine added to the reaction mixture and the organopolysiloxane product, referred to as Organopolysiloxane III, IV, V or VI hereinbelow, were as shown in the following by the respective structural formula, when appropriate. In Preparation 3, 2.8 g of methyl alcohol were additionally added to the reaction mixture. The organopolysiloxane VI was prepared for comparative purpose.

(PREPARATION 3)

Chlorine-containing organopolysiloxane 3: 424 g

Cl.sub.2 Si(ME--CH.sub.2).sub.2 SiMe.sub.2 --O--SiMe.sub.2 --O).sub.100 (SiMe(CH.sub.2 CH.sub.2 CF.sub.3)--O].sub.20 SiMe.sub.2 --CH.sub.2).sub.2 SiMeCl.sub.2

Pentaerithritol triacrylate: 34 g

Triethyl amine: 18 g

Organopolysiloxane III:

(CH.sub.2 ═CHCOOCH.sub.2).sub.3 CCH.sub.2 O--SiMe(OMe)--CH.sub.2).sub.2 SiMe.sub.2 --O--(SiMe.sub.2 --O).sub.100 [SiMe(CH.sub.2 CH.sub.2 CF.sub.3)--O].sub.20 SiMe.sub.2 --(CH.sub.2).sub.2 SiMe(OMe)--OCH.sub.2 C(CH.sub.2 OCOCH═CH.sub.2).sub.3
(PREPARATION 4)

Chlorine-containing organopolysiloxane 4: 448 g

ClSiMe.sub.2 --O(SiMe.sub.2 --O).sub.68 [SiMe(CH.sub.2 CH.sub.2 SiMe.sub.2 Cl)--O].sub.2 --SiMe.sub.2 Cl

Trimethylolpropane dimethylacrylate: 45 g

Triethyl amine: 18 g

Organopolysiloxane IV: ##STR1##

(PREPARATION 5)

Chlorine-containing organopolysiloxane 5: 344 g

[ClSiMe.sub.2 --CH.sub.2).sub.2 SiMe.sub.2 --O--SiMe.sub.2 --O).sub.7.5 ].sub.3 SiMe

pentaerithritol triacrylate: 200 g

Triethyl amine: 50 g

Organopolysiloxane V:

[(CH.sub.2 ═CHCOOCH.sub.2).sub.3 CCH.sub.2 O--SiMe.sub.2 --CH.sub.2).sub.2 SiMe.sub.2 --O--(SiMe.sub.2 --O).sub.7.5 ].sub.3 SiMe
(PREPARATION 6)

Chlorine-containing organopolysiloxane 6: 380 g

ClSiMe.sub.2 (O--SiMe.sub.2 --O).sub.100 SiMe.sub.2 Cl

2-Hydroxyethyl acrylate: 12 g

Triethyl amine: 11 g

Organopolysiloxane VI:

CH.sub.2 ═CHCOO--CH.sub.2).sub.2 O(SiMe.sub.2 --O--SiMe.sub.2 --O).sub.100 --SiMe.sub.2 --O--CH.sub.2).sub.2 OCOCH═CH.sub.2
EXAMPLES 1 to 5 AND COMPARATIVE EXAMPLES 1 to 3

A curable organopolysiloxane composition was prepared by uniformly blending 2 parts of benzophenone with 100 parts of one of the Organopolysiloxanes I to VI obtained in the above described Preparations 1 to 6. The Organopolysiloxanes I to V were for Examples 1 to 5, respectively, and the Organopolysiloxane VI was for Comparative Example 1. An optical fiber base of fused quartz glass having a diameter of 125 μm and obtained by spinning at a velocity of 30 meters/minute was coated with the composition in a coating thickness of 50 μm and irradiated with ultraviolet light from a high-pressure mercury lamp having a linear output of 80 watts/cm at a distance of 10 cm for 0.4 second to give a dose of 100 mJ/cm2 so that it was found that the coating layers in Examples 1 to 5 had been fully cured into a uniform coating film having a smooth and uniform surface without stickiness. On the other hand, curing of the coating layer in Comparative Example 1 was not complete leaving considerable stickiness on the surface.

For further comparison, the Organopolysiloxanes I to VI and two non-silicone coating materials conventionally used in optical fiber coating (Comparative Examples 2 and 3) with admixture of 2% by weight of benzophenone were each shaped into a sheet of 1 mm thickness, which was irradiated with a high-pressure mercury lamp having a linear output of 80 watts/cm to give a dose of 300 mJ/cm2. The coating materials used in Comparative Examples 2 and 3 were a polyether urethane acrylate and a polybutadiene urethane acrylate, respectively, expressed by the following formulas, in which (C6 H3 Me) is a 1,4-tolylene group.

(COMPARATIVE EXAMPLE 2)

CH.sub.2 ═CHCOO--CH.sub.2).sub.2 OCONH--(C.sub.6 H.sub.3 Me)--NHCOO[(CH.sub.2).sub.4 --O].sub.14 CONH--(C.sub.6 H.sub.3 Me)--NHCOO--CH.sub.2).sub.2 OCOCH═CH.sub.2
(COMPARATIVE EXAMPLE 3) ##STR2##

These ultraviolet-cured sheets were examined for the surface condition and subjected to the determination of water absorption and temperature dependency of the Young's modulus at low temperatures to give the results shown in the table below. In the table, the results of the evaluation are given by rating in two, four or three grades for the surface condition, water absorption and temperature dependency of Young's modulus according to the following criteria. The water absorption was determined in the following manner. Thus, a cured sheet of 0.5 mm by 50 mm by 50 mm which was immersed for 24 hours in pure water at 25° C. and the weight W1 was determined after being freed from water on the surface. Thereafter, the test piece was kept in a desiccator of calcium chloride until the test piece lost no additional weight to have a constant weight W2. The water absorption in % was given by (W1 -W2)/W2 +100.

Surface condition

A: The sheet was uniformly cured without surface tackiness.

B: The surface had tackiness to retain finger prints by touching with a finger tip.

Water absorption

A: less than 1.0%

B: 1.0 to 2.0%

C: larger than 2.0%

Temperature dependency of Young's modulus

A: small temperature dependency at -30° C. or below

B: small dependency at -30° to -10° C.

C: relatively large at -10° C. or higher

              TABLE______________________________________                     Comparative    Example          Example    1    2      3      4    5    1   2    3______________________________________Surface condition      A      A      A    A    A    B   A    BWater absorption      A      A      A    A    B    A   C    AYoung's modulus      A      B      A    A    A    A   C    A______________________________________

Claims (3)

What is claimed is:
1. A coated optical fiber which comprises:
(a) a fused quartz glass-made optical fiber base; and
(b) a coating layer on the optical fiber base formed of a coating material comprising, as the principal ingredient thereof, an organopolysiloxane represented by the average unit formula
(R.sup.1).sub.a [(R.sup.3 O).sub.n (R.sup.4).sub.3--n--m (R.sup.5 O).sub.m Si--R.sup.2 --].sub.b SiO.sub.(4--a--b)/2,
in which the groups denoted by R1 and R4 are each, independently from the others, a substituted or unsubstituted monovalent hydrocarbon groups, R2 is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, R3 is a monovalent organic group having 4 to 25 carbon atoms and 1 to 3 ethylenically unsaturated groups, R5 is a monovalent hydrocarbon group free from aliphatic unsaturation having 1 to 18 carbon atoms or an organosilyl group represented by the general formula
--SiR.sup.6.sub.2 --O).sub.p SiR.sup.6,
R6 being a monovalent hydrocarbon group having 1 to 9 carbon atoms and p being zero or a positive integer, a is a positive number in the range from 1.6 to 2.2, b is a positive number in the range from .[.0.02.]. .Iadd.0.002 .Iaddend.to 0.5 with the proviso that a+b is in the range from 1.8 to 2.2, n is 1, 2 or 3, m is zero, 1 or 2 with the proviso that n+m is 1, 2 or 3 and R3 has at least two ethylenically unsaturated groups when n is 1.
2. A method for the preparation of a coated optical fiber which comprises the steps of:
(a) coating a fused quartz glass-made optical fiber base with a coating material comprising, as the principal ingredient thereof, an organopolysiloxane represented by the average unit formula
(R.sup.1).sub.a [(R.sup.3 O).sub.n (R.sup.4).sub.3--n--m (R.sup.5 O).sub.m Si--R.sup.2 --].sub.b SiO.sub.(4--a--b)/2,
in which the groups denoted by R1 and R4 are each, independently from the others, a substituted or unsubstituted monovalent hydrocarbon group, R2 is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, R3 is a monovalent organic group having 4 to 25 carbon atoms and 1 to 3 ethylenically unsaturated groups, R5 is a monovalent hydrocarbon group free from aliphatic unsaturation having 1 to 18 carbon atoms or an organosilyl group represented by the general formula
--SiR.sup.6.sub.2 --O).sub.p SiR.sup.6.sub.3,
R6 being a monovalent hydrocarbon group having 1 to 9 carbon atoms and p being zero or a positive integer, a is a positive number in the range from 1.6 to 2.2, b is a positive number in the range from .[.0.02.]. .Iadd.0.002 .Iaddend.to 0.5 with the proviso that a+b is in the range from 1.8 to 2.2, n is 1, 2 or 3, m is zero, 1 or 2 with the proviso that n+m is 1, 2 or 3 and R3 has at least two ethylenically unsaturated groups when n is 1, to form a coating layer; and
(b) irradiating the coating layer with ultraviolet light to cure the organopolysiloxane.
3. The method as claimed in claim 2 wherein the group denoted by R3 is selected from the class consisting of 2-acryloxyethyl of the formula CH2 ═CHCOOCH2 --CH2 --, 2,2,2-tri(methacryloxymethyl)ethyl of the formula [CH2 ═C(CH3)COOCH2 ]3 C--CH2 -- and 2,2-di(acryloxymethyl)butyl of the formula (CH2 ═CHCOOCH2)2 C(C2 H5)--CH2 --.
US07492779 1985-11-12 1990-03-13 Optical fiber coated with an organopolysiloxane curable actinic rays Expired - Lifetime USRE33737E (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP60-259275 1985-11-12
JP25927585A JPH0425231B2 (en) 1985-11-19 1985-11-19
US07492779 USRE33737E (en) 1985-11-12 1990-03-13 Optical fiber coated with an organopolysiloxane curable actinic rays

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07492779 USRE33737E (en) 1985-11-12 1990-03-13 Optical fiber coated with an organopolysiloxane curable actinic rays

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06930002 Reissue US4733942A (en) 1985-11-19 1986-11-12 Optical fiber coated with an organopolysiloxane curable with actinic rays

Publications (1)

Publication Number Publication Date
USRE33737E true USRE33737E (en) 1991-11-05

Family

ID=26544047

Family Applications (1)

Application Number Title Priority Date Filing Date
US07492779 Expired - Lifetime USRE33737E (en) 1985-11-12 1990-03-13 Optical fiber coated with an organopolysiloxane curable actinic rays

Country Status (1)

Country Link
US (1) USRE33737E (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5212762A (en) * 1990-11-27 1993-05-18 Mitsubishi Rayon Co., Ltd. Plastic-clad silica (PCS) fibers and methods and apparatuses for producing the same
US5296511A (en) * 1991-02-08 1994-03-22 Shin-Etsu Chemical Co., Ltd. Film-former composition
US5585201A (en) * 1995-06-05 1996-12-17 Minnesota Mining And Manufacturing Company Radiation-curable composition comprising a polydimethylsiloxane
US6198867B1 (en) * 1998-07-08 2001-03-06 Shin-Etsu Chemical Co., Ltd. Radiation-curable liquid resin composition and optical fiber

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB897696A (en) * 1957-11-08 1962-05-30 Standard Telephones Cables Ltd Flexible light guide
US3933678A (en) * 1973-10-01 1976-01-20 Dow Corning Corporation Optically clear organosilicon compounds
GB2038021A (en) * 1978-11-07 1980-07-16 Sumitomo Electric Industries Optical transmission fibre having organo-polysiloxane coatings
US4270840A (en) * 1978-05-25 1981-06-02 Nippon Telegraph And Telephone Public Corporation Glass fibers for optical transmission
US4322473A (en) * 1978-03-08 1982-03-30 Consortium Fur Elektrochemische Industrie Gmbh Organosiloxanes with SiC-bonded groups and a process for preparing the same
US4380367A (en) * 1979-03-28 1983-04-19 Toray Silicone Co., Ltd. Coating material for optical communication glass fibers
US4505542A (en) * 1980-03-31 1985-03-19 Raychem Corporation Thermostatic fiber optic waveguides
US4725648A (en) * 1985-10-15 1988-02-16 Toshiba Silicone Co., Ltd. Polyorganosiloxane composition
US4895917A (en) * 1987-10-16 1990-01-23 Th. Goldschmidt Ag Organopolysiloxanes with Bunte salt groups

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB897696A (en) * 1957-11-08 1962-05-30 Standard Telephones Cables Ltd Flexible light guide
US3933678A (en) * 1973-10-01 1976-01-20 Dow Corning Corporation Optically clear organosilicon compounds
US4322473A (en) * 1978-03-08 1982-03-30 Consortium Fur Elektrochemische Industrie Gmbh Organosiloxanes with SiC-bonded groups and a process for preparing the same
US4270840A (en) * 1978-05-25 1981-06-02 Nippon Telegraph And Telephone Public Corporation Glass fibers for optical transmission
GB2038021A (en) * 1978-11-07 1980-07-16 Sumitomo Electric Industries Optical transmission fibre having organo-polysiloxane coatings
US4344669A (en) * 1978-11-07 1982-08-17 Nippon Telegraph & Telephone Corporation Coated glass fibers for optical transmission
US4380367A (en) * 1979-03-28 1983-04-19 Toray Silicone Co., Ltd. Coating material for optical communication glass fibers
US4505542A (en) * 1980-03-31 1985-03-19 Raychem Corporation Thermostatic fiber optic waveguides
US4725648A (en) * 1985-10-15 1988-02-16 Toshiba Silicone Co., Ltd. Polyorganosiloxane composition
US4895917A (en) * 1987-10-16 1990-01-23 Th. Goldschmidt Ag Organopolysiloxanes with Bunte salt groups

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5212762A (en) * 1990-11-27 1993-05-18 Mitsubishi Rayon Co., Ltd. Plastic-clad silica (PCS) fibers and methods and apparatuses for producing the same
US5296511A (en) * 1991-02-08 1994-03-22 Shin-Etsu Chemical Co., Ltd. Film-former composition
US5585201A (en) * 1995-06-05 1996-12-17 Minnesota Mining And Manufacturing Company Radiation-curable composition comprising a polydimethylsiloxane
US6198867B1 (en) * 1998-07-08 2001-03-06 Shin-Etsu Chemical Co., Ltd. Radiation-curable liquid resin composition and optical fiber

Similar Documents

Publication Publication Date Title
US5468826A (en) Adhesion promoting additives and curable organosiloxane compositions containing same
US5532398A (en) Silanes, process for their preparation and their application to prepare polymers and polycondensates
US5024507A (en) Photopolymerizable composition for cladding optical fibers
US5412053A (en) Polymers containing alternating silsesquioxane and bridging group segments and process for their preparation
US4640967A (en) Ultraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionality
US4248992A (en) Gaunidyl-containing organosilicon compounds
US4503208A (en) Acrylic functional silicone copolymers
US4585669A (en) Novel dual cure silicone compositions
US4980443A (en) Fluorosilicone compounds and compositions for adhesive release liners
US5466768A (en) Ultraviolet light absorbing compounds, silicone compositions and methods for making same
US4491508A (en) Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer
US4435259A (en) Radiation curable composition of vinyl polysiloxane and hydrogen polysiloxane with photosensitizer
US4455205A (en) UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator
US4563514A (en) Curable polysilarylene-polysiloxane copolymers
US4534838A (en) Siloxane polyphotoinitiators of the substituted acetophenone type
US5237082A (en) Radiation-curable silicone elastomers and pressure sensitive adhesives
US5539013A (en) UV-curable epoxysilicone-polyether block copolymers combined with UV-detectable dye-marker
US5147957A (en) Hydrosilated azlactone functional silicon containing compounds and derivatives thereof
US4921880A (en) Adhesion promoter for UV curable siloxane compositions and compositions containing same
US4640940A (en) Polyol terminated silicones and derivatives thereof
US4504629A (en) Polymers with graft α-alkylacrylate functionality
US5463084A (en) Photocurable silicone oxetanes
US5082914A (en) Grafted cellulose esters containing a silicon moiety
US4558111A (en) Method for preparing acrylic functional halosilanes and halosiloxanes
US5776658A (en) Silicone-compatible photoinitiators, and photosensitive mixtures comprising them

Legal Events

Date Code Title Description
FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12