• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention provides at least one monomer or oligomer having a radiation-curable functional group in an uncured state; Photoinitiators for the monomers or oligomers; And radiation-curable compositions for ink bases, ink compositions, external primary compositions, buffer materials or matrix materials for optical fibers comprising secondary amino or tertiary amino silicone-containing additives.
    公开号:KR20020067046A
    申请号:KR1020027008146
    申请日:2000-12-18
    公开日:2002-08-21
    发明作者:머피에드워드조지프；자호라에드워드폴；코스터-무르낸시루이스；에반스글렌제프리
    申请人:디에스엠 엔.브이；
    IPC主号:
    专利说明:

    Optical Fiber Coating Composition {OPTICAL FIBER COATING COMPOSITIONS}
    [2] The optical glass fibers are coated with two or more overlapping radiation-curable coatings that together form the primary coating immediately after the glass fibers are made by drawing in a furnace. The coating material in direct contact with the optical glass fibers is called "inner primary coating material" and the overcoated coating material is called "outer primary coating material". In some documents, the inner primary coating is also simply referred to as "primary coating" and the outer primary coating is referred to as "secondary coating". The inner primary coating is softer than the outer primary coating.
    [3] Single layer coatings (“single coatings”) may also be used to coat optical fibers. Single coatings usually have intermediate properties (eg, hardness) between the soft inner primary coating and the hard outer primary coating properties.
    [4] Relatively soft inner primary coatings are resistant to microbending. This is undesirable because it attenuates the signal transduction capability of the coated optical fiber by fine bending. The hard outer primary coating provides resistance to the handling forces that may be experienced when the coated fibers become ribbons and / or cables.
    [5] Although the optical fiber coating composition is an inner primary coating, an outer primary coating or a single coating, the optical fiber coating composition is usually a polyethylene-unsaturated monomer or oligomer and photoinitiator dissolved or dispersed in a liquid ethylene-unsaturated medium prior to curing. It includes. The coating composition is typically added to optical fibers in liquid form and exposed to actinic radiation to cure.
    [6] For multichannel delivery, an optical fiber assembly comprising a plurality of coated optical fibers is used.
    [7] Examples of optical fiber assemblies include ribbon assemblies and cables. Typical ribbon assemblies are made by combining a matrix material with a plurality of parallel oriented individual coated optical fibers. The matrix material has the function of fixing the individual optical fibers in a straight line and protecting the fibers during handling and installation. Often the fibers are arranged in a "tape-shaped" ribbon structure and have a flat strand-like structure, usually comprising about 2 to 24 fibers. Depending on the application, a number of ribbon assemblies can be combined to result in a cable having several to less than about 1000 coated optical fibers. An example of a ribbon assembly is disclosed in published European patent application 194891. Multiple ribbon assemblies can be combined together in a cable, which is disclosed in US Pat. No. 4,906,067.
    [8] The term "ribbon assembly" includes the fiber-shaped bundle as well as the tape-shaped ribbon assembly described above. The optical fiber bundles can be substantially circularly arranged, for example with at least one central fiber surrounded by a number of other optical fibers. Optionally, the bundle may have the shape of another cross section, such as square, trapezoidal or the like.
    [9] Whether glass or recently used plastic is used in the optical fiber assembly, the coated optical fiber (or waveguide) can be colored to facilitate identification of the individual coated optical fibers. Typically the optical fibers may be coated with an outer colored layer, which is referred to as an ink coating, or optionally a colorant is added to the outer primary coating to impart the desired color.
    [10] Typically, the matrix material of the fiber optic ribbon assembly or cable is separated from the individual coated fibers to facilitate splitting the two cables or connecting the fibers to the input or output. The matrix material can be removed from the coated fibers with little or no effect on the outer primary coating or on the colored ink coating of the fibers. Good removability of the matrix material not only facilitates visual identification of color coded fibers, but also does not damage the waveguide during the removal process.
    [11] Therefore, it is suggested that certain forms of silicon-containing compounds are included in the colored layer and / or matrix material to improve the removability of the matrix material of the ribbon from the color coated optical fibers. For example, US Pat. No. 4,828,349 discloses a multinuclear fiber unit, wherein each fiber element is covered with a release layer, and the cover layer is bonded with a ribbon or cable. The release layer of each optical fiber comprises ultraviolet cured or thermosetting fluorocarbon resin or ultraviolet cured or thermosetting silicone resin.
    [12] U.S. Patent 5,621,838 discloses a number of fibers coated with optical fiber units, each coated optical fiber having a colored layer as the outermost layer and coated with a bundling or matrix layer. The colored layers on the coated fiber and matrix layer comprise a release agent consisting of silicone resins or oils or fluororesins or fluoro-oils known in the art at the time the present application is filed.
    [13] Japanese Laid-Open Patent H1-152405 discloses an optical fiber tape type core in which a plurality of flatly arranged optical core wires are covered with a single unit. Each optical fiber core wire is covered with a resin cured with ultraviolet light and has a colored layer as its outermost layer. The colored layer included an organic polysiloxane compound to improve the removal of the matrix coating material. The organic polysiloxane compound includes at least one functional group.
    [14] Ink compositions comprising silicone-based release agents are used in the art and are generally not satisfactory. Silicone release agents, especially those that do not react under UV curing conditions, have been found to migrate in the ribbon assembly over time. Migration deforms the release property of the matrix material from the optical fiber to the outermost coating, for example from the outer primary coating or the ink coating, which is undesirable. Silicone release agents are known to cause pigment coagulation by impairing the stability of the pigment dispersion in the ink composition, especially when the silicone release agent is added to the finished ink composition. The silicone release agent also slows the line speed and decreases the curing rate of the ink composition. By doing so, the manufacturing efficiency of the optical fiber ribbon can be reduced.
    [15] Despite the conventional efforts to provide an optical fiber coating composition and ink composition in which the matrix material of the ribbon assembly is easily removed from the ink composition when a plurality of optical fibers are formed into the ribbon assembly, the release agent of the matrix material is improved and the release agent is Even when added to finished ink compositions, there is a need for new release agents for ink compositions that can improve the stability of pigment dispersions in ink compositions and improve the manufacturing efficiency and manufacturing speed of optical fiber ribbons.
    [16] Summary of the Invention
    [17] The present invention relates to radiation curable compositions in which secondary and tertiary amino silicone-containing compounds are typically used as coatings in the field of optical fibers, including ink base compositions, inks, outer primary coatings, single coatings, buffers and matrix materials. It has been found that it can be added and can separate adjacent coatings from others as required in the field of use. Secondary and tertiary amino silicone-containing compounds are compatible with the ink base, are also compatible with the finished ink composition, and both the ink base and the ink composition even when the silicon-containing additive is later added to the finished ink. Shows excellent pigment dispersion stability. Secondary and tertiary amino additives are preferably not discolored and do not tend to migrate significantly in the ribbon structure, thereby avoiding changes in release properties over time.
    [1] The present invention relates to an optical fiber coating composition, in particular an optical fiber coating composition comprising a silicone-containing release agent, and an optical fiber coated with the composition.
    [18] According to the present invention there is provided an optical fiber coating composition comprising a secondary amino or tertiary amino silicone-containing release agent. It will also be appreciated by one of ordinary skill in the art that secondary and tertiary amino silicone-containing release agents may be included in the optical fiber coating compositions as desired. The use of the silicone-containing release agent according to the invention facilitates the removal or separation of two adjacent layers on the coated optical fiber.
    [19] The release agents according to the invention are used in ink base compositions, such as uncoloured compositions, for example later colored with pigments, dyes and the like. Similarly, the release agents of the present invention can be used in ink compositions, ie compositions comprising the desired colorant. The addition of secondary or tertiary amino silicone-containing release agents to the colored coating on the optical fiber in accordance with the present invention aids in the removal or separation of the ribbon matrix material from the colored coating. As such, when the optical fiber coated with the ink composition of the present invention is ribboned, the removal of the ribbon material from the fiber may, for example, cause the unwanted matrix material to peel off from the colored coating while maintaining the colored coating on each optical fiber. To facilitate the connection work. The release agents described herein can be used in outer primary coatings, in buffer materials used as coatings on single optical fibers, in single coatings, and in matrix materials.
    [20] Many variants of secondary and tertiary amino silicone-containing release additives can be used in the coating compositions of the present invention. Secondary and tertiary amino derivatives of disubstituted disiloxanes and polydisubstituted siloxanes are the desired silicone-containing additives according to the invention. Silicone-containing release additives found to be useful are compounds comprising the structure of Formula 1 below:
    [21]
    [22] (In Chemical Formula 1, each of R 1 , R 2 , R 3, and R 4 may be the same or different, and each is an aliphatic or aromatic hydrocarbon.)
    [23] Examples of aliphatic hydrocarbons which may be any of R 1 to R 4 are alkyl groups of 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms, more preferably 1 to about 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl and the like. Examples of aromatic groups which may be any of R 1 to R 4 are phenyl and phenyl derivatives. Examples of compounds having the structure of Formula 1 wherein R 1 , R 2 , R 3 and R 4 are alkyl and aromatic are diphenyl dimethylsiloxanes such as Mirasil DPDM available from Rhone-Poulenc.
    [24] Dimethyl disiloxane silicone-containing additive is used as one preferred embodiment. Examples of dimethyl disiloxane silicone-containing additives useful in the optical fiber compositions of the present invention are secondary and tertiary amino derivatives of epoxycyclohexylethyl dimethyl disiloxane.
    [25] Secondary and tertiary amino polydisubstituted siloxanes useful in the optical fiber compositions of the present invention are the α, ω-aminoorganofunctional polydisubstituted siloxanes of the formula:
    [26]
    [27] (In Formula 2, R 1 , R 2 , R 3 and R 4 are as defined above, n is an integer from about 5 to about 50, preferably from about 10 to about 35.)
    [28] The substituents R 5 and R 6 are not of great importance in the present invention. Each of R 5 and R 6 may be the same or different. R 5 and R 6 typically form part of a silicon-containing additive, increasing the molecular weight of the compound to a molecular weight high enough to achieve the desired release properties and making the silicon-containing compound soluble in the UV-curable composition. Preferably each of R 5 and R 6 is alkoxy or ring-opened epoxy, such as ethoxy, propoxy, butoxy and more preferably repeating units thereof. Such materials are preferred for improving the compatibility of the silicone-containing compound with the components used in the UV-curable composition. Usually R 5 and R 6 have a molecular weight between 14-500.
    [29] The substituents R 7 and R 8 are not important in the present invention and may be the same or different. Typically R 7 and R 8 may be aliphatic or aromatic hydrocarbons. Preferably, each of R 7 and R 8 is a hindered group, such as a branched alkyl group, a long chain aliphatic group or a cycloaliphatic or heterocyclic hydrocarbon, having at least three carbon atoms. Alkyl, cycloaliphatic and aromatic hydrocarbons may also be substituted with, for example, alkyl, alkenyl, hydroxyl, carboxyl or carbonyl groups and the like. Examples of branched alkyl groups include isopropyl, t-butyl, isopentyl and the like. For the purposes of illustration, examples of cycloaliphatic hydrocarbons and aromatic hydrocarbons include cyclopentyl, cyclohexyl, phenyl, toluyl and the like. Examples of heterocyclic hydrocarbons include furan, thiophene, oxazole, thiazole, pyridine, pyrimidine, quinoline and the like. The hindered group may also be a long chain fatty acid of at least 12 carbon atoms, preferably 12-32 carbon atoms.
    [30] Preferred α, ω-aminoorganofunctional polydisubstituted siloxanes are α, ω-aminoorganofunctional polydimethyl siloxanes having the structure of formula (2) above. The functional group in the compound is a secondary amino group, and the compound has two functional groups. One of the compounds (additive A) additionally contains about 10 repeating units, for example n ≒ 10, about 3% nitrogen, effective hydrogen corresponding to the weight of the amine of about 460, about 10 mPa. a viscosity of s and a specific gravity of about 0.93 g / cm 3 at 25 ° C. The other compound (additive B) has about 30 repeating units, for example n ≒ 30, a nitrogen content of about 1.2, an effective hydrogen corresponding to the weight of an amine of about 1,160, a viscosity of about 35 mPa.s at 25 ° C. and 25 ° C. At about 0.96 g / cm 3.
    [31] Preference is given to using secondary amino silicone-containing release agents. Secondary amino silicone-containing release agents do not discolor, do not migrate in the composition over time, and provide desirable release properties.
    [32] The amount of secondary or tertiary amino silicone-containing agent included in the composition is not critical. The silicone-containing additive is added in an amount sufficient to achieve the desired release property, peelability and separability, and the exact amount added to the specific optical fiber composition can be easily determined by one of ordinary skill in the art. . For example, the silicon-containing additive may be from about 0.1 wt.% To about 10 wt.% Of the composition, preferably from about 0.5 wt.% To about 5 wt.% Of the composition, more preferably from about 1 wt.% To about 4 wt. Included as.%.
    [33] Ink compositions according to the present invention, unlike ink compositions comprising non-reactive silicon-containing additives, tend to minimize or avoid discoloration of the silicon-containing additives, and in silicones in ribbon assemblies made of ink coated optical fibers There is a tendency to minimize or avoid the mobility of the containing additives. The ink compositions of the present invention may be added to the optical fibers at faster line speeds than compositions with previously known silicon-containing additives. Thus, the discharge rate was improved.
    [34] Advantageously, the ink compositions of the present invention exhibit good release from the matrix material in the ribbon assembly and maintain good adhesion to the outer primary coating. They also exhibit good MEK resistance and breakout. As such a ribbon assembly made of colored fibers with the ink composition of the present invention is suitable in the art, wherein the matrix material is removed for continuous operation, and only the exposed colored fibers to facilitate identification of the colored fibers for connection. Remains.
    [35] The coating compositions of the present invention can be used in all radiation-curable, fiber optic coating compositions that can be used to coat glass or plastic waveguides.
    [36] Examples of suitable radiation-curable compositions that can be used in various ways are disclosed in US Pat. Nos. 4,624,994, 4,682,851, 4,782,129, 4,794,133, 4,806,574, 4,849,462, 5,219,896, and 5,336,563. It includes. The composition can be recombined and used as a radiation-curable carrier system in the ink base and ink composition according to the present invention.
    [37] The inner primary, outer primary, ink base and ink radiation-curable compositions include one or more radiation-curable oligomers or monomers having at least one functional group that can polymerize when exposed to actinic radiation. Suitable radiation-curable oligomers or monomers are now well known to those of ordinary skill in the art.
    [38] Usually, the radiation-curable functional groups used are ethylenically unsaturated groups and can be polymerized via radical polymerization or cation polymerization. Particular examples of suitable ethylenically unsaturated groups include groups comprising acrylates, methacrylates, styrenes, vinylethers, vinyl esters, N-substituted acrylamides, N-vinyl amides, maleate esters and fumarate esters. Preferably, the ethylenically unsaturated group is provided by a group comprising an acrylate, methacrylate, N-vinyl or styrene functional group.
    [39] Other types of functional groups usually used are provided by, for example, epoxy groups or thiol-ene or amine-ene systems. Epoxy groups polymerize through cation polymerization, while thiol-ene and amine-ene systems polymerize through radical polymerization. For example, the epoxy group may be homopolymerized. In thiol-ene and amine-ene systems, for example, polymerization may take place between a group comprising allyl unsaturated groups and a group comprising tertiary amines or thiols.
    [40] For ink bases and ink compositions, preferably at least about 80 mole%, more preferably at least about 90 mole% of the radiation-curable functional groups present in the oligomer are acrylates, methacrylates and N-vinyl.
    [41] Mixtures of oligomers having mono-, di-, tri-, tetra- and more functional groups can be used to achieve a balance of the desired properties, with the functional group being the number of radiation-curable functional groups present in the oligomer.
    [42] The oligomers usually comprise a carbon-containing main chain structure to which the radiation-curable functional groups are bound. For example, the oligomer can be represented by the following formula:
    [43] R-X-R: or
    [44] R-L-X-L-R
    [45] Wherein R is a radiation-curable functional group, X is a carbon-containing polymer main chain, a component comprising an aromatic group, or a combination thereof, and L is a linking group.
    [46] The size of the carbon-containing main chain is chosen to provide the desired molecular weight, and if the linking group is included in the oligomer, the selection of the main chain should take into account the limiting group (L). The number average molecular weight of the oligomer is about 200 to about 30,000, preferably about 500 to about 7,000, more preferably about 1,000 to about 5,000.
    [47] Examples of suitable carbon-containing polymer main chains include polymer main chains of polyethers, polyolefins, polyesters, polyamides, polycarbonates, alkyds or mixtures thereof.
    [48] In addition, as an example, the carbon-containing main chain of the oligomer may include an aromatic group and a ring-opening epoxy group or an alkoxy group.
    [49] Aromatic groups can be derived, for example, from bisphenol units such as bisphenol A. Suitable oligomers are known to those of ordinary skill in the art. Preferred oligomers are diglycidyl ether derivatives of bisphenol A to which acrylate functional groups are bound. Commercially available examples of such oligomers are CN-120 (Sartomer), have a molecular weight of about 500, and have a Tg of about 65 ° C. when cured.
    [50] Examples of suitable linking groups include alkoxy or ring-opening epoxy such as ethoxy, propoxy, butoxy and repeating units thereof. L may also be a urethane or urea linking group.
    [51] Another example of a preferred oligomer is a trifunctional polyether or polyester having a molecular weight of about 500 to about 5000. Preferred examples of trifunctional oligomers are commercially available polyurethane triacrylates, “Oligomer B”, which have a molecular weight of about 2000 and a Tg of about 42 ° C. when cured.
    [52] The tertiary amino silicone-containing release agent may be an oligomer, and in preferred embodiments, an intermediate linker may be used. The oligomer release agent can be represented by the following general structural formula:
    [53] RL 1 -AL 2 -R
    [54] In the above, A represents a silicon-containing component, R does not need to include but represents an amino-containing group which may comprise a radiation-curable component, and L 1 and L 2 represent a linking group.
    [55] L 1 and L 2 may each be a specific group capable of providing a covalent bond between an “R” component and an “A” component. Based on the description herein, one of ordinary skill in the art can readily understand which connector is suitable for the particular "A" and "R" selected.
    [56] In particular, a urethane group is preferable. Urethane linkages may, for example, (i) link low molecular weight diisocyanate compounds and hydroxy end-capped oligomers at both oligomer ends without extensive bonding of oligomers, or (ii) low molecular weight amines and isocyanate end-capsulated It is formed by linking oligomers.
    [57] In a preferred embodiment of the present invention, secondary or tertiary amino silicone-containing mold release agents are prepared into composite oligomers using the following components: silicone-containing compound having two hydroxy end groups (A), isophorone di A hydroxyl-containing radiation-curable component capped with isocyanates (L 1 , L 2 ) and amines. Isophorone diisocyanate (IPDI) end-capsulates both ends of the silicone diol oligomer and provides a linking site with a radiation-curable component capped with an amine.
    [58] Examples of diisocyanates that may be used in the embodiments of the present invention in the preparation of tertiary amino silicone-containing release agents include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylene diisocyanate (PDI), naphthalene di Isocyanate (NDI), tetramethylxylene diisocyanate (TMXDI), meta-xylene diisocyanate (MXDI), bis 4,4 '-(isocyanatocyclohexyl) methane (DES W) (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), trans-cyclohexane diisocyanate (Elate 166), 1,3-bis (isocyanatomethyl) cyclohexane (1,3 BIC), dimer acid diisocyanate (DDI-1410), norbornene diisocyanate (NBDI), dimethyl meta-isopropenyl benzyl isocyanate (meta-TMI), trifunctional biuret adduct of HDI, iso of HDI When iso cyanurate trimer, IPDI and the like isocyanurate trimer.
    [59] Without limiting the present invention, for the sake of explanation, silicone urethane may be prepared by reacting an isocyanate group with a silicon-containing compound to form a urethane-containing silicon precursor. And the precursor may react with a secondary or tertiary amino-containing compound to form a secondary or tertiary amino silicone-containing urethane. For example, hydroxy functional alkoxy-polydimethylsiloxanes can be reacted with diisocyanates to form silicon-containing urethane precursors including isocyanato groups. And the silicon-containing urethane precursor may react with a compound comprising a tertiary amine to form an amino silicon-containing compound. Preferably, the amino silicon-containing compound reacts with isocyanato groups of the precursor. The reaction takes place via certain reactive substituents on the compound.
    [60] Preferably, the secondary or tertiary amino compound has a reactive component such as a hydroxyl group component that can react with the urethane precursor to form a silicone urethane. Examples of secondary and tertiary amine compounds that can be used in embodiments of the present invention include, for example, dialkyl alcohol amines such as dimethylethanol amine, dimethyl propanol amine, diethanol amine, hydroxyethyl morpholine, 1-ethyl-3 Cyclic amines including hydroxy piperidine and the like.
    [61] The inner primary, outer primary, ink base and ink radiation-curable compositions may also include reactive diluents used to adjust the viscosity. The reactive diluent may be a low viscosity monomer having at least one functional group that can polymerize when exposed to actinic radiation. Usually, the viscosity of the low viscosity diluent monomer is from about 50 to about 500 centipoise at 25 ° C. Examples of suitable viscosities for the optical fiber coating compositions range from about 500 to about 50,000 centipoise at 25 ° C. Preferred amounts of radiation-curable diluent monomer comprise from about 5 to about 70 weight percent, more preferably from about 10 to about 60 weight percent, based on the total amount of the composition.
    [62] Functional groups in reactive diluents may have the same properties as may be used in radiation-curable monomers or oligomers. Preferably, the functional groups present in the reactive diluent can copolymerize with the radiation-curable functional groups present on the radiation-curable monomer or oligomer. More preferably, the radiation-curable functional groups form free radicals during curing that can react with free radicals produced on the surface of the surface treated optical fibers.
    [63] For example, the reactive diluent can be a monomer or a mixture of monomers having acrylate or vinyl ether functional groups and a C 4 -C 20 alkyl or polyether component. Specific examples of the reactive diluent include hexyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, decyl-acrylate, lauryl acrylate, stearyl acrylate, 2-ethoxyethoxy-ethyl acrylate. , Lauryl vinyl ether, 2-ethylhexyl vinyl ether, N-vinyl formamide, isodecyl acrylate, isooctyl acrylate, vinyl-caprolactam, N-vinylpyrrolidone and the like.
    [64] Another form of reactive diluent that can be used is a compound having an aromatic group. Specific examples of reactive diluents having aromatic groups include ethylene glycol phenyl ether acrylate, polyethylene glycol phenyl ether acrylate, polypropylene glycol phenyl ether acrylate and alkyl-substituted phenyl derivatives of the monomers, such as polyethylene glycol nonylphenyl ether acrylate. It includes.
    [65] The reactive diluent also includes two or more functional groups that can polymerize. Specific examples of such monomers include C 2 -C 18 hydrocarbondioldiacrylate, C 4 -C 18 hydrocarbondivinylether, C 3 -C 18 hydrocarbon triacrylate and polyether analogs thereof, such as 1,6 -Hexanediol diacrylate, trimethylol-propane triacrylate, hexanediol divinyl ether, triethylene glycol diacrylate, pentaerythritol triacrylate, ethoxylated bisphenol-A-diacrylate and tripropylene glycol diacryl Includes the rate.
    [66] If the radiation-curable functional group of the radiation-curable monomer or oligomer is an epoxy group, for example one or more of the following compounds may be used as reactive diluents:
    [67] Diglycidyl ether of epoxy-cyclohexane, phenylepoxyethane, 1,2-epoxy-4-vinylchlorohexane, glycidyl acrylate, 1,2-epoxy-4-epoxyethyl-cyclohexane, polyethylene-glycol And diglycidyl ether of bisphenol-A.
    [68] If the radiation-curable functional group of the radiation-curable monomer or oligomer has an amine-ene or thiol-ene system, examples of reactive diluents having allyl unsaturated groups that can be used include diallylphthalate, triallyl trimellitate, triallyl cyanurate. Latelate, triallyl isocyanurate and diallyl isophthalate.
    [69] In amine-ene systems, amine functional diluents that can be used include, for example:
    [70] Adducts of trimethylolpropane, isophorone diisocyanate and di (meth) ethylethanolamine, adducts of hexanediol, isophorone diisocyanate and dipropylethanolamine, trimethylol propane, trimethylhexamethylene diisocyanate and di (meth) Adducts of ethylethanolamine.
    [71] The radiation-curable ink composition may include a photoinitiator that generates free radicals. Examples of suitable free radical type photoinitiators include, but are not limited to, isobutyl benzoin ether; 2,4,6-trimethylbenzoyl, diphenylphosphine-oxide; 1-hydroxycyclohexylphenyl ketone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; 2,2-dimethoxy-2-phenylacetophenone; Perfluorinated diphenyl titanocene; 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone; 2-hydroxy-2-methyl-1-phenyl propan-1-one; 4- (2-hydroxyethoxy) phenyl-2-hydroxy-2-propyl ketone dimethoxyphenylacetophenone; 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-propyl) -ketone; Diethoxyphenyl acetophenone; A mixture of (2,6-dimethoxy benzoyl) -2,4,4-trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Benzophenones; 1-propanone, 2-methyl-1,1- (4- (methylthio) phenyl) 2- (4-morpholinyl) and mixtures thereof.
    [72] Other additives that may be used in the coating compositions include, but are not limited to, catalysts, lubricants, wetting agents, antioxidants, and stabilizers. The additives can be selected and used by one of ordinary skill in the art.
    [73] Single coatings may also be used. Examples of single coatings are disclosed in US Pat. No. 4,932,750. Single coatings, similar internal primary coatings usually include oligomers, reactive diluents and optional photoinitiators and additives. Conventional outer primary coatings can be used in the practice of the present invention as disclosed in US Pat. No. 4,472,019.
    [74] The ink base and ink composition of the present invention may comprise an adhesion promoter as disclosed in US Pat. No. 5,812,725.
    [75] The colorant for the ink composition of the present invention may be any dye or dye suitable for preparing a radiation-curable ink composition. The term "pigment" refers to both inorganic and organic pigments. Preferably, the dye is used in the form of a pigment dispersion to simply disperse the pigment in the ink coating composition. The pigment dispersions are usually low viscosity liquids in an amount that the pigment dispersions can easily be put at room temperature, and include one or more pigments dispersed in a reactive diluent, for example. For example, it has been found that an amount of about 1% to about 80% by weight of the pigment dispersed in the reactive diluent is suitable. Since pigment dispersions are well known, those skilled in the art can use well known pigment dispersions for preparing the improved ink composition according to the present invention based on the contents described herein.
    [76] Ribbon assemblies using up to 12 coated optical glass fibers require only 12 colors to properly distinguish the coated optical fibers from each other. However, in larger ribbon combinations, more than 12 colors can be used to properly distinguish the coated optical glass fibers from each other. Examples of twelve colors that can normally be used to make ribbon combinations include black, white, yellow, blue, red, green, orange, brown, pink, turquoise, purple and gray.
    [77] Specific examples of suitable black pigments include carbon black.
    [78] Particular examples of suitable white pigments include titanium dioxide.
    [79] Specific examples of suitable yellow pigments include diaryl yellow and diazo pigments.
    [80] Specific examples of suitable blue pigments include phthalocyanine blue, basic dye pigments and phthalocyanine.
    [81] Specific examples of suitable red pigments include anthraquinone (red), naphtholyl red, monoazo pigments, quinacridone pigments and perylenes.
    [82] Specific examples of suitable green pigments include phthalocyanine green and nitroso-based pigments.
    [83] Specific examples of suitable orange pigments include monoazo and diazo pigments, quinacridone pigments, anthraquinones and perylenes.
    [84] Specific examples of suitable purple pigments include quinacridone violet, basic dye pigments and carbazole dioxazine-based pigments.
    [85] Suitable turquoise, brown, gray and pink pigments can be readily prepared by combining different colors. One skilled in the art can form the specific color as desired by combining other colorants.
    [86] The pigment may be present in the ink composition in an amount capable of providing a visible color without magnification to facilitate identification of the individual colored optical glass fibers. The amount of the pigment significantly reduces the cure rate of the ink composition and It should not be large enough to produce an undesired effect. A suitable amount of pigment was found to be about 1 to about 20 wt.%, Preferably about 1 to about 15 wt%, more preferably about 1 to about 10 wt%, based on the total amount of the ink composition.
    [87] Preferably, the ink composition comprises at least one photoinitiator in an amount of about 1 to about 20 weight percent, more preferably about 1 to about 10 weight percent, based on the total amount of the ink composition.
    [88] The ink coating composition can be added to the coated optical glass and cured using any suitable method. Examples of suitable methods are disclosed in US Pat. No. 4,629,285, which is incorporated herein by reference in its entirety. The ink composition can also be used in a similar manner as in optical glass fiber drawing and the use of an external primary coating on a coating tower.
    [89] Ink coatings are typically about 3 to about 10 microns thick and concentric to prevent attenuation of signal transmission. However, if desired, the ink coating can be used in any form suitable for visually identifying the color of the individual coated optical glass fibers. Examples of suitable coatings include desiccants, dots, lines and rings. Preferably the ink coating is substantially concentric. The ink coating composition according to the present invention can provide substantially concentric ink coatings as well as discontinuous coatings such as desiccants, dots, lines and rings.
    [90] Ribbon assemblies are currently known in the art, and the content described herein enables one of ordinary skill in the art to make novel ribbon assemblies that include at least one improved coated fiber of the present invention for its intended use. Novel ribbon assemblies made in accordance with the present invention can be used in communication systems. The communication system typically includes a ribbon assembly comprising an optical fiber, a transmitter, a receiver and a switch. The ribbon assembly comprising the coated optical fibers of the present invention is a basic connecting unit in a communication system. The ribbon assembly may be buried underground or for underwater connection for long distance connections such as intercity connections. The ribbon assembly can also be used to connect directly to a dwelling house.
    [91] The novel ribbon assemblies made in accordance with the present invention can be used in cable television systems. The cable television system typically includes a ribbon assembly comprising an optical fiber, a transmitter, a receiver and a switch. The ribbon assembly comprising the coated optical fibers of the present invention is the basic connecting unit of the cable television system and can be buried underground or underwater for long distance connections, such as a communication system, or used to connect directly to a resident's home.
    [92] The present invention may be further understood in light of the following examples which illustrate without limiting the invention.
    [93] In the examples, the following abbreviations and names are used in the following chemical names:
    [94] Oligomer A: Bisphenol A epoxy acrylate oligomer
    [95] Oligomer B: Aliphatic urethane acrylate oligomer
    [96] Oligomer C: Aliphatic urethane acrylate oligomer
    [97] PETTA: pentaerythritol tetraacrylate
    [98] TMPTA: trimethylolpropane triacrylate
    [99] HDDA: 1,6-hexanediol diacrylate
    [100] IBOA: Isobonylacrylate
    [101] IPDI: isophorone diisocyanate
    [102] TMDI: trimethylhexamethylene diisocyanate
    [103] DESW: Bis 4,4 '-(isocyanatocyclohexyl) methane
    [104] BHT: Inhibitor
    [105] Additive A: Secondary amino α, ω-aminoorganofunctional polydimethylsiloxane of Formula 2, wherein n ≒ 10
    [106] Additive B: Secondary amino α, ω-aminoorganofunctional polydimethylsiloxane of Formula 2, wherein n ≒ 30
    [107] Additive C: hydroxy functional polydimethylsiloxane copolymer with a number average molecular weight of 950 ± 80
    [108] Additive D: hydroxy functional polydimethylsiloxane copolymer with a number average molecular weight of 2500 ± 250
    [109] Additive E: acrylate terminated polydimethylsiloxane copolymer with a number average molecular weight of 1100 ± 100
    [110] Photoinitiator A: Phenyl bis (2,4,6-trimethylbenzoyl) phosphene oxide
    [111] Photoinitiator B: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine propane-1-one
    [112] Photoinitiator C: 2-hydroxy-2-methyl-1-phenylpropan-1-one
    [113] Photoinitiator D: acrylate benzophenone
    [114] White Colorant: TMPTA Pigment Dispersion
    [115] Yellow Colorant: TMPTA Pigment Dispersion
    [116] Red colorant: TMPTA pigment dispersion
    [117] Blue colorant: TMPTA pigment dispersion
    [118] Stabilizer A: Stabilized surfactant owned by BYK Chemie
    [119] Optical fibers coated with the ink compositions described in the examples were prepared by standard techniques. The ink composition used for the fiber was cured on the fiber at 600 m / m. The fibers are then coated with a matrix resin added to the coated optical fibers and cured at 260 m / m.
    [120] In the examples herein, the releasability of the optical fibers of the compositions made with secondary or tertiary amino silicone-containing release agents is measured according to the following method:
    [121] Ribbon Breakout
    [122] Ribbon breakout is measured using strands of four fiber ribbons of approximately 1 m. The ribbon strand is held between the thumb and forefinger of one hand and extends approximately ½-1 cm of ribbon at the grip. Drag or peel the tear or exposed edge of the ribbon with the nail of the other hand. Breakout is good if the matrix material is easily fragmented after scraping with nails on the ribbon and the fibers are peeled off at the expanded portion of the matrix material. If the matrix material is not easily fragmented and is twisted or broken by some other method, it is determined that the "breakout" is bad.
    [123] Mid-Span Access
    [124] 75 micron thickness stretching of the radiation-cured outer primary coating composition is applied to a Mylar Sheet and cured by exposure to 1 Joule / cm 2 of UV light in a Fusion D lamp under a nitrogen atmosphere to form a cured outer primary film. . 5-10 micron stretching of the sample radiation-curable ink composition is formed in the cured outer primary film. The ink composition is cured by exposure to 1 Joule / cm 2 of UV light in a Fusion D lamp in air to form a cured ink coating. 75 micron thick stretching of the radiation-curable matrix composition is formed in the ink coating. The matrix composition is cured by exposure to 1 Joule / cm 2 of UV light in a Fusion D lamp under nitrogen atmosphere to form a cured matrix material on the ink coating.
    [125] The strip of the formed multilayer film is cut to have a width of about 6.4 mm to about 12.7 mm. At one end of each strip, a portion of the matrix material is separated from the ink coating using a knife. A force is applied to the separated portion of the matrix material to peel off the remaining matrix material from the ink coating. When the remaining matrix material peeled off cleanly from the ink coating, the ink coating remained intact and the matrix material did not break, so the ink coating passed the mid-span approach test.
    [126] Example 1-5
    [127] This example describes an ink base composition and ink composition comprising a secondary amino silicon-containing release additive according to the present invention. The additive is a secondary amino polydimethylsiloxane represented by additive A. The ink base composition and ink composition are disclosed in Table 1 below.
    [128] Example 1Example 2Example 3Example 4Example 5Clear ink baseWhiteRedyellowblue Oligomer A30.4526.0023.5224.3526.58 PETTA15.2613.0311.7912.2013.32 TMPTA9.107.777.037.287.94 HDDA7.136.095.515.706.22 IBOA7.036.005.435.626.14 Oligomer B20.0017.0715.4516.0017.46 BHT0.570.490.440.460.50 Additive A3.883.313.003.103.39 Photoinitiator A2.001.711.551.601.75 Photoinitiator C4.583.913.543.664.00 Colorant: white0.014.382.3810.561.00 Colorant: Yellow0.00.000.009.210.00 Colorant: Red0.00.0016.010.000.00 Colorant: Blue0.00.000.000.0011.45 Stabilizer A0.250.250.250.250.25 all100.00100.00100.00100.00100.00
    [129] Each of the compositions of Examples 1-5 tests their releasability according to the breakout and mid-span approach tests described above. All of the above compositions show very good release properties. The matrix material is easily removed from the fiber, the remaining matrix material does not adhere to the fiber, and the matrix material does not remove the ink coating from the fiber.
    [130] Example 6-7
    [131] This example illustrates an ink composition prepared according to the present invention, wherein the silicon-containing release agent is additive B. The composition and mid-span access test results are shown in Table 2 below:
    [132] ingredientExample 6Example 7 Oligomer A31.3532.31 HDDA21.8322.48 Oligomer C20.9021.54 Additive B2.202.27 BHT0.480.50 Photoinitiator A1.371.41 Photoinitiator B2.752.83 Photoinitiator C3.853.96 Colorant: white15.021.00 Colorant: Blue0.011.45 Stabilizer A0.250.25 all100.00100.00 Mid-span approachPassPass
    [133] Synthesis of Additive F-R
    [134] This synthesis describes the synthesis of tertiary-amino polydimethylsiloxane release agents used in ink bases and ink compositions. The release agent (F) is prepared using the Michael amine reaction of a low molecular weight secondary amine with the acrylate group of the acrylate functional siloxane compound (E). Other release agents are prepared using the method as described above for the synthesis of urethane acrylate oligomers. The chemicals used to prepare the tertiary amino silicon-containing release agents are set forth in Table 3 below:
    [135] ingredientEx.FEx.GEx.HEx.JEx.KEx.LEx.MEx.NEx.PEx.QEx.R Dimethylethanolamine 5.7211.6110.8911.45 Diethanol amine12.14 1-ethyl-3-hydroxy piperidine 16.27 8.28 Hydroxyethyl morpholine 8.24 16.33 Dimethyl propanol amine 8.6416.91 IPDI 14.24 28.5 TMDI 26.0513.26 26.0313.225.8513.2527.46 DESW 31.99Additive D 78.580.04 78.16 18.47 Additive C 57.68 57.64 57.24 60.9357.1260.05 Additive E87.86 all100100100100100100100100100100100
    [136] Examples 8-13 and Experimental A-D
    [137] Tertiary amino polydimethylsiloxane release agents F, P and R are added to the ink as disclosed in Table 4 below. For comparison, aminohydrocarbons are also tested as described in Experiments a through d.
    [138] Example 8-13 and Experiments a-d test the mid-span approach as described above.
    [139] ingredientEx.8Ex.9Ex.10Ex.11Ex.12Ex.13Ex.aEx.bEx.cEx.d Oligomer A30.3231.2430.3231.2430.3231.2430.3231.2430.3231.24 HDDA18.2918.8418.2918.8418.2918.8418.2918.8418.2918.84 Oligomer C15.8216.3015.8216.3015.8216.3015.8216.3015.8216.30 Additive F4.414.54 Additive P 4.414.54 Additive R4.414.54 Cocamide DEA 4.414.54 Cocamidopropyl DMA4.414.54 BHT0.480.500.480.500.480.500.480.500.480.50 Photoinitiator A0.960.990.960.990.960.990.960.990.960.99 Photoinitiator B3.863.973.863.973.863.973.863.973.863.97 Photoinitiator C2.892.982.892.982.892.982.892.982.892.98 Photoinitiator D7.707.947.707.947.707.947.707.947.707.94 Colorant: white15.021.0015.021.0015.021.0015.021.0015.021.00 Colorant: Blue 11.45 11.45 11.45 11.45 11.45 Stabilizer A0.250.250.250.250.250.250.250.250.250.25 all100.00100.00100.00100.00100.00100.00100.00100.00100.00100.00 Mid-span approachPassPassPassPassPassPassfailurefailurefailurefailure
    [140] Each ink (Examples 8-13) containing tertiary amino polydimethylsiloxane release agents shows good release properties. Inks with only aminohydrocarbons (Experiment a-d) do not show releasability.
    [141] Although the present invention has been disclosed in the preferred embodiments, it is not intended to limit the invention, and it will be apparent to those skilled in the art that the preferred embodiments may be modified. The invention may be practiced otherwise than as specifically described herein. Accordingly, the invention is intended to embrace all such modifications as come within the spirit and scope of the appended claims.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] At least one monomer or oligomer having a radiation-curable functional group in the uncured state; Photoinitiators for the monomer or oligomer present in sufficient amounts to effect radiation curing of the monomer or oligomer; And a secondary amino or tertiary amino silicone-containing additive.
    [2" claim-type="Currently amended] At least one monomer or oligomer having a radiation-curable functional group in the uncured state; Photoinitiators for the monomer or oligomer present in sufficient amounts to effect radiation curing of the monomer or oligomer; And a secondary amino or tertiary amino silicone-containing additive, wherein the radiation curable optical fiber coating composition for a member selected from the group comprising an outer primary coating, an ink coating, a buffer material or a matrix material.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    The silicon-containing additive is a composition, characterized in that the compound having a structure of formula (1).
    (Formula 1)

    (In Chemical Formula 1, each of R 1 , R 2 , R 3, and R 4 may be the same or different, and each is an aliphatic or aromatic hydrocarbon.)
    [4" claim-type="Currently amended] The method according to claim 1 or 3,
    And the silicone-containing additive is selected from the group comprising secondary amino-functional polydimethylsiloxanes, tertiary amino-functional polydimethylsiloxanes or mixtures thereof.
    [5" claim-type="Currently amended] The method according to claim 1 or 4,
    A composition further comprising a colorant.
    [6" claim-type="Currently amended] The method of claim 5,
    And the colorant comprises a dye.
    [7" claim-type="Currently amended] The method of claim 5,
    And the colorant comprises a pigment.
    [8" claim-type="Currently amended] An optical fiber, which is coated with the composition according to any one of claims 1 to 7.
    [9" claim-type="Currently amended] At least one of the coated optical fibers comprises a colored layer as the outermost layer, the fiber is coated with a matrix material, and in the uncured state the colored layer comprises a secondary amino or tertiary amino silicone-containing additive; And at least two coated optical fibers.
    [10" claim-type="Currently amended] At least one monomer or oligomer having a radiation-curable functional group in the uncured state; Photoinitiators for the monomer or oligomer present in sufficient amounts to effect radiation curing of the monomer or oligomer; And a silicone-containing additive comprising a reaction product of a secondary amino-functional polydisubstituted siloxane with an ethylenically unsaturated compound.
    [11" claim-type="Currently amended] The method of claim 10,
    Wherein said ethylenically unsaturated compound comprises only one double bond such that the reaction product of said secondary aminofunctional polydisubstituted siloxane and said ethylenically unsaturated compound contains substantially no ethylenically unsaturated groups. Composition.
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    同族专利:
    公开号 | 公开日
    WO2001047823A2|2001-07-05|
    US20030176523A1|2003-09-18|
    US7041712B2|2006-05-09|
    CN100347116C|2007-11-07|
    EP1240117A2|2002-09-18|
    BR0017045A|2002-11-05|
    JP2003519249A|2003-06-17|
    US6538045B1|2003-03-25|
    AU3243401A|2001-07-09|
    CN1434788A|2003-08-06|
    WO2001047823A3|2001-12-06|
    KR100729045B1|2007-06-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-12-23|Priority to US09/471,694
    1999-12-23|Priority to US09/471,694
    2000-12-18|Application filed by 디에스엠 엔.브이
    2002-08-21|Publication of KR20020067046A
    2007-06-14|Application granted
    2007-06-14|Publication of KR100729045B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/471,694|US6538045B1|1999-12-23|1999-12-23|Optical fiber coating compositions containing secondary or tertiary amino silicone-containing additive|
    US09/471,694|1999-12-23|
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