JP4728576B2 - Colored radiation curable composition - Google Patents

Description

  This application is a continuation-in-part of co-pending US patent application Ser. No. 09 / 870,482, which is a part of co-pending US patent application Ser. No. 09 / 360,951. It is a continuation application.

This application discloses and claims the subject matter of the invention from the following applications:
1) co-pending application No. 09 / 870,482 filed on June 1, 2001 2) co-pending application No. 09 / 360,951 filed July 27, 1999;
3) Patent Cooperation Treaty Application No./US 01 / 05,814 filed on March 16, 2001;
4) Co-pending provisional application 60 / 356,160, filed February 14, 2002. The disclosures of these applications are incorporated herein by reference.

  The present invention relates to colored radiation curable compositions for use in various applications, including coating compositions for communication elements such as colored radiation curable optical fibers and optical fiber ribbons, textiles, The invention relates to colored radiation curable ink compositions for other applications such as electronic components and printing applications. Furthermore, the present invention relates to a colored radiation curable composition for producing a cured and colored coating on a support such as a communication element, wherein the cured composition is in the composition after curing. Having an identification color provided by a compound containing a chromophore covalently bonded to another device.

  For many years now, optical fibers have been used as reliable transmission media in communication cables. An optical fiber typically has a core, a cladding layer, and one or more coatings applied over the cladding layer.

  One purpose of the coating is to protect the surface of the optical fiber from mechanical scratches and scratches, usually caused by post-manufacture handling and use. Another purpose of the coating is to protect the glass from exposure to moisture. Since the coating is physically responsive to external mechanical forces and temperatures, the coating or multiple coatings also have some effect on the optical properties of the fiber. The composition of this coating applied to the optical fiber is usually a liquid and a radiation curable composition. Typically, the coating composition is cured on the optical fiber by exposing it to ultraviolet radiation, electron beam radiation or ionizing radiation at a predetermined time deemed appropriate for effective curing.

  There are various types of structures for communication cables such as optical fibers. In some cable types, the optical fiber is loosely held inside the buffer tube, and in other cables, the optical fibers are arranged in a planar array to form an optical fiber ribbon. This planar array is usually encapsulated in one or more layers of radiation curable matrix material. The radiation curable matrix layer is cured by exposing the matrix material to ultraviolet radiation, electron beam radiation, ionizing radiation or infrared radiation at a predetermined time deemed appropriate for effective curing.

  In communication cables containing multiple optical fibers, the optical fibers can be distinguished from one another using a color coating layer applied over the coated optical fiber. The color of this color coating layer is usually obtained by dispersing colored pigment particles in a suitable liquid phase carrier and applying the liquid phase carrier onto the coating. Alternatively, the optical fibers can be distinguished from each other using so-called colored primary coatings, which are applied directly onto the optical fiber.

  Unfortunately, the use of pigment particles to impart color to color coatings for optical fibers has presented manufacturing and performance problems. For example, the pigment particles and the liquid phase carrier tend to gradually separate into two separate phases, resulting in a color coating containing the pigment having a relatively short shelf life.

  Furthermore, when a colored system containing pigment undergoes phase separation, the resulting pigment particles aggregate simultaneously, further complicating the system. Unfortunately, the presence of aggregated pigment particles in the color coating on the coated optical fiber can induce microbends that result in transmission loss.

  Usually, pigment materials are required to have a relatively high concentration in order to obtain opaque color coatings curable with ultraviolet radiation. This pigment has the property to refract, reflect and scatter incident radiation, so when high concentrations are required, it unfortunately impedes the transmission of incident ultraviolet radiation necessary to cure this color coating material Will do. The phenomenon of inhibiting ultraviolet radiation results in a decrease in the processing speed of the optical fiber along the manufacturing line, thereby increasing the manufacturing cost. Also, if the curing speed of the color coating containing the pigment is slow, the processing and curing of these materials are more susceptible to the effect of small changes in the thickness of the color coating.

  As an alternative to pigment-based color coatings, the use of dyes to provide color to the color coating has been considered. Some dyes absorb light, which can slow the cure, but dyes have the advantage of curing faster than pigments because they do not scatter curing radiation. However, dyes are generally not recommended because they diffuse (bleed) into common cable filling compounds, resulting in loss of color. In an attempt to reduce bleed, US Pat. No. 5,074,643 teaches the use of polymeric dyes in the color coating. A polymeric dye refers to a polymeric chromophore containing molecules that become trapped within a cross-linked coating network. Because of this trapping, the dye bleeds nonetheless, although it eventually delays the bleed process. Even with the use of entrapped polymer dyes, this color imparted to the fiber can easily be lost over time, and if the color is lost from the fiber, the fibers are very difficult to distinguish from each other and the fiber is spliced in the field. Sometimes you will spend time.

  The color imparted to this fiber will disappear over time if the dye itself lacks stability. In particular, the dyes used here must have sufficient thermal stability and lightfastness, which gives the desired color over a long period of time.

  If a communication cable has multiple optical fiber ribbons, it is generally desirable to distinguish one from the other optical fiber ribbons by coloring each of the optical fiber ribbons. Usually, the color of the colored optical fiber ribbon is obtained in the same manner as that obtained with a color coated optical fiber. The matrix composition of the optical fiber ribbon is obtained with either a pigment or a polymer dye. The same problems described above with respect to colored optical fibers apply to colored optical fiber ribbons.

  Therefore, durable and hardened color coding that can be used for communication elements such as optical fiber and its coating has the ability to withstand the conditions of normal operating environment in which such elements are normally found It is desirable to provide a composition that can provide It would be desirable to provide a composition capable of providing a cured ink, dye coating, pigment that has durability that can be used for substrates in other fields such as textile materials, electronic components, printed materials, etc. The dyes, coatings, pigments, etc. will have the ability to withstand typical operating environment conditions such as those normally found.

  The present invention provides such a composition.

  In one aspect of the invention, a compound comprising a chromophore is provided, the compound comprising the chromophore sharing the chromophore-containing compound with any other molecule or series of molecules in the radiation curable composition. A compound containing one or more functional groups capable of reacting with a bond and containing the chromophore is incorporated into the radiation curable composition via a covalent bond.

  In a first embodiment of the first aspect of the present invention, the compound containing a chromophore has one or more radiation curable groups as one or more functional groups. A compound containing a chromophore containing one or more radiation curable groups becomes covalently bonded to other components of the radiation curable composition by one or more covalent bonds during the curing process.

  In a second embodiment of the first aspect of the present invention, the compound containing a chromophore is a colored oligomer. For example, a compound containing a chromophore that is covalently bonded to or within the oligomer backbone is obtained, whereby the chromophore of the compound containing the chromophore is bonded with one or more covalent bonds. Will bind to other parts of the oligomer. The colored oligomers may contain radiation curable groups and become covalently bonded to other components of the radiation curable composition during the curing process.

  In another aspect of the present invention, there is provided a radiation curable composition comprising a compound comprising a chromophore, wherein the compound comprising the chromophore comprises a compound comprising the chromophore as a radiation curable composition. Contains one or more functional groups that can be covalently reacted with any other molecule or series of molecules in the object. Upon receipt of an appropriate level of radiation, the radiation curable composition comprises a compound containing a chromophore covalently bonded to another molecule or series of molecules in the radiation cured composition, A cured composition is produced.

  In yet another aspect of the invention, there is provided a color concentrate or masterbatch comprising a compound containing a chromophore, wherein the color concentrate or masterbatch is for applications where a compound containing a chromophore is specifically desired. Or a vehicle for delivery for an embodiment. A method for producing such a concentrate or masterbatch is also provided.

  In a further aspect of the invention, there is provided a communication element having thereon a color identifying coating, the communication element being applied to at least one elongate communication transmission medium and at least a portion of the transmission medium. A coating having a distinguishing color, the coating comprising a radiation-cured and crosslinked polymer network, and the distinguishing color in the coating being covalently bonded to the polymer network with at least one covalent bond Provided by at least one chromophore molecule. The color of the communication element thus prepared according to the invention does not bleed even in the presence of the cable filling compound. For example, the communication element may be a fiber optic ribbon, the ribbon having a colored matrix or colored coating applied over an uncolored matrix, where it is colored. Matrix or colored coating color does not bleed even in the presence of cable filling compounds.

  In a further aspect of the invention, there is provided a method of making a colored, radiation curable composition having a compound comprising at least one chromophore, the compound comprising the chromophore comprising the compound comprising the chromophore as the radiation. Having one or more functional groups capable of covalently reacting with any other molecule or series of molecules in the curable composition, and including at least one chromophore in at least a portion of the support A method of applying a radiation curable composition with a compound is provided, wherein the compound containing the chromophore is covalently bound to another molecule or series of molecules within the radiation cured composition.

  The method includes providing, for example, a transmission medium to a support; providing a colored radiation curable composition comprising a compound containing a chromophore; and applying the radiation curable composition to at least a portion of the support. Applying a radiation curable composition to radiation of an appropriate wavelength and intensity for an appropriate period of time and curing the composition to a radiation-cured crosslinked polymer network, the polymer network; Providing at least one chromophore molecule covalently bound by at least one covalent bond to its distinguishing color in the coating.

  The invention will be more fully understood with reference to the following detailed description, taken in conjunction with the accompanying drawings, in which:

  A typical communication element has an elongated transmission medium such as a metal wire or an optical fiber. Referring to FIG. 1A, a typical optical fiber 10 transmission medium is shown. A typical optical fiber 10 is formed of a glass core 12 surrounded by a glass cladding layer 14. The glass cladding layer 14 of the optical fiber 10 is typically surrounded by one or more protective polymer coatings, such as primary, secondary polymer coatings, or primary, secondary, tertiary polymer coatings.

  For example, as shown in FIG. 1A, the inner protective polymer coating 16 covers at least a portion of the cladding layer 14 and the outer protective polymer coating 18 typically covers at least a portion of the inner coating 16. The inner 16 and outer 18 protective coatings are also referred to as inner primary and outer primary coatings or primary and secondary coatings. The inner coating 16 is usually obtained by applying a radiation curable (polymerizable) composition capable of forming a polymer coating that cures over the cladding layer 14.

  The radiation curable composition is typically applied by passing the optical fiber through a first die or coating applicator using techniques well known in the art and therefore will not be described here. Once the radiation curable composition is applied over the cladding layer 14, the composition is exposed to radiation such as ultraviolet radiation, electron beam radiation or ionizing radiation to initiate its curing (polymerization). Can be cured. In this case, ultraviolet light is most often used.

  After the radiation curable composition for forming the inner coating 16 is applied and cured, another radiation curable composition capable of forming a polymer coating that forms the outer coating 18 may be applied and cured. Good. This ordering scheme is known as wet-on-dry application of the outer coating 18. In some cases, subsequent to the application of the radiation curable composition to form the inner coating 16, immediately thereafter, the application of the radiation curable composition to form the outer coating 18 is performed prior to exposure to the curing radiation. Also good. This is known in the art as wet on wet coating. Each coating technique is well known in the art.

  As used herein, the term “primary coating” is defined as a coating that directly contacts the glass portion of the optical fiber. The uncured primary coating must be liquid at room temperature. The uncured primary coating must have a viscosity suitable for high speed processing, and the uncured primary coating must have a high cure rate. The cured primary coating must have suitable adhesion to the glass, which can prevent the coating from peeling off from the glass portion of the optical fiber when it is immature. . The cured primary coating must have a low modulus at low temperatures to minimize microbend attenuation when the optical fiber itself is under low stress.

  As used herein, a “secondary coating” is defined as a coating that covers a primary coating on an optical fiber. The cured secondary coating must have sufficient modulus to provide impact resistance, provide a protective barrier, and provide break strength to the optical fiber. After curing, the secondary coating must exhibit little physical change over a wide range of temperatures and must have good resistance to water and solvent absorption. If this secondary coating is colored, the color stability must be good.

The uncured liquid primary and secondary coating composition must have a sufficiently low viscosity so that the composition can be easily applied to form a continuous protective coating on the glass fiber. Will be able to. Suitable viscosities are on the order of about 10 ³ cP at 45-50 ° C., for example, about 2 × 10 ³ to about 8 × 10 ³ cP at room temperature. The viscosity is not particularly limited and may be adjusted by a coating method using a known method. For example, the viscosity can be adjusted depending on the type of fiber optic material being assembled and the method of application, and also the processing temperature used.

  Usually, the thickness of the cured primary and secondary coatings depends on the intended use of the optical fiber, but about 20 to 35 microns, in particular 25 to 30 microns is suitable.

When used as a primary coating, a cured coating, according to the present invention, has a glass transition temperature (T _g ) of about −60 ° C. to about 0 ° C., for example, about −50 ° C. to about −30 ° C., specifically May have a glass transition point of about −40 ° C. and a low elastic modulus of about 0.5 to about 3.0 MPa at room temperature (20 ° C.) and 50% relative humidity, for example about 1.0 To an elastic modulus of about 2.5 MPa.

When used as a secondary coating, the cured coating may have a glass transition point (T _g ) of about 25 ° C. to about 100 ° C. according to the present invention. The cured secondary coating may have a T _g of about 50 ° C. to about 80 ° C., eg, about 75 ° C. The cured secondary coating may have a low modulus of elasticity of about 5.0 to about 60 MPa, eg, about 20 to about 40 MPa, specifically about 30 MPa at about 80 ° C. and 50% relative humidity. .

  Conventional radiation curable conventional compositions capable of forming polymer coatings for the inner 16 and outer 18 coatings include acrylated oligomers, which include polyether diols, polyester diols, It is a urethane acrylated oligomer which is a reaction product of a polyol (1) such as a hydrocarbon diol, a polyisocyanate (2) such as an aliphatic diisocyanate, and a terminal capping monomer such as hydroxyalkyl acrylate or hydroxyalkyl methacrylate. These oligomers usually have monofunctionality, difunctionality, and trifunctionality. Other materials such as photoinitiators, inert diluents, etc., and adhesion promoters such as organofunctional silane adhesion promoters may be included in the radiation curable composition, so that Physical properties are tailored to specific end use applications, such as providing coatings with heat resistance, oxidation resistance, hydrolysis resistance, and flexible, responsive, low glass transition points. Radiation curable primary and secondary coating compositions can be found in US Pat. No. 5,146,531, which is hereby incorporated by reference in its entirety.

  Although there are specific reference materials in the case of communication elements that are coated with primary and secondary coatings, such elements can be coated with additional coatings such as tertiary coatings or just with one coating. Those skilled in the art will readily understand that this is possible. The tertiary coating is usually thinner than the secondary coating, eg, 10% thicker than the secondary coating. In this way, the tertiary coating is applied to a thickness of 2 to 5 microns.

  In accordance with the present invention, for example, an uncolored radiation curable composition that is applied onto a cladding layer and cured to form an inner coating 16 includes a chromophore of a compound containing the chromophore in the composition, and the radiation. It may be colored by adding a compound containing a chromophore containing one or more functional groups that can be covalently attached to any other molecule or series of molecules in the curable composition.

  This chromophoric portion of the compound containing the chromophore may be selected, for example, from the following dye chemical family including non-consumable chemicals, anthraquinones, methines and azos. Even if the chromophore portion of the compound containing the chromophore is anthraquinone type, methine type, azo type, a mixture thereof or other types, the selected chromophore portion of the compound containing the chromophore has good thermal stability and light resistance It is preferable to exhibit properties. Moreover, the molecular weight of the chromophore part of the compound containing a chromophore is not limited. The moiety may be a monomer moiety that includes a chromophore, or it may be an oligomer moiety that includes a chromophore in the backbone chain of the oligomer chain, or includes a chromophore as a terminal or side chain of the oligomer chain. There may be.

  In general, the functional group (s) of a compound containing a chromophore according to the present invention can covalently link the chromophore of the compound containing the chromophore to any other compound or series of compounds in the radiation curable composition. All groups that can be reacted and thereby incorporate the chromophore molecule itself into the radiation curable composition. For example, a compound containing a chromophore can be radiation curable, such as an ethylenically unsaturated group such as an acrylate group that is covalently bonded to other similar groups in the radiation curable composition when exposed to radiation. It may contain a functional group.

  In certain embodiments, the functional group (s) of a compound comprising a chromophore of the invention is reacted with a monomer or oligomer comprising a radiation curable group to form at least one covalent bond with the monomer or oligomer. A radiation curable monomer or oligomer can be formed that binds the chromophore to the. A radiation curable monomer or oligomer containing a covalently linked chromophore is itself covalently bonded, eg, a radiation curable monomer or oligomer in a radiation curable composition that does not contain a chromophore. Can be bound to any other compound or series of compounds.

  For example, a radiation curable monomer or oligomer containing a chromophore covalently attached thereto may also have radiation curable end group (s) or side group (s). Good. When exposed to radiation, the end group (s) or side group (s) are covalently bonded to a compound containing similar groups in the radiation curable composition. As a specific example, a radiation curable composition may have a compound that contains an acrylate group, a vinyl group, or an epoxy group, and includes a chromophore molecule that is covalently bonded thereto. Possible monomers or oligomers become capable of covalent bonding.

  More specific examples where the functional group (s) of the compound containing the chromophore of the embodiment reacts with a monomer or oligomer containing a radiation curable group include hydroxy functionality and chromophore covalently bound thereto Mention may be made of polyols containing chromophores containing molecules. Polyols containing this chromophore may have ester or carboxy functionality in addition to the hydroxy functionality. For example, by reacting a polyol containing a chromophore moiety covalently bonded to it with an oligomer of a radiation curable composition, the chromophore can only be a radiation curable oligomer by means of at least one covalent bond. Eventually, it will also be incorporated into the cured composition.

  Common examples of colored monomer or oligomer components of radiation curable compositions include polyols containing chromophore molecules and hydroxy end groups or side groups covalently bonded thereto, such as aliphatic diisocyanates and the like. Typical hydrocarbon diols that react with isocyanates and radiation curable monomer (s) to form the usual acrylate oligomer reaction products used in radiation curable compositions for optical fibers and the like It can be used in addition to or in place of some or all of the polyols. An example of a suitable polyol containing a chromophore molecule covalently bonded thereto is the group of dyes marketed by Milliken Chemical Company under the trademark REACTINT ™. If a sufficient amount of polyol containing a chromophore molecule covalently bound to it reacts with an isocyanate and a radiation curable monomer, the resulting monomer or oligomer is covalently bound to that monomer or oligomer. One skilled in the art will now recognize that it will be colored depending on the color of its chromophore molecule (or a mixture of chromophore molecules to obtain a color spectrum). .

  A radiation curable composition comprising a compound comprising a chromophore according to the invention, such as a colored and acrylated monomer or oligomer, is applied, for example, directly to the cladding of an optical fiber as a colored radiation curable composition, to form an inner coating. 16 can be formed, or it can be applied directly as an outer coating 18 over a previously applied inner coating. A person skilled in the art has previously applied a radiation curable composition comprising a compound comprising the chromophore of the present invention, such as a colored monomer or oligomer, previously applied as a tertiary coating 20, as illustrated in FIG. 1B. It will be appreciated that it may be applied over the outer coating. Alternatively, a radiation curable composition comprising a compound comprising a chromophore according to the present invention, such as a colored and acrylated monomer or oligomer, is applied onto or within a ribbon matrix to produce a colored optical fiber ribbon. May be.

In a commercially advantageous alternative, compounds containing the chromophore according to the invention, such as colored and acrylated monomers or oligomers, such as compositions that are usually prepared to provide a protective coating for optical fibers, A commercially available, uncolored radiation curable composition that is blended or diluted with a chromophore-free analog, thus containing a chromophore-containing compound and chromophore according to the present invention. The combination of analogs that do not include forms a colored radiation curable composition that is applied, for example, to the optical fiber cladding layer 14, inner coating 16 or outer coating 18 (or onto or in the ribbon matrix). Can be done. Such radiation curable compositions further comprise one or more uncolored acrylated oligomers, reactive diluents, one or more photoinitiators, organofunctional silane adhesion promoters, TiO _It may contain pigments such as ₂ and stabilizers. In other words, the chromophore-containing compounds described herein are commercially known and uncolored used to provide a protective coating over the optical fiber in an amount sufficient to provide color. It may be added to the radiation curable composition.

  After curing or polymerizing a radiation curable composition containing a compound containing a chromophore, such as colored monomers and / or oligomers, for a suitable time by exposure to radiation of the appropriate wavelength and intensity Thus, the resulting cured composition will include chromophore molecules covalently bonded thereto. Since this chromophore molecule is covalently bonded to other components in the cured composition, color loss due to bleeding is negligible. In this way, the dye provides the manufacturing advantage of being faster to apply and cure than the pigment, thereby not being covalently bonded when used in an optical fiber environment or other work environment. The disadvantage of bleeding that the dye would have can be avoided.

According to one embodiment, a compound comprising a chromophore adapted to impart color to a communication element, such as a coated optical fiber or a coated optical fiber ribbon, is also provided in other applications. Compounds containing this chromophore can be formed using chemical techniques for isocyanates. For example, a compound containing a chromophore containing an isocyanate-reactive functional group (s), such as —OH, —NH ₂ , —SH, etc. can be synthesized with a radiation curable group, eg, an isocyanate containing an ethylenically unsaturated bond. Can react. An example of an isocyanate containing a radiation curable group is meta-isopropenyl-α, α-dimethyl isocyanate, but any monoisocyanate or polyisocyanate containing a diisocyanate may be used as long as the radiation curable group is included. be able to.

  According to another embodiment, a compound containing a particular type of chromophore, i.e. an oligomer containing a chromophore, is provided, which can be applied to other application methods to impart color to a communication element such as a coated optical fiber. Is also adapted. The oligomer containing this chromophore can be formed by various methods. For example, the chromophore portion of the oligomer containing the chromophore may be one covalent bond to the remaining portion of the oligomer, thereby making the chromophore portion a terminal or side chain group of the oligomer. . In some cases, the chromophore portion of the oligomer containing the chromophore may be bound to the remainder of the oligomer by a pair of covalent bonds, whereby the chromophore portion is attached to the backbone chain of the oligomer. Part.

  An example of providing an oligomer comprising a chromophore having the chromophore moiety as part of the oligomer backbone includes generating an oligomeric precursor having at least two terminal isocyanate groups. This oligomer precursor is said to be end-capped by isocyanate groups.

This isocyanate end-capped oligomer can be converted to an oligomer capped with a radiation curable group. For example, an isocyanate end-capped oligomer precursor comprises (i) a functionality that reacts with the isocyanate group of the isocyanate end-capped oligomer precursor, and (ii) a radiation curable functional group that includes ethylenic unsaturation. You may make it react with the radiation-curable monomer containing both. Examples of the group having reactivity with an isocyanate group include —OH, —NH ₂ , and —SH. Reaction with an isocyanate group produces a covalent bond. For example, a urethane bond is generated by the reaction of an —OH group with an isocyanate group, and a urea bond is generated by a reaction of the —NH _{2 with} an isocyanate group.

Isocyanate end-capped oligomer precursors are at least one multifunctional having at least two groups that react at least one isocyanate such as a polyisocyanate, for example a diisocyanate, with an isocyanate group such as —OH, —NH ₂ , —SH. It is prepared by reacting with a sex compound. A specific multifunctional compound of this type is a diol.

  At least some of the multifunctional compounds such as diols contain chromophores such as anthraquinone, methine or azo chromophores. For example, a suitable example of an anthraquinone chromophore is given in a paper entitled “Dyes, Anthraquinone”, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 8, 1979, pages 212-279. Yes.

  A specific example of a polyfunctional compound containing a chromophore is an anthraquinone dye having the following structural formula:

[式中、Ｒ^１からＲ^８の少なくとも２つが、−ＯＨ、−ＮＨ_２、−ＳＨからなる群から選択される少なくとも１つのイソシアネート反応性の官能基を有することを条件に、Ｒ基Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、水素、アミノ、ヒドロキシ、ハロゲン、ニトロ、カルボキシル化アルカリ金属、硫酸化アルカリ金属、場合によっては１つまたは複数のヘテロ原子を含むヒドロカルビル基からなる群からそれぞれに選択され、さらにＲ基Ｒ^１からＲ^８の隣り合うＲ基環を形成することができる]。

[Wherein R ¹ to R ⁸ have at least one isocyanate-reactive functional group selected from the group consisting of —OH, —NH ₂ , —SH, and R group R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal, optionally one or more Are each selected from the group consisting of hydrocarbyl groups containing heteroatoms, and can further form adjacent R group rings of R groups R ¹ to R ⁸ ].

An example of a compound in which R groups adjacent to R groups R ¹ to R ⁸ form a ring is a compound in which R ¹ and R ² are bonded to form a benzene ring.

The R group in the R groups R ¹ to R ⁸ is a hydrocarbyl group containing a heteroatom, which may be anywhere in the group, for example the heteroatom is (1) an anthraquinone nucleus As a linking group directly attached to (2), as a side chain group, (3) a linking group for linking two or more hydrocarbyl groups may be present.

For example, one to three of the R groups R ¹ to R ⁸ can have the following structural formula:

[式中、Ｒ^９は、水素または、１から約１２の炭素原子を有するアルキル基であり、Ｘは−ＣＨ_２−であり、ａは１から約６の整数であり、Ｙは、ヒドロキシアルキレン類、またはエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、シクロヘキサンオキサイド、グリシドールからなる群から選択されるアルキレンオキサイドモノマー類の重合体単位を表し、ｂは、０か１であり、Ｚは、反応性の−ＯＨ、−ＮＨ_２、または−ＳＨ基である]。

Wherein R ⁹ is hydrogen or an alkyl group having 1 to about 12 carbon atoms, X is —CH ₂ —, a is an integer from 1 to about 6, and Y is hydroxyalkylene Or a polymer unit of an alkylene oxide monomer selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, glycidol, b is 0 or 1, and Z is a reactive − OH, -NH _2, or -SH group.

  Specific examples of this type of anthraquinone dye are described in US Pat. No. 4,846,846 and have the following structural formula:

[式中、Ｒ^９およびＲ^１０は、水素または１から約１２の炭素原子を有するアルキル基から独立して選択され、Ｘは−ＣＨ_２−であり、ａおよびａ’は、独立して１から約６の整数であり、ＹおよびＹ’は、独立して、ヒドロキシアルキレン類、またはエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、シクロヘキサンオキサイド、グリシドールからなる群から選択されるアルキレンオキサイドモノマー類の重合体単位を表し、ｂおよびｂ’は、独立して０か１であり、ＺおよびＺ’は、独立して−ＯＨ、−ＮＨ_２、または−ＳＨ基である]。

Wherein R ⁹ and R ¹⁰ are independently selected from hydrogen or an alkyl group having 1 to about 12 carbon atoms, X is —CH ₂ —, a and a ′ are independently 1 And Y and Y ′ are independently hydroxyalkylenes or polymers of alkylene oxide monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, glycidol Represents a unit, b and b ′ are independently 0 or 1, and Z and Z ′ are independently an —OH, —NH ₂ , or —SH group].

  As described in US Pat. No. 4,846,846, a particular subclass of this type of anthraquinone dye can have the following structural formula:

[式中、ｎ、ｎ’、ｍ、ｍ’、ｐ、及びｐ’は、独立して０から約４０の値を有する]。

[Wherein n, n ′, m, m ′, p, and p ′ independently have a value from 0 to about 40].

  A specific example of an anthraquinone dye described in US Pat. No. 4,846,846 has the following structural formula:

  Other examples of anthraquinone dyes include 1,5-bis ((3-hydroxy-2,2-dimethylpropyl) amino) -9,10-anthracenedione, which is a red dye, and 2,2′-, which is a yellow dye. ((9,10-dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester, 1,5-bis ((2, 2-dimethyl-3-hydroxypropyl) amino) -4,8-bis ((4-methylphenyl) thio) anthraquinone. Other colors, pink, green, black, brown and purple can be produced by mixing these dyes or oligomers containing them.

  There are compounds, inks, and pigments that contain additional types of chromophores that contain functional groups that can be covalently attached to attach the chromophore to the polymeric matrix of the coating composition. For example, a radiation curable anthraquinone dye containing an anthraquinone core group having at least one substituent, including a radiation curable group. The radiation curable group may be an ethylenically unsaturated group such as a (meth) acryl group or an epoxy group.

  A radiation curable anthraquinone dye comprising an anthraquinone core group having at least one substituent may have the following formula:

[式中、Ｒ^１１からＲ^１８のうちの少なくとも１つが少なくとも１つのエチレン性不飽和の放射線硬化可能な官能基を有するという条件で、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８のＲ基は、水素、アミノ、ヒドロキシ、ハロゲン、ニトロ、カルボキシル化アルカリ金属、硫酸化アルカリ金属、場合によっては１つまたは複数のヘテロ原子を含むヒドロカルビル基からなる群からそれぞれ選択される]。

[Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , with the proviso that at least one of R ¹¹ to R ¹⁸ has at least one ethylenically unsaturated radiation curable functional group. The R group of R ¹⁶ , R ¹⁷ , R ^{18 is} a group consisting of hydrogen, amino, hydroxy, halogen, nitro, alkali metal carboxylate, alkali metal sulfate, hydrocarbyl group optionally containing one or more heteroatoms Each selected from].

For example, one or two of the R groups from R ¹¹ to R ¹⁸ may have (meth) acryl functionality, and at least four of the R groups from R ¹¹ to R ¹⁸ may be hydrogen. .

  A radiation curable anthraquinone pigment comprising an anthraquinone core group having at least one substituent containing a radiation curable group is produced by an esterification reaction of a hydroxy functional anthraquinone pigment having an acrylic acid type monomer. Can. For example, the dihydroxy functional anthraquinone pigments described above, ie, 1,5-bis ((3-hydroxy-2,2-dimethylpropyl) amino) -9,10-anthracenedione, 2,2 ′-((9,10 -Dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester, 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) If it is amino) -4,8-bis ((4-methylphenyl) thio) anthraquinone, such esterification reaction is carried out to produce the following compounds, respectively:

[式中、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４は、同一であるか異なり、独立して水素か、場合によっては、−ＯＨ、−ＮＨ_２、−ＳＨ、−ＮＯ_２、−ＣＮ、ハロゲンからなる群から選択される１つ以上の置換基で置換されているＣ_１からＣ_６のアルキルである]。

[Wherein R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ are the same or different and are independently hydrogen or, in some cases, —OH, —NH ₂ , —SH, — A C ₁ to C ₆ alkyl substituted with one or more substituents selected from the group consisting of NO ₂ , —CN, halogen].

  The compound of the present invention comprising a radiation curable chromophore is a standard radiation curable composition for coating communication elements such as optical fibers, optical fiber ribbons or a plurality of optical fibers arranged in an array. It may be mixed with components of a standard radiation curable composition, such as a component or a standard component of a radiation curable composition to form an ink or colorant package. Such components include one or more of (1) a radiation curable compound that does not include at least one chromophore, (2) at least one photoinitiator, and (3) at least one reactive diluent. May be included.

  Specific examples of radiation curable compounds that do not contain chromophores are radiation curable oligomers that do not contain chromophores, such as oligomers end-capped with (meth) acrylates, which are available from UCB Chemical Corp. It may be one of polyether aliphatic urethane acrylic compounds commercially available from This commercial product is called EBECRYL and includes EBECRYL230. EBECRYL230 is a bifunctional aliphatic urethane acrylate oligomer having a polyether skeleton chain.

  An example of another (meth) acrylate end-capped urethane oligomer is one of the polyester-based aliphatic urethane acrylate oligomers available from Sartomer. They are sold as CN966xxx and are bifunctional aliphatic urethane acrylate oligomers containing CN966J75 and having a polyester backbone. These oligomers are also available from Henkel, which manufactures PHOTOMER products, such as PHOTOMER 6010. The polyester polyol used to produce the polyester-based urethane acrylate oligomer is DESMOPHEN 2001KS, which is available from Bayer. This product is ethylene butylene adipate diol.

  In some cases, conventional urethane acrylate oligomers may be produced by reacting polyfunctional isocyanates such as diisocyanates with polyols such as diols and then end-capping with hydroxy-functional (meth) acrylates.

  The polyol may be a polyol having a number average molecular weight of about 200 to 10,000, such as polyether polyol, polyester polyol, polycarbonate polyol and hydrocarbon polyol.

The polyether polyol may be a homopolymer or copolymer of alkylene oxides including C ₂ to C ₅ alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and 3-methyl. Tetrahydrofuran; homopolymers or copolymers of the above alkylene oxides such as 12-hydroxystearyl alcohol and hydrogenated dimer diol obtained using C ₁₄ to C ₄₀ polyols as initiators; bisphenol A or hydrogenated bisphenol A and the above And the adducts of alkylene oxide. These polyether polyols may be used alone or in combination of two or more.

The polyester polyol is, for example, an addition reaction product of a diol component and a lactone, an addition reaction product of three components including the reaction product of the diol component and a polycarboxylic acid, the diol component, a dibasic acid, and the lactone. There may be. The diol component may be a C ₂ to C ₄₀ aliphatic diol having a low molecular weight, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentane. Diol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexane glycol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol , 12-hydroxystearyl alcohol, hydrogenated dimer diol; alkylene oxide adduct of bisphenol A. The lactone may be epsilon-caprolactone, delta-valerolactone, beta-methyl-delta-valerolactone, for example. These polycarboxylic acids are aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid; aromatics such as hexahydrophthalic acid, tetrahydrophthalic acid, phthalic acid, isophthalic acid and terephthalic acid It may be a dicarboxylic acid.

Polycarbonate polyols include short-chain dialkyl carbonates and the above-described polyether polyols, polyester polyols, and 2-methylpropanediol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1, The polycarbonate diol obtained by reaction of components selected from diol components such as 5-pentanediol, neopentyl glycol, 1,5-octanediol and 1,4-bis- (hydroxymethyl) cyclohexane may be used. The short chain dialkyl carbonate may be a C ₁ to C ₄ alkyl carbonate such as dimethyl carbonate and diethyl carbonate.

  Low molecular weight polyols may be used. Examples of polyols having a low molecular weight include the following: ethylene glycol, propylene glycol, tripropylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol 1,9-nonanediol, 1,10-decanediol, higher fatty acid polyol, higher hydrocarbon polyol, ie, castor oil, palm oil, monomyristins (1-monomyristin and 2-monomyristin), monopalmitin ( 1-monopalmitin and 2-monopalmitin), monostearin (1-monostearin and 2-monostearin), monoolein (1-monoolein and 2-monoolein), 9,10-dioxystearic acid, 12- Hydroxyricinoleyl alcohol 12-hydroxy stearyl alcohol, 1,16 (reduction product of juniper acid or Tapuku acid) hexadecane diol, 1,21- Heng equalizer Sanji ol, chimyl alcohol, batyl alcohol, selachyl alcohol, diol dimer acid.

  As noted above, any of the above-described polyols used to prepare conventional (meth) acrylate end-capped oligomers can be mixed with polyols containing chromophores or reacted with isocyanates to form colored oligomers. It may be generated.

  For example, the isocyanate used to produce a colored or uncolored monomer or oligomer may be an aromatic polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate or an aliphatic polyisocyanate. . The molecular weight of the particular isocyanate selected is not limited. The isocyanate may be so-called monomeric isocyanate or oligomeric isocyanate.

  Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6. -Diisocyanates such as tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate; triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanate benzene, 2 , 4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate and other polyisocyanates.

  Examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene, or Mixtures thereof; polyisocyanates such as 1,3,5-triisocyanate methylbenzene.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate or IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI or DESMODUR W (available from Bayer)), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1 Diisocyanates such as 1,4-bis (isocyanatomethyl) cyclohexane; 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanate Chlohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatemethyl) -Bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2 -Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2. 2.1) Heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanate Polyisocyanates such as ropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl) -2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane Is mentioned.

  Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1, Diisocyanates such as 3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate; lysine ester triisocyanate, 1,4,8-triisocyanate Octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane, Include 5,7-trimethyl-1,8-isocyanate-5-isocyanatomethyl octane polyisocyanates.

  Furthermore, derivatives of the above polyisocyanates can be used. Examples of derivatives include dimers, trimers, burettes, allophanates, carbodiimides, polymethylene polyphenyl polyisocyanates (referred to as crude MDI or polymer MDI), crude TDI, adducts of low molecular weight isocyanate compounds and polyols.

  Although several polyisocyanates including diisocyanates have been disclosed herein, it should be noted that monoisocyanates can be used as the polyisocyanates if they contain radiation curable functional groups. An example of a monoisocyanate containing a radiation curable group is meta-isopropenyl-α, α-dimethyl isocyanate.

  “(Meth) acrylate” shall mean acrylate, methacrylate, and mixtures thereof.

  The reaction product of a polyol and a polyisocyanate can be reacted with one or more hydroxy-functional (meth) acrylates. Examples of the hydroxy functional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentanediol. Mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, neopentyl Examples include glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate. Further examples include compounds obtained by the addition reaction of a compound containing a glycidyl group such as alkyl glycidyl ether and glycidyl (meth) acrylate with (meth) acrylic acid. The above (meth) acrylates containing a hydroxyl group may be used alone or in combination of two or more.

  The molecular weight range of the radiation curable oligomer is not particularly limited, however, according to the present invention, preferably 5,000 based on the specific requirements for the properties of the primary, secondary and tertiary coatings. To 25,000.

  The radiation curable composition of the present invention may comprise any suitable free radical photoinitiator. More specific examples of suitable free radical type photoinitiators include acylphosphine oxide photoinitiators, and more specifically, benzoyl diarylphosphine oxide photoinitiators. Suitable examples of benzoyldiarylphosphine oxide photoinitiators include 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide (LUCERIN TPO: available from BASF). Additional examples of free radical type photoinitiators include: hydroxycyclohexyl phenyl ketone; hydroxymethylphenylpropanone; dimethoxyphenylacetophenone; 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropanone-1 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; 1- (4-dodecyl-phenyl) -2-hydroxy-2-methylpropan-1-one; 4- (2 -Hydroxyethoxy) phenyl-2 (2-hydroxy-2-propyl) -ketone; diethoxyphenylacetophenone; 2,4,6-trimethylbenzoyldiphenylphosphine; (2,6-dimethoxybenzoyl) -2,4,4 -Trimethylpentylphosphine oxide and 2-hydro Shi-2-methyl-1-phenyl - mixtures of propan-1-one; and mixtures of the foregoing products can be mentioned. Many of these are sold under the names IRGACURE® and DAROCUR®, and are available from Ciba Additives.

  The free radical photoinitiator may be a mixture of phosphine oxide photoinitiators, for example DAROCUR 4265 available from Ciba Additives. This particular photoinitiator is a 50:50 weight percent mixture of diphenyl-2,4,6-trimethylbenzoylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Another example is IRGACURE 1700 (available from Ciba Additives), which includes bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl. -1-phenyl-propan-1-one).

  Free radical type photoinitiators may be used in amounts up to 10% by weight, based on the total weight of the composition, for example from about 0.25 to about 6% by weight, for example using about 4% by weight May be.

  The composition can promote curing in the presence of one or more reactive diluents. This reactive diluent can also serve as a solvent for the urethane acrylate oligomer. Use of this reactive diluent (s) can adjust viscosity and thus improve processability. In other words, the reactive diluent increases the viscosity of the composition of the present invention excessively to ensure that the composition remains in a suitable state for application, for example, as a primary or secondary coating on an optical fiber. And avoid the phenomenon of losing flexibility.

  The monofunctional or bifunctional reactive diluent (s) may be, for example, low molecular weight, liquid (meth) acrylate reactive compounds, examples of which include the following di (meth) acrylates, Functional (meth) acrylates include: tridecyl acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol Diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, tetra Chi glycol diacrylate, triethylene isopropylene glycol diacrylate, triethylene isopropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, tetrahydrofurfuryl acrylate (THFA). Other examples of reactive diluents include N-vinylcaprolactam. Further examples include SR489 or tridecyl acrylate, and SR506 or isobornyl acrylate, products available from Sartomer.

  The radiation curable composition of the present invention may not contain water or a non-reactive diluent such as an organic solvent having no ethylenic unsaturation.

  If the radiation curable composition is to be used as a primary coating composition for an optical fiber, the radiation curable composition may include an adhesion promoter. Examples of adhesion promoters include substances having functionality with acids and organofunctional silanes. For example, the organofunctional silane may be an amino functional silane, acrylamide functional silane, mercapto functional silane, allyl functional silane, vinyl functional silane, methyl acrylate functional silane, acrylate functional silane. The organofunctional silanes include mercaptoalkyltrialkoxysilane, methacryloxyalkyltrialkoxysilane, aminoalkyltrialkoxysilane, vinyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxy-propyltriethoxysilane, gamma -Mercaptopropyltrimethoxysilane, Gama-mercaptopropyl (gamma-mercaptopropyl) triethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-vinylthio Propyltrimethoxysilane, vinyl-tris (beta-methoxyethoxy) silane, vinyltriacetoxysilane, and mixtures thereof may also be used. A specific trialkoxysilane adhesion promoter is UCT7840KG obtained from United Chemical Technologies. A further adhesion promoter is KBM803, 3- (trimethoxysilyl) propylthiol, available from Shin-Etsu Chemical Co., Ltd.

  When using this adhesion promoter, in the primary coating composition, from about 0.1 to about 10% by weight, for example from about 0.1 to about 3% by weight, based on the total weight of the composition, For example, it may be present as about 1% by weight.

Other ingredients that can be used in the radiation curable composition include pigments such as TiO _{2 and the} antioxidant IONOL available from Aldrich, which is 2,4,6-tri-tert-butyl-4-methylphenol. A flow control agent such as BYK331, a polysiloxane available from BYK-Chemie USA; sensitizers such as thioxanthone or isopropylthioxanthone (ITX) and their derivatives; stabilizers and wetting agents. Appropriate amounts are those known to those skilled in the art.

  In a preferred embodiment of the present invention, a method comprising preparing a dye concentrate or masterbatch is used to produce a radiation curable monomer or oligomer comprising chromophore (s). This dye concentrate may comprise a compound comprising a chromophore according to the invention, such as a solvent and a radiation curable monomer or oligomer comprising a chromophore molecule of the invention. In particularly preferred embodiments, the solvent acts as both a solvent and a reactive diluent. In the most preferred embodiment, the solvent and the solvent that acts as the reactive diluent is tetrahydrofurfuryl acrylate (THFA).

  Specifically, a compound containing a chromophore containing a radiation curable functional group, or a functional group that reacts to form a radiation curable monomer or oligomer containing a chromophore moiety of the present invention. The compound containing the chromophore may be prepared in liquid or powder form. For example, compounds containing so-called “directly acrylated” chromophores can exist in the liquid state. This type of compound can be used without further manipulation with other components such as, for example, chromophores, photoinitiators, reactive diluents, monomers and oligomers that do not contain others, and are colored according to the invention. Radiation curable coatings, colorants, inks or printing compositions can be provided.

  However, if the compound containing the chromophore is in the form of a powder, it will dissolve into a solution whether it already has a radiation-curable functional group or not yet. Thus, a colored radiation curable composition according to the present invention must be formed. For example, a pigment powder containing a chromophore lacking a radiation curable functional group is reacted with a polyisocyanate, for example, a radiation curable group such as a group containing one or more ethylenic unsaturations. Before or at the end capping by the compound, the compound must be dissolved into solution.

  As a result of extensive research, we have obtained a solution in which the compound containing the powdered chromophore is most preferably dissolved by using THFA as a combination solvent and reactive diluent. I found that I could do it. By using THFA, several advantages are obtained. For example, THFA can be photocured. Thus, the THFA will not need to be removed from the solution before the solution can be added to the coating composition. When other solvents such as tetrahydrofuran (THF) are used to dissolve the chromophore containing compound to obtain a solution, any excess solvent may be added before the solution can be added to the coating composition. All will have to be removed from the solution. Otherwise, as a result, undesirable properties such as bubble formation may appear in the coating layer. As another example of the advantages of using THFA, it is noted that compounds containing chromophores showed a high degree of solubility in THFA compared to their solubility in compounds containing other acrylates. The

Thus, in one method for obtaining a dye concentrate, an isocyanate such as a diisocyanate is added in THFA, at least a portion of the compound comprising a chromophore such as an anthraquinone, methine or azo chromophore. _OH, -NH 2, is reacted with at least one compound having a reactive group with the isocyanate of -SH like.

  The compound containing the chromophore can be charged to the reactor containing isocyanate, catalyst and THFA at a rate sufficient to prevent the solution from becoming saturated with the compound containing the chromophore. For example, the chromophore-containing compound is charged to the reactor over about 30 to 75 minutes, preferably over 60 minutes, and the reactor is brought to a temperature of about 40 ° C. to about 60 ° C., preferably about 50 ° C. Keep it. The isocyanate may be present in stoichiometric amounts, for example, the isocyanate may be present in two equivalents of diisocyanate per equivalent of compound containing the chromophore. The catalyst may be any suitable catalyst such as dibutyltin dilaurate. Once the compound containing the chromophore is charged to the reactor, the reaction is allowed to proceed, for example, for 120 to 240 minutes, preferably 180 minutes, keeping the temperature at 50 ° C.

On the other hand, while putting (i) an isocyanate-reactive functional group such as an ethylenically unsaturated compound such as an acrylate monomer, and (ii) a radiation-curable compound containing a radiation-curable functional group into the reactor, Lowering the temperature from about 30 ° C. to about 50 ° C., preferably about 40 ° C., and maintaining that temperature introduces one or more radiation curable groups into the isocyanate-capped compound containing the chromophore. The Moreover, it is preferable to add an inhibitor to the reaction solution. The reaction is completed by measuring and monitoring the 2270 cm ⁻¹ isocyanate peak by FTIR, a procedure known in the prior art.

  When the reaction is complete, a dye concentrate or masterbatch comprising the solvent of the invention, the radiation curable monomer and / or oligomer of the chromophore of the invention is obtained. In a preferred embodiment, the radiation curable monomer and / or oligomer containing chromophore is greater than 5% by weight, preferably greater than about 10% by weight, for example from about 10% to about 35% by weight. It is present in the dye concentrate in an amount such that an amount of lumps is obtained. Here, this particular weight percent of the chromophore moiety is calculated by dividing the total weight of the total amount of chromophore moieties in the monomer and / or oligomer containing the radiation curable chromophore by the total weight of the dye concentrate. (That is, for example, an amount of 15% by weight chromophore moiety does not include, for example, any urethane or acrylate amount that may be present).

  In this preparation of the dye concentrate or masterbatch, excellent versatility is obtained, whereby the monomers and / or oligomers containing radiation curable chromophores contained in the dye concentrate can be used in various fields of application. Can be used easily.

  For example, the various components of the present invention, including dye concentrates or masterbatches, can be mixed and blended using any known equipment to produce a colored radiation curable coating composition. Any optical fiber manufacturing technique that can be provided and used can be used to coat an optical fiber with the coating composition. In one embodiment, the radiation curable coating composition for obtaining the secondary coating on the optical fiber is less than 20% by weight, for example less than 15% by weight, preferably less than 15% by weight, based on the total weight of the radiation curable composition. It comprises less than 10% by weight, more preferably less than 5% by weight, for example from 0.1% to 10% by weight of dye concentrate. Of course, radiation curable coating compositions may be prepared that provide a primary, tertiary, or single layer coating on the optical fiber, with the amount of dye concentrate specifically tailored to the particular end use. May be adjusted. Similarly, radiation curable compositions can be provided that provide a coating on a plurality of optical fibers or optical fiber ribbons arranged in an array array, where again the amount of dye concentrate is specifically specified. It may be adjusted according to the final use.

  The technique of the present invention can use a draw tower that heats a preformed glass rod to produce thin glass fibers. The fiber passes vertically through a draw tower, in the process, the fiber passes through one or more coating stations, where various coatings are applied, cured inline, and a new drawn fiber. become. The coating station may include a die having an exit orifice that is sized to apply a particular coating to the fiber at a desired thickness. Monitoring and measuring equipment is placed near each station to ensure that the coating applied at that station can be coated concentrically and to the desired diameter. Examples of optical fiber coating techniques include U.S. Pat. Nos. 4,351,657, 4,512,281, 4,531,959, 4,539,219, 4,792,347. No. 4,867,775, and the like.

  Alternatively, a composition comprising a dye concentrate or masterbatch serves as a colored coating or colorant package for a variety of other supports including, for example, glass, plastic, ceramic, metal, textile, electronic components and wood. May be prepared for. Where it is desired to replace a conventional pigment with a dye material in a radiation curable vehicle such as an ultraviolet curable vehicle, the composition containing the dye concentrate or masterbatch is coated or colored in the printing and ink industry. Can be used as an agent package. Other components of the ink or colorant package may include other radiation curable monomers or other functional radiations, as found in optical fiber applications, in order to adapt the viscosity and flowability to the required application method. Curable materials, photoinitiator (s), stabilizer (s), surfactant (s), and the like can be included.

  The ink, coating or colorant package of the present invention can be applied to a support other than an optical fiber by a number of methods including printing methods such as gravure printing, inkjet printing and the like. In one embodiment, the radiation curable ink or colorant package is less than 60 wt%, preferably less than 40 wt%, such as 0.1 wt% to 35 wt%, based on the total weight of the radiation curable composition. Up to% dye concentrate.

After coating the support with a radiation curable composition, the composition can be cured by exposure to a sufficient amount of UV radiation for curing. For example, the coated fiber is exposed to UV radiation at a rate of about 5 to 1000 mJ / cm ² .

  Further inventive details are described in several examples. Specifically, some syntheses for forming colored radiation curable compounds suitable for use in radiation curable compositions for coating optical fibers and for forming optical fiber ribbon matrices. Examples are given below. Examples of radiation curable compositions containing colored compounds are also given. Finally, an example of the preparation of a dye concentrate will be given, where the dye concentrate can be applied to a wide range of applications as described above.

Example 1-Yellow Oligomer 202.89 g of Milliken Reactint (TM) yellow dye X15 was added dropwise to 67.44 g of a mixture of isophorone diisocyanate (IPDI) and dibutyltin dilaurate that had been heated to 40 <0> C. Care was taken to control the rate of addition so that the exothermic reaction did not exceed 45 ° C. The total time required for the addition was 2 hours. After the last addition of IPDI, 200 g of 1,6 hexanediol diacrylate (HDODA) was used as a reactive diluent to reduce the viscosity, and 4.4 g of the inhibitor 2,6-di-tert-butyl-4- Added with methylphenol. After maintaining the mixture at 40 ° C. for 2 hours, 35.24 g of 2-hydroxyethyl acrylate (HEA) was added dropwise while maintaining the temperature below 50 ° C. by controlling the HEA addition rate. One hour after the addition, there was no detectable 2270 cm ⁻¹ isocyanate peak as observed by FTIR. The resulting urethane acrylate oligomer reaction product was yellow.

Example 2 Blue Oligomer 152.09 g of Milliken Reactint ™ Blue Dye X3LV was added dropwise to a mixture of 101.13 g of isophorone diisocyanate (IPDI) and 2.98 g of dibutyltin dilaurate heated to 40 ° C. . Care was taken to control the rate of addition so that the exothermic reaction did not exceed 45 ° C. The total time taken for the addition was 2 hours. After the last addition of IPDI, 2.03 g of inhibitor 2,6-di-tert-butyl-4-methyl with 200 g of 1,6 hexanediol diacrylate (HDODA) as reactive diluent to reduce viscosity Added with phenol. After the mixture was maintained at 40 ° C. for 2 hours, 52.96 g of 2-hydroxyethyl acrylate (HEA) was added dropwise while maintaining the temperature below 50 ° C. by controlling the HEA addition rate. Two hours after the addition, there was no detectable 2270 cm ⁻¹ isocyanate peak as observed by FTIR. The resulting reaction product of urethane acrylate oligomer was blue.

Example 3-Black Oligomer 226.67 g Milliken Reactint ™ black dye X95AB was added dropwise to a mixture of 93.30 g isophorone diisocyanate (IPDI) and 2.74 g dibutyltin dilaurate heated to 40 ° C. . Care was taken to control the rate of addition so that the exothermic reaction did not exceed 45 ° C. The total time taken for the addition was 2 hours. After the last addition of IPDI, 200 g of tetrahydrofuran (THF) solvent was added as a reactive diluent with 2.38 g of inhibitor 2,6-di-tert-butyl-4-methylphenol to reduce the viscosity. After maintaining the mixture at 40 ° C. for 2 hours, 48.78 g of 2-hydroxyethyl acrylate (HEA) was added dropwise while maintaining the temperature below 50 ° C. by controlling the rate of HEA addition. Two hours after the addition, there was no detectable 2270 cm ⁻¹ isocyanate peak as observed by FTIR. Thereafter, the THF solvent was removed on a rotary evaporator over 10 hours at room temperature until a weight equal to the original charge (subtracting the solvent) was reached. The resulting reaction product of urethane acrylate oligomer is black.

  Several liquid coating compositions that use colored radiation curable oligomers are described below.

Example 4-Yellow Colored Optical Fiber Outer Coating Composition A yellow ultraviolet radiation curable coating composition for providing a colored outer coating has a molecular weight of about 1500 sold by UCB Chemicals. 60% by weight EBECRYL ™ 4827, an aromatic urethane diacrylate oligomer, 30% by weight trimethylolpropane trimethacrylate (TMPTA), a reactive diluent sold by UCB Chemicals, as described in Example 1. It was made by mixing 6% by weight of a yellow colored urethane acrylate oligomer, the reaction product of synthesis, and about 4% by weight of DAROCUR ™ 4268, a photoinitiator. The coating composition was applied over the inner coating layer and cured by exposure to ultraviolet radiation of the appropriate wavelength range and intensity to form a yellow colored outer protective polymer coating.

Example 5 Composition of Blue Colored Optical Fiber Inner Coating A blue UV radiation curable coating composition for providing a colored inner coating is a high molecular weight aliphatic sold by UCB Chemicals. 60% by weight of EBECRYL ™ 230, which is a urethane diacrylate oligomer (bulk oligomer), 29% by weight of β-carboxyethyl acrylate (13-CEA), which is a monofunctional reactive diluent sold by UCB Chemicals, It was made by mixing 6% by weight of the blue colored urethane acrylate oligomer, the synthetic reaction product described in Example 2, and about 5% by weight of DAROCUR ™ 4265, the photoinitiator. This coating composition was applied onto the cladding layer of an optical fiber and cured by exposure to ultraviolet radiation of the appropriate wavelength range and intensity to form a blue colored inner protective coating.

Example 6-Blue Colored Optical Fiber Outer Coating Composition A blue UV radiation curable coating composition to provide a colored outer coating is 60 wt% EBECRYL ™ 4827 (bulk oligomer) ), 30 wt% TMPTA (reactive diluent), 6 wt% blue colored urethane acrylate oligomer and about 4 wt% DAROCUR ™ 4268, the reaction product of the synthesis described in Example 2. It was prepared by mixing. This coating composition was applied over the inner coating of the optical fiber and formed an outer protective polymer coating colored blue after being cured by exposure to ultraviolet radiation in the appropriate wavelength range.

Example 7-Blue Colored Ink (Tertiary) Coating Composition A blue UV radiation curable coating composition for providing a colored tertiary coating is 30% by weight sold by UCB Chemicals. 25% by weight EBECRYL ™ 4866, 25% by weight TMPTA (reactive diluent), an aliphatic urethane triacrylate diluted with 1% of tripropylene glycol diacrylate (TRPGDA), of the synthesis described in Example 2 By mixing the reaction product 35 wt% blue colored urethane acrylate oligomer, 10 wt% hexanediol diacrylate (HDODA) (reactive diluent) and about 5 wt% DAROCUR ™ 4268 Produced. This coating composition was applied over the outer coating of the optical fiber and cured by exposure to ultraviolet radiation in the appropriate wavelength range to form a blue colored tertiary protective polymer coating.

Example 8-Blue urethane acrylate 11.16 g of isophorone diisocyanate and 0.35 g of dibutyltin dilaurate were heated to 50C. 16.34 g of 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) -4,8-bis ((4-methylphenyl) thio) anthraquinone was mixed with THF to dissolve the anthracenedione of the solution. And slowly added to the reaction. The reaction temperature was maintained at 50 ° C. for 3 hours. The temperature was lowered to 40 ° C. and 0.25 g 2,6-di-tert-butyl-4-methylphenol and 30 g 1,6 hexanediol diacrylate were added to the reaction. Thereafter, 5.819 g of 2-hydroxyethyl acrylate was added dropwise. The reaction was allowed to proceed to completion by measuring the 2270 cm ⁻¹ isocyanate peak by FTIR. THF was removed from the mixture by evaporation. The resulting urethane acrylate composition was blue.

Example 9-Blue Colored Optical Fiber Outer Coating A blue UV radiation curable coating composition for providing a colored outer coating is a 65 wt% EBECRYL which is a urethane acrylate oligomer (bulk oligomer) (Trademark) 4827, 30% by weight of a reactive diluent, tripropylene glycol diacrylate (TPGDA), 1% of a blue colored urethane acrylate and photoinitiated reaction product of the synthesis described in Example 8 It was made by mixing about 4% DAROCUR ™ 4268 agent. This coating composition was applied over the inner coating layer and cured by exposure to ultraviolet radiation in the appropriate wavelength range to form a blue colored outer protective polymer coating.

Example 10-Blue Colored Optical Fiber Inner Coating A blue UV radiation curable coating composition for providing a colored inner coating is a 65 wt% EBECRYL ™ 230 which is a urethane acrylate oligomer. 29% by weight β-CEA monofunctional reactive diluent, 1% blue-colored urethane acrylate which is the reaction product of the synthesis described in Example 8, and about 5% DAROCUR which is a photoinitiator. Made by mixing TM 4265. This coating composition was applied to the cladding layer of an optical fiber and cured by exposure to ultraviolet radiation in the appropriate wavelength range to form a blue colored inner protective fiber coating.

Colored Fiber Optic Ribbon Referring to FIG. 2, a conventional splittable fiber optic ribbon 22 including two planar arrays 24a, 24b of a plurality of optical fibers 21 is shown. Each of the plurality of optical fiber arrays is encapsulated with primary matrices 26a, 26b that hold the fiber array together. Both primary matrices 26a, 26b are encapsulated with a secondary matrix 28. The primary matrix 26a, 26b, the secondary matrix 28 or both are colored according to the present invention. Examples of matrices to be colored are described below.

Example 11-Blue Ribbon Matrix A composition for forming a blue colored fiber optic ribbon matrix is 6% by weight of the blue oligomer reaction product described in Example 2, 60% by weight of EBECRYL ™. It was made by mixing 4866 trifunctional oligomer (bulk oligomer), 30 wt% TMPTA (reactive diluent) and 4 wt% DAROCUR ™ 4268 photoinitiator. The resulting composition was applied on a plurality of optical fiber planar arrays using conventional coating methods in a die or applicator. The composition was cured by exposure to ultraviolet radiation in the appropriate wavelength range to form a blue colored matrix on a multi-fiber planar array.

Example 12-Yellow reactive dye color concentrate A reactive dye color concentrate containing a functional yellow dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, tetrahydrofurfuryl acrylate (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate) to the reactor. Filled, stirred at 650 rpm and heated to 50 ° C. 1 equivalent of 2,2 ′-((9,10-dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester anthraquinone yellow dye Slowly added over 1 hour. The tetrahydrofurfuryl acrylate monomer acted as a solvent and dissolved the dye into a solution and reacted with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. No free isocyanate remained in the mixture as determined by FTIR at the end of the 2 hour reaction.

  The resulting yellow color concentrate was filtered through a 1 micron absolute filter, which contained 15% by weight of chromophore portion (ie, 15% by weight of this chromophore), based on the total weight of the color concentrate. The chromophore portion did not include the weight of urethane or acrylate). No solid was recovered from the filter.

Example 13-Orange Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional orange dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, tetrahydrofurfuryl acrylate (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate) to the reactor. Filled, stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,5-bis- (phenylamino) terephthalic acid-bis (2-hydroxyethyl) ester anthraquinone orange dye was slowly added to the reactor over 1 hour. The tetrahydrofurfuryl acrylate monomer acted as a solvent and dissolved the dye into a solution and reacted with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. No free isocyanate remained in the mixture as determined by FTIR at the end of the 2 hour reaction.

  The resulting orange color concentrate was filtered through a 1 micron absolute filter, which contained 15% by weight of chromophore moiety (ie, 15% by weight based on the total weight of the color concentrate). The chromophore part of the urine contained no weight of urethane or acrylate. No solid was recovered from the filter.

Example 14-Red Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional red dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, tetrahydrofurfuryl acrylate (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate) to the reactor. Filled, stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 1,5-bis-{(3-hydroxypropyl) amino} -9,10-anthracenedione red anthraquinone dye was slowly added to the reactor over 1 hour. The tetrahydrofurfuryl acrylate monomer acted as a solvent and dissolved the dye into a solution and reacted with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. No free isocyanate remained in the mixture as determined by FTIR at the end of the reaction time.

  The resulting red color concentrate was filtered through a 1 micron absolute filter, which contained 15% by weight chromophore moiety (ie, 15% by weight of this chromophore portion based on the total weight of the color concentrate). The chromophore portion did not include the weight of urethane or acrylate). No solid was recovered from the filter.

Comparative Example 1 Yellow Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional yellow dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, tripropylene glycol diacrylate (TPGDA) (amount sufficient to give a final concentration of 15 wt% chromophore moiety in the color concentrate) Was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Next, 1 equivalent of 2,2 ′-((9,10-dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyester anthraquinone yellow dye is reacted Slowly added to the vessel over 1 hour. The tripropylene glycol diacrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. At the end of the 2 hour reaction, about 0.5 equivalents of free isocyanate was present.

  The resulting yellow color concentrate was filtered through a 1.2 micron absolute filter. About 0.6 equivalents of solid diol dye (unreacted) was recovered on the filter. When using monomer TPGDA, the reaction was unsuccessful due to the lack of solubility of the yellow anthraquinone dye in the reaction mixture.

Comparative Example 2 Orange Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional orange dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, tripropylene glycol diacrylate (TPGDA) (amount sufficient to give a final concentration of 15 wt% chromophore moiety in the color concentrate) Was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,5-bis- (phenylamino) terephthalic acid-bis- (2-hydroxyethyl) ester anthraquinone orange dye was slowly added to the reactor over 1 hour. The tripropylene glycol diacrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.2 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting orange color concentrate was filtered through a 1.2 micron absolute filter. About 0.2 equivalents of unreacted solid orange anthraquinone dye was recovered on the filter. When monomeric TPGDA was used, the reaction was unsuccessful due to the limited solubility of the orange diol dye in the reaction mixture.

Comparative Example 3-Red reactive dye color concentrate A reactive dye color concentrate containing a functional red dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, tripropylene glycol diacrylate (TPGDA) (amount sufficient to give a final concentration of 15 wt% chromophore moiety in the color concentrate) Was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Then 1,5-bis-{(3-hydroxypropyl)} amino-9,10-anthracenedione red anthraquinone dye was slowly added to the reactor over 1 hour. The tripropylene glycol diacrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.8 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting red color concentrate was filtered through a 1 micron absolute filter. About 0.6 equivalents of unreacted solid red diol dye was recovered on the filter. When monomeric TPGDA was used, the reaction was unsuccessful due to the limited solubility of the red anthraquinone dye in the reaction mixture.

Comparative Example 4-Yellow Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional yellow dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, 2-phenoxyethyl acrylate (2-PEA) (sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate Amount) was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,2 ′-((9,10-dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester anthraquinone yellow dye Slowly added to the reactor over 1 hour. The 2-phenoxyethyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. At the end of the 2 hour reaction, about 0.8 equivalents of free isocyanate was present.

  The resulting yellow color concentrate was filtered through a 1.2 micron absolute filter. About 0.5 equivalents of solid diol dye (unreacted) was recovered on the filter. When monomer 2-PEA was used, the reaction was unsuccessful due to insufficient solubility of the yellow anthraquinone dye in the reaction mixture.

Comparative Example 5-Orange Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional orange dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, 2-phenoxyethyl acrylate (2-PEA) (sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate Amount) was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,5-bis- (phenylamino) terephthalic acid bis- (2-hydroxyethyl) ester anthraquinone orange dye was slowly added to the reactor over 1 hour. The 2-phenoxyethyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.8 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting orange color concentrate was filtered through a 1.2 micron absolute filter. About 0.7 equivalents of unreacted solid orange anthraquinone dye was recovered on the filter. When monomer 2-PEA was used, the reaction was unsuccessful due to the limited solubility of the orange diol dye in the reaction mixture.

Comparative Example 6-Red Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional red dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mol of dibutyltin dilaurate, 2-phenoxyethyl acrylate (2-PEA) (sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate Amount) was charged to the reactor, stirred at 650 rpm and heated to 50 ° C. Then 1,5-bis-{(3-hydroxypropyl) amino} -9,10-anthracenedione red anthraquinone dye was slowly added to the reactor over 1 hour. The 2-phenoxyethyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with diisocyanate to produce a compound containing isocyanate and dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.8 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting red color concentrate was filtered through a 1 micron absolute filter. About 0.6 equivalents of unreacted solid red diol dye was recovered on the filter. When monomer 2-PEA was used, the reaction was unsuccessful due to the limited solubility of the red anthraquinone dye in the reaction mixture.

Comparative Example 7-Yellow Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional yellow dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, isobornyl acrylate (IBOA) (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate). The reactor was charged and stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,2 ′-((9,10-dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester anthraquinone yellow dye Slowly added to the reactor over 1 hour. The isobornyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. At the end of the 2 hour reaction, approximately 0.6 equivalents of free isocyanate was present.

  The resulting yellow color concentrate was filtered through a 1.2 micron absolute filter. About 0.6 equivalents of solid diol dye (unreacted) was recovered on the filter. When using monomer IBOA, the reaction was unsuccessful due to the lack of solubility of the yellow anthraquinone dye in the reaction mixture.

Comparative Example 8-Orange Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional orange dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, isobornyl acrylate (IBOA) (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate). The reactor was charged and stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 2,5-bis- (phenylamino) terephthalic acid bis- (2-hydroxyethyl) ester anthraquinone orange dye was slowly added to the reactor over 1 hour. The isobornyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.4 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting orange color concentrate was filtered through a 1.2 micron absolute filter. About 0.4 equivalents of solid orange anthraquinone dye was recovered on the filter. When using monomer IBOA, the reaction was unsuccessful due to the limited solubility of the yellow diol dye in the reaction mixture.

Comparative Example 9-Red Reactive Dye Color Concentrate A reactive dye color concentrate containing a functional red dye compound was prepared by the following procedure.

  2 equivalents of isophorone diisocyanate (IPDI), 0.01 mole of dibutyltin dilaurate, isobornyl acrylate (IBOA) (amount sufficient to give a final concentration of 15% by weight chromophore moiety in the color concentrate). The reactor was charged and stirred at 650 rpm and heated to 50 ° C. Then 1 equivalent of 1,5-bis-{(3-hydroxypropyl) amino} -9,10-anthracenedione red anthraquinone dye was slowly added to the reactor over 1 hour. The isobornyl acrylate monomer acted as a solvent to dissolve the dye into a solution and react with the diisocyanate to produce a compound containing the isocyanate and the dye. The dye was slowly added to the reactor so as not to saturate the solution and substantially stop the urethanation reaction.

After complete addition of the dye, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 50 ° C. After reacting for 3 hours, the temperature was lowered to 40 ° C., and 0.02 mol of 2,6-di-tert-butyl-4-methylphenol (inhibitor) was added to the reaction solution. One equivalent of 2-hydroxyethyl acrylate was added slowly and reacted with the isocyanate of the compound containing the isocyanate and the dye. The temperature was kept at 40 ° C. and the mixture was stirred for 2 hours. The completion of the reaction was monitored by measuring the isocyanate peak at 2270 cm ^{−1 by} FTIR. Approximately 0.8 equivalents of free isocyanate were present as determined by FTIR at the end of the 2 hour reaction.

  The resulting red color concentrate was filtered through a 1 micron absolute filter. About 0.7 equivalents of unreacted solid red diol dye was recovered on the filter. When IBOA was used, the reaction was unsuccessful due to limited solubility of the red anthraquinone dye in the reaction mixture.

  The embodiments disclosed herein successfully achieve the objectives of the present invention. However, one of ordinary skill in the art appreciates that the person skilled in the art can practice away from the invention without departing from the spirit and scope of the invention which is limited only in the claims.

FIG. 3 shows a cross section of an optical fiber coated with primary and secondary coatings. FIG. 4 shows a cross section of an optical fiber coated with primary, secondary and tertiary coatings. FIG. 3 shows a cross section of a splittable fiber optic ribbon having at least one colored matrix.

Claims (116)

(I) a compound comprising a radiation curable chromophore comprising at least one radiation curable group and at least one chromophore moiety,
The compound containing the radiation curable chromophore is
A compound comprising (a) (i) at least one isocyanate group and (ii) an isocyanate comprising said at least one chromophore moiety;
(B) comprising a reaction product of (i) at least one isocyanate-reactive functional group and (ii) a radiation curable compound comprising said at least one radiation curable group;
The at least one radiation curable group of the compound containing the radiation curable chromophore is a compound containing the radiation curable chromophore, the isocyanate group (i) of the compound (a) containing the isocyanate, and the radiation curing. A covalent bond by at least one covalent bond formed by reacting the isocyanate-reactive functional group (i) of the functional compound (b),
Compound (a) containing the isocyanate is
(C) including a radiation curable chromophore that is a reaction product of (i) a chromophore moiety and (ii) a chromophore containing at least one isocyanate-reactive functional group; and (d) a polyisocyanate. A compound ,
(II) Tetrahydrofurfuryl acrylate (THFA) as reactive diluent
A dye concentrate . The at least one isocyanate-reactive functional group (i) of the radiation curable compound (b) and the at least one isocyanate-reactive functional group (ii) of the compound (c) containing the chromophore are − The dye concentrate of claim 1, independently selected from the group consisting of OH, —NH ₂ , —SH. The dye concentrate of claim 1, wherein the at least one radiation curable group (ii) of the radiation curable compound (b) comprises ethylenic unsaturation. 4. The dye concentrate according to claim 3, wherein the ethylenically unsaturated and radiation curable group (ii) of the radiation curable compound (b) comprises (meth) acrylate. The dye concentrate according to claim 1, wherein the at least one radiation curable group (ii) of the radiation curable compound (b) comprises an epoxy group. The dye concentrate according to claim 1, wherein the polyisocyanate (d) is a diisocyanate. The dye concentrate according to claim 1, wherein the at least one chromophore moiety (i) of the compound (c) comprising the chromophore is a methine dye. The dye concentrate according to claim 1, wherein said at least one chromophore moiety (i) of compound (c) comprising said chromophore is an azo dye. The dye concentrate according to claim 1, wherein the at least one chromophore moiety (i) of the compound (c) comprising the chromophore is an anthraquinone dye. The dye concentrate of claim 9, wherein the anthraquinone dye has the following structural formula:

[Where
Provided that at least two of the R groups R ¹ to R ⁸ have at least one isocyanate-reactive functional group selected from the group consisting of —OH, —NH ₂ and —SH,
R groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal, optionally Are independently selected from the group consisting of hydrocarbyl groups containing one or more heteroatoms, and further adjacent R groups from R ⁸ to R ¹ can form a ring]. The dye concentrate according to claim 10, wherein one to three of R ¹ to R ⁸ of the R group have the following structural formula:

[Where
R ⁹ is hydrogen or an alkyl group having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a is an integer of 1 or et al. 6,
Y represents a hydroxyalkylene or a polymer unit of an alkylene oxide monomer selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide and glycidol,
b is 0 or 1, Z is a —OH, —NH ₂ , or —SH group;
Furthermore, the remainder of the R groups R ¹ to R ⁸ is selected from the group consisting of hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal]. The dye concentrate of claim 10, wherein the anthraquinone dye has the following structural formula:

[Where
R ⁹ and R ¹⁰ are independently selected from hydrogen or an alkyl radical having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a and a 'is an integer of 1 or et 6 independently
Y and Y ′ independently represent hydroxyalkylenes or polymer units of alkylene oxide monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide and glycidol;
b and b ′ are independently 0 or 1,
Z and Z ′ are independently —OH, —NH ₂ , or —SH groups]. The dye concentrate of claim 12, wherein the anthraquinone dye has the following structural formula:

Wherein, n, n ', m, m', p, p ' has a value independently 0 to 4 0]. The dye concentrate of claim 12, wherein the anthraquinone dye has the following structural formula.

The anthraquinone dye is 1,5-bis ((3-hydroxy-2,2-diethylpropyl) amino) -9,10-anthracenedione, 2,2 ′-((9,10-dihydro-9,10- Dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester and 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) -4,8- The dye concentrate of claim 9 selected from the group consisting of bis ((4-methylphenyl) thio) anthraquinone. The dye concentration according to claim 9, wherein the anthraquinone dye is 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) -4,8-bis ((4-methylphenyl) thio) anthraquinone. Thing . Radiation-curable oligomers that does not include the outgoing chromophore
The dye concentrate of claim 1 further comprising: Further comprising a T iO _2, the dye concentrate of claim 17. One or more photoinitiators, reactive diluents, stabilizers and further comprises a surfactant, a dye concentrate according to claim 17. A support having the dye concentrate of claim 17 on at least a portion thereof . The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
21. The support according to claim 20 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a dye concentrate for identifying a color on at least a portion of a support, comprising:
The dye concentrate for identifying the color has at least one chromophore moiety covalently bonded to at least one other component of the dye concentrate for identifying the color;
Said method providing a support;
Providing a dye concentrate according to claim 17 ;
Applying the dye concentrate of claim 17 to at least a portion of the support;
The appropriate time the applied dye concentrate, the method comprising the steps you violence exposure to radiation of a suitable wavelength and intensity. The support is (i) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
23. The method of claim 22 , selected from the group consisting of (iv) an optical fiber ribbon. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 1 . Wherein the composition further radiation-curable composition according to claim 24 including TiO _2. 25. The radiation curable composition of claim 24 , wherein the composition further comprises one or more photoinitiators, reactive diluents, stabilizers and surfactants. 25. A support having the radiation curable composition according to claim 24 on at least a part thereof. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
28. The support according to claim 27 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a radiation cured composition that identifies a color on at least a portion of a support, comprising:
The radiation-cured composition identifying the color has at least one chromophore moiety covalently bonded to at least one other component of the radiation-cured composition identifying the color;
The method comprises
Supplying a support;
Feeding the radiation curable composition of claim 24 ;
Applying the radiation curable composition of claim 24 to at least a portion of the support;
Exposing the applied composition to radiation of an appropriate wavelength and intensity for an appropriate time to cure the composition to a radiation-cured composition that identifies color. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
30. The method of claim 29 , selected from the group consisting of (iv) an optical fiber ribbon. The dye concentrate of claim 1 , wherein the dye concentrate comprises more than 5 wt% chromophore moieties based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 31 . The dye concentrate, dye concentrate according to claim 1 comprising a chromophore moiety of 1-0 wt% to 35 wt% based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 33 . The compound comprising a radiation curable chromophore comprises a compound comprising a first radiation curable chromophore and a compound comprising a second radiation curable chromophore;
At least the chromophore moiety of a compound containing the first radiation curable chromophore is different from the chromophore moiety of a compound containing the second radiation curable chromophore
Dye concentrate according to claim 1, characterized in that (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 35 . (I) a compound comprising a radiation curable chromophore comprising at least one radiation curable group and at least one chromophore moiety,
The compound containing the radiation curable chromophore is
(A) a compound comprising a chromophore comprising (i) at least one isocyanate-reactive functional group and (ii) at least one said chromophore moiety;
(B) comprising a reaction product of (i) a radiation curable compound comprising at least one isocyanate group and (ii) at least one said radiation curable group;
The at least one radiation curable group of the compound containing the radiation curable chromophore is an isocyanate reactivity of the isocyanate group (i) of the radiation curable compound (b) and the compound (a) containing the chromophore. a compound covalently bonded to the of by at least one covalent bond is formed by reacting the functional group (i) a compound comprising the radiation curable chromophore,
(II) Tetrahydrofurfuryl acrylate (THFA) as reactive diluent
A dye concentrate . Wherein the at least one isocyanate-reactive functional group (i) is _-OH, -NH 2, dye concentrate according to claim 37 which is selected from the group consisting of -SH compound containing the chromophore (a). 38. The dye concentrate of claim 37, wherein the at least one radiation curable group (ii) of the radiation curable compound (b) comprises ethylenic unsaturation. 40. The dye concentrate of claim 39, wherein the ethylenically unsaturated and radiation curable group (ii) of the radiation curable compound (b) comprises meta (acrylate). 38. The dye concentrate of claim 37, wherein the at least one radiation curable group (ii) of the radiation curable compound (b) comprises an epoxy group. 38. A dye concentrate according to claim 37, wherein said at least one chromophore moiety (ii) of compound (a) comprising said chromophore is a methine dye. 38. A dye concentrate according to claim 37, wherein said at least one chromophore moiety (ii) of compound (a) comprising said chromophore is an azo dye. 38. A dye concentrate according to claim 37, wherein said at least one chromophore moiety (ii) of compound (a) comprising said chromophore is an anthraquinone dye. The dye concentrate according to claim 37, wherein the compound (a) containing the chromophore is an anthraquinone dye having the following structural formula:

[Where
Provided that at least two of the R groups R ¹ to R ⁸ have at least one isocyanate-reactive functional group selected from the group consisting of —OH, —NH ₂ and —SH,
R groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal, optionally Are independently selected from the group consisting of hydrocarbyl groups containing one or more heteroatoms, and further adjacent R groups from R ⁸ to R ¹ can form a ring]. 46. The dye concentrate of claim 45, wherein one to three of R ¹ to R ⁸ of the R group have the following structural formula:

[Where
R ⁹ is hydrogen or an alkyl group having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a is an integer of 1 or et al. 6,
Y represents a hydroxyalkylene or a polymer unit of an alkylene oxide monomer selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide and glycidol,
b is 0 or 1, Z is a —OH, —NH ₂ , or —SH group;
Furthermore, the remainder of the R groups R ¹ to R ⁸ is selected from the group consisting of hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal]. The dye concentrate of claim 45, wherein the anthraquinone dye has the following structural formula:

[Where
R ⁹ and R ¹⁰ are independently selected from hydrogen or an alkyl radical having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a and a 'is an integer of 1 or et 6 independently
Y and Y ′ independently represent hydroxyalkylenes or polymer units of alkylene oxide monomers selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide and glycidol;
b and b ′ are independently 0 or 1,
Z and Z ′ are independently —OH, —NH ₂ , or —SH groups]. 48. The dye concentrate of claim 47, wherein the anthraquinone dye has the following structural formula:

Wherein, n, n ', m, m', p, and p 'has a value of 0 to 4 0 independently. 48. The dye concentrate of claim 47, wherein the anthraquinone dye has the following structural formula.

The compound (a) containing the chromophore is 1,5-bis ((3-hydroxy-2,2-dimethylpropyl) amino) -9,10-anthracenedione, 2,2 ′-((9,10- Dihydro-9,10-dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester and 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino 38. The dye concentrate of claim 37, selected from the group consisting of:)-4,8-bis ((4-methylphenyl) thio) anthraquinone. Claim compound containing the chromophore (a) is 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) 4,8-bis ((4-methylphenyl) thio) anthraquinone 50. The dye concentrate according to 50 . Further comprising a radiation-curable oligomer containing no outgoing chromophore dye concentrate according to claim 37. Further comprising a T iO _2, the dye concentrate of claim 52. One or more photoinitiators, reactive diluents, stabilizers and further comprises a surfactant, a dye concentrate according to claim 52. 53. A support having the dye concentrate of claim 52 on at least a portion thereof . The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
56. The support of claim 55 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a dye concentrate for identifying a color on at least a portion of a support, comprising:
The dye concentrate for identifying the color has at least one chromophore moiety covalently bonded to at least one other component of the dye concentrate for identifying the color;
Said method providing a support;
Providing a dye concentrate according to claim 52 ;
Applying the dye concentrate of claim 52 to at least a portion of the support;
The appropriate time the applied dye concentrate, the method comprising the steps you violence exposure to radiation of a suitable wavelength and intensity. The support is (i) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
58. The method of claim 57 , selected from the group consisting of (iv) an optical fiber ribbon. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 37 . Radiation curable composition according to claim 59 comprising TiO ₂ on of et. One or more photoinitiators, reactive diluents, stabilizers and radiation-curable composition according to claim 59, further comprising a surfactant. 60. A support having the radiation curable composition of claim 59 on at least a portion thereof. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
64. The support of claim 62 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a radiation cured composition that identifies a color on at least a portion of a support, comprising:
The radiation-cured composition identifying the color has at least one chromophore moiety covalently bonded to at least one other component of the radiation-cured composition identifying the color;
The method comprises
Supplying a support;
Supplying to the radiation curable composition of claim 59 ;
Applying the radiation curable composition of claim 59 to at least a portion of the support;
Exposing the applied composition to radiation of an appropriate wavelength and intensity for an appropriate time to cure the composition to a radiation-cured composition that identifies color. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
65. The method of claim 64 , selected from the group consisting of (iv) an optical fiber ribbon. 38. The dye concentrate of claim 37 , wherein the dye concentrate comprises more than 5 wt% chromophore moieties based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 66 . The dye concentrate, dye concentrate of claim 37 containing a chromophore moiety of 1-0 wt% to 35 wt% based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 68 . The compound comprising a radiation curable chromophore comprises a compound comprising a first radiation curable chromophore and a compound comprising a second radiation curable chromophore;
At least the chromophore moiety of a compound containing the first radiation curable chromophore is different from the chromophore moiety of a compound containing the second radiation curable chromophore
38. A dye concentrate according to claim 37, characterized in that (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 70 . (I) a compound comprising a radiation curable chromophore comprising at least one radiation curable group and at least one chromophore moiety ;
(II) Tetrahydrofurfuryl acrylate (THFA) as reactive diluent
A dye concentrate . 74. The dye concentrate of claim 72, wherein the at least one radiation curable group comprises ethylenic unsaturation. 74. The dye concentrate of claim 73, wherein the ethylenically unsaturated and radiation curable group comprises (meth) acrylate. The dye concentrate of claim 72, wherein the at least one radiation curable group comprises an epoxy group. The at least one chromophore moiety is a methine dye;
73. The dye concentrate of claim 72, wherein the methine dye comprises a methine nucleus group having at least one substituent comprising at least one radiation curable group. The at least one chromophore moiety is an azo dye;
75. The dye concentrate of claim 72, wherein the azo dye comprises an azo nucleus group having at least one substituent comprising at least one radiation curable group. The at least one chromophore moiety is an anthraquinone dye;
73. The dye concentrate of claim 72, wherein the anthraquinone dye comprises an anthraquinone core group having at least one substituent comprising at least one radiation curable group. A dye concentrate according to claim 78 , comprising:
The anthraquinone dye has the following structural formula:

[Wherein at least one of the R groups R ¹¹ to R ¹⁸ comprises at least one ethylenically unsaturated radiation curable group,
R groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are each independently hydrogenated, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated Or an alkali metal, optionally selected from the group consisting of hydrocarbyl groups containing one or more heteroatoms]. One or two of the R groups R ¹¹ to R ¹⁸ have (meth) acryl functionality,
At least four of the dye concentrate according to claim 79 is hydrogen of ^{R 18} from the R radicals ^{R 11.} 79. The dye concentrate of claim 78, wherein the anthraquinone dye has one of the following structural formulas:

[Where
R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are the same or different and are independently hydrogen, or in some cases from C ₁ to C ₆ —OH, —NH ₂ , — SH, —NO ₂ , —CN, alkyl substituted with one or more substituents selected from the group of halogen]. Radiation-curable oligomers that does not include the outgoing chromophore
73. The dye concentrate of claim 72, further comprising: Dye concentrate of claim 82 containing TiO ₂ in the of et. One or more photoinitiators is found, reactive diluents, stabilizers and dyes concentrate according to claim 82 comprising a surfactant. 84. A support having the dye concentrate of claim 82 on at least a portion thereof . The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
The support according to claim 85 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a dye concentrate for identifying a color on at least a portion of a support, comprising:
The dye concentrate for identifying a color has at least one chromophore moiety covalently bonded to at least one other component of the dye concentrate for identifying a color;
The method comprises
Supplying a support;
Providing to the dye concentrate of claim 82 ;
Applying the dye concentrate of claim 82 to at least a portion of the support;
Suitable time the applied composition, the method comprising the steps you violence exposure to radiation of a suitable wavelength and intensity. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
90. The method of claim 87 , selected from the group consisting of (iv) an optical fiber ribbon. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 72 . Wherein the composition further radiation-curable composition of claim 89 containing TiO _2. 90. The radiation curable composition of claim 89 , wherein the composition further comprises one or more photoinitiators, reactive diluents, stabilizers, and surfactants. 90. A support having the radiation curable composition of claim 89 on at least a portion thereof. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
93. The support according to claim 92 , selected from the group consisting of (iv) an optical fiber ribbon. A method for making a radiation cured composition that identifies a color on at least a portion of a support, comprising:
A radiation-cured composition that identifies the color has at least one chromophore moiety covalently bonded to at least one other component of the radiation-cured composition that identifies the color;
The method comprises
Supplying a support;
Providing to the radiation curable composition of claim 89 ;
Applying the radiation curable composition of claim 89 to at least a portion of the support;
Exposing the applied composition to radiation of an appropriate wavelength and intensity at an appropriate time to cure the composition into a radiation-cured composition that identifies the color. The support is
(I) an optical fiber having a core and a cladding layer surrounding the core;
(Ii) an optical fiber having a core, a cladding layer surrounding the core, and one or more polymer coatings on the cladding layer;
(Iii) a plurality of optical fibers arranged in an array;
95. The method of claim 94 , selected from the group consisting of (iv) an optical fiber ribbon. 75. The dye concentrate of claim 72 , wherein the dye concentrate comprises greater than 5 wt% chromophore moieties based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 96 . The dye concentrate, dye concentrate of claim 72 containing a chromophore moiety of 1-0 wt% to 35 wt% based on the total weight of the dye concentrate. (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 98 . The compound comprising a radiation curable chromophore comprises a compound comprising a first radiation curable chromophore and a compound comprising a second radiation curable chromophore;
At least the chromophore moiety of a compound containing the first radiation curable chromophore is different from the chromophore moiety of a compound containing the second radiation curable chromophore
A dye concentrate according to claim 72, characterized in that (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate of claim 100 . (A) a radiation curable oligomer containing no chromophore;
The following (b) a dye concentrate according to claim 1,
(C) the dye concentrate of claim 37 ;
(D) The dye concentrate of claim 72
A radiation curable composition comprising two or more of the above . (A) a radiation curable oligomer containing no chromophore;
(B) A radiation curable composition comprising the dye concentrate according to claim 102 . (I) a colored oligomer for providing color to the coating on the communication element,
The colored oligomer is
(A) an oligomer end-capped with isocyanate;
(B) a reaction product of (i) an isocyanate-reactive functional group and (ii) a radiation curable monomer having both ethylenic unsaturation;
The colored oligomer is radiation cured by a covalent bond formed by reacting the reactive functionality (i) of the radiation curable monomer (b) with the isocyanate end-capped oligomer (a). End-capped with sex groups,
The isocyanate end-capped oligomer (a)
(C) at least one polyfunctional compound having at least two isocyanate-reactive groups;
(D) a reaction product of at least one polyisocyanate;
A colored oligomer comprising the polyfunctional compound (c) comprising at least one dye having at least two isocyanate-reactive functional groups ;
(II) Tetrahydrofurfuryl acrylate (THFA) as reactive diluent
A dye concentrate . 105. The dye concentrate of claim 104, wherein the dye is an anthraquinone dye, and the anthraquinone dye has the following structural formula:

[Where
At least two R groups from _{^{R 1 R 8, -OH, -NH}} 2, on condition that at least one isocyanate-reactive functional groups selected from the group consisting of ^-SH, R 1, ^{R 2} R ³ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal, optionally one or more Are each independently selected from the group consisting of hydrocarbyl groups containing heteroatoms, and adjacent R groups from R ¹ to R ⁸ can form a ring]. 107. The dye concentrate of claim 105, wherein one to three of R ¹ to R ⁸ of the R group have the following structural formula:

[Where
R ⁹ is hydrogen or an alkyl group having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a is an integer of 1 or et al. 6,
Y represents a hydroxyalkylene or a polymer unit of an alkylene oxide monomer selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide and glycidol,
b is 0 or 1,
Z is a reactive —OH, —NH ₂ , or —SH group;
Furthermore, the remainder of the R groups R ¹ to R ⁸ is selected from the group consisting of hydrogen, amino, hydroxy, halogen, nitro, carboxylated alkali metal, sulfated alkali metal]. 107. The dye concentrate of claim 105, wherein the anthraquinone dye has the following structural formula:

[Where
R ⁹ and R ¹⁰ are independently selected from hydrogen or an alkyl radical having 1 or al 1 2 carbon atoms,
X is —CH ₂ —;
a and a 'is an integer of 1 or et 6 independently
Y and Y ′ each independently represent a hydroxyalkylene or a polymer unit of an alkylene oxide monomer selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, and glycidol;
b and b ′ are independently 0 or 1,
Z and Z ′ are reactive —OH, —NH ₂ , or —SH groups]. 108. The dye concentrate of claim 107, wherein the isocyanate end-capped oligomer (a) is a urethane oligomer and the anthraquinone dye has the following structural formula:

Wherein, n, n ', m, m', p, and p 'has a value of 0 to 4 0 independently. 108. The dye concentrate of claim 107, wherein the anthraquinone dye has the following structural formula.

The anthraquinone dye is 1,5-bis ((3-hydroxy-2,2-dimethylpropyl) amino) -9,10-anthracenedione, 2,2 ′-((9,10-dihydro-9,10- Dioxo-1,5-anthracenediyl) bis (thio)) bis-benzoic acid, 2-hydroxyethyl ester, 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) -4,8- 106. The dye concentrate of claim 105, selected from the group consisting of bis ((4-methylphenyl) thio) anthraquinone. 106. The dye concentration of claim 105, wherein the anthraquinone dye is 1,5-bis ((2,2-dimethyl-3-hydroxypropyl) amino) -4,8-bis ((4-methylphenyl) thio) anthraquinone. Thing . 105. The dye concentrate of claim 104 , wherein a (meth) acrylic group is the ethylenic unsaturation (ii) in the radiation curable monomer (b). A photocurable resin composition for forming a colored and cured coating on an optical fiber comprising:
The resin composition is
(E) at least one (meth) acrylate end-capped urethane oligomer; (f) at least one photoinitiator;
(G ) A photocurable resin composition comprising at least one dye concentrate according to any one of claims 1, 37, 72 and 104 . An optical fiber comprising a colored and cured coating comprising:
114. An optical fiber wherein the colored and cured coating is formed from the photocurable resin composition of claim 113 . An optical fiber comprising a colored and cured coating comprising:
114. An optical fiber wherein the colored and cured coating is formed from the photocurable resin composition of claim 113 . A communication element having a color identification coating thereon,
117. A communication element comprising the optical fiber of claim 115 .

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