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WO1997019029A1 - Procede de formation d'un revetement durci et colore - Google Patents

Procede de formation d'un revetement durci et colore Download PDF

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Publication number
WO1997019029A1
WO1997019029A1 PCT/NL1996/000460 NL9600460W WO9719029A1 WO 1997019029 A1 WO1997019029 A1 WO 1997019029A1 NL 9600460 W NL9600460 W NL 9600460W WO 9719029 A1 WO9719029 A1 WO 9719029A1
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WO
WIPO (PCT)
Prior art keywords
coating
composition
acrylate
meth
optical fiber
Prior art date
Application number
PCT/NL1996/000460
Other languages
English (en)
Inventor
Miyuki Ishikawa
Yuji Naito
Takashi Ukachi
Original Assignee
Dsm N.V.
Japan Synthetic Rubber Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm N.V., Japan Synthetic Rubber Co., Ltd. filed Critical Dsm N.V.
Priority to AU75906/96A priority Critical patent/AU7590696A/en
Publication of WO1997019029A1 publication Critical patent/WO1997019029A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4479—Manufacturing methods of optical cables
    • G02B6/4482—Code or colour marking
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings

Definitions

  • the present invention relates to a process for forming a colored layer on an optical fiber on which a cured coating of a photocurable resin composition has been applied.
  • an optical fiber A generally has a construction consisting of a primary coating 2 of a soft resin around a quartz fiber 1, a secondary coating 3 of a hard resin around the primary coating 2, and a colored coating 4 around secondary coating 3.
  • the primary coating 2 of a soft resin is omitted in some embodiments.
  • a plurality of optical fibers A are made into a unit (a ribbon assembly) via a matrix material 5 which generally is made from a radiation curable resin composition.
  • the colored layer 4 is provided over the hard, secondary coating 3 in order to make it easy to identify each optical fiber from others when optical fibers are taken out from the ribbon assembly.
  • An object of the present invention is to provide a process for forming a color layer for optical fiber which is strongly adhered to a secondary coating provided on a quartz fiber.
  • This object of the present invention is solved in the present invention by a process for the manfacture of a coated optical fiber with a color layer comprising: (i) coating an optical fiber with a radiation curable resin composition,
  • composition I a radiation curable resin composition
  • composition II a radiation curable coloring composition
  • the irradiation-cured color layer for optical fiber produced by means of the present invention is strongly adhered to a secondary coating provided on a quartz fiber, the colored layer is not peeled off from the secondary coating when the matrix material is to be removed from the optical fiber ribbon assembly, so that it is possible to identify individual optical fibers in the ribbon assembly.
  • the strong adhesion in the interface of the two layers obtained by the process of the present invention exhibits excellent reproducibility.
  • Figure 1 shows an illustrative cross-sectional view of coating layers provided to an optical fiber.
  • Figure 2 is an illustrative cross-sectional view of a ribbon assembly, or multi-core structure, of optical fibers.
  • This embodiment is also the process of producing optical fiber itself and comprises the aforementioned steps (i) to (iv). Specifically, the cured coating produced by irradiation in step (ii) is activated by being irradiated again in step (iii), and Composition IIB is coated on the activated surface of coating and irradiated with light in step (iv).
  • Composition I is first applied to the quartz fiber in step (i). This Composition I may be applied directly to the quartz fiber as a secondary coating or may be applied over the primary coating which has been previously applied to the quartz fiber.
  • step (i) comprises (ia) coating the pristine optical fiber with a radiation curable primary coating composition, (ib) curing said composition with radiation, preferably UV-light at a dose between 10-1000 J/cm 2 , and (ic) coating said optical fiber with a radiation curable secondary coating composition.
  • the primary and secondary coatings can also be applied "wet on wet", i.e. without first curing the primary coating.
  • step (i) comprises (ia) coating a pristine optical fiber with a radiation curable primary coating composition and (ib) coating said optical fiber with a radiation curable secondary coating composition.
  • the quantity of Composition I to be applied should be such that the secondary coating after cure by irradiation has a thickness of about 10-100 ⁇ m, preferably of about 15-40 ⁇ m.
  • the coated surface is irradiated in step (ii) with UV light for example from a high pressure mercury lamp or a metal halide lamp, at a dose of about 10-1,000 J/cm 2 in the first photo-chamber to form a cured secondary coating.
  • the photo-reaction rate of the Composition I in the cured coating thus obtained is about 50% or more, and preferably about 70% or more. Most preferably, the rate is between about 80% and about 100%.
  • the photo-reaction rate is determined by measuring the concentration of ethylenically unsaturated groups by IR spectrum or NMR before and after the step (ii) and calculated according to the following formula.
  • Eo is the concentration of ethylenically unsaturated groups of Composition I and El is the concentration of ethylenically unsaturated groups after step (ii ) .
  • the cured coating of Composition I is again irradiated with a light with a wavelength of 200-450 nm in a photo-chamber.
  • a high pressure mercury lamp or a metal halide lamp can for example be used as the light source. It is desirable to eliminate light with wavelength outside the 200-450 nm range which is contained in the spectrum from these light sources by means of spectroscopic filter.
  • the cured coating is formed in the first photo-chamber, following which the cured coating is successively irradiated again in the second photo-chamber with a light having a wavelength of 200-450 nm in step (iii).
  • the step (ii) is carried out while the quartz fiber passes through this photo-chamber, the quartz fiber with the cured coating thereon is wound and irradiated again in a photo-chamber to perform the step (iii).
  • This photo-chamber wherein the step (iii) is carried out may be either the same as or different from the photo-chamber used for carrying out the step (ii).
  • the above second irradiation be carried out under an atmosphere containing oxygen preferably at a concentration of about 0.1-21 mol%.
  • the dose for the second irradiation is about 50-1,000 mJ/cm 2 , preferably about 100-600 mJ/cm 2 , on the cured coated surface.
  • the photocurable coloring composition (Composition II) is successively coated on the surface of the cured coating of Composition I (the secondary coating).
  • the formation of the coating of Composition II may be carried out either continuously after the completion of step (iii) or after a certain period of time, but, preferably, within two days after the completion of step (iii), and more preferably within one hour after the completion of step ( iii ) .
  • the quantity of Composition II to be applied preferably is suitable to make a cured coating
  • (colored layer) with a thickness of about 1-20 ⁇ m. Most preferred is a thickness of about 3-8 ⁇ m, as the industry standard is about 5 ⁇ m.
  • the Composition II is cured by irradiation in the same manner as the method for curing the coating of Composition I mentioned above, thereby producing a cured colored layer.
  • the peel strength between the secondary coating and the colored layer in the state of the art generally is not very high, i.e. 10-30 g/cm. With the method of the invention it is possible to achieve much higher peel strength without the need for special additives.
  • the present invention also relates to a coated and colored optical fiber in which the peel strength between the secondary coating and the colored layer is higher than about 70 g/cm both before and after a hot water test as described below. More preferably, the peel strength is higher than about 100 g/cm.
  • the coated and colored optical fibers are very well suited for use in a ribbon assembly comprising a plurality of coated and colored optical fibers bonded to each other with a matrix material, wherein the peel strength between the secondary coating and the coloring layer is higher than 70 g/cm, and wherein the peel strength between the colored layer and the matrix material is less than 50 g/cm. Preferably, the latter peel strength is less than 30 g/cm.
  • Radiation curable matrix materials can suitable be formulated from components as described for resin Composition IA.
  • the photo-curable resin composition in general comprises the following components (A), (B), and (C), which is given as a typical example and hereinafter referred to from time to time as Composition IA.
  • the several components described for use in composition IA can be choosen and formulated to achieve a variety of properties so that the compositions are useful for primary coatings, secondary coatings and for matrix materials.
  • the components are useful to formulate the binder composition for the radiation curable coloring composition.
  • the coating generally comprise:
  • (A) about 10-80% by weight of a polymer containing an ethylenically unsaturated group and at least one structural unit selected from the following groups (l)-(4), -(R'O)- (l)
  • R 1 is an alkylene group having 2-6 carbon atoms
  • n denotes an integer of 3-10
  • R 2 and R 3 individually represents a divalent organic group having 2-13 carbon atoms
  • n is an integer of 1-50 and R 4 is an alkylene group having 2-6 carbon atoms or a divalent organic group of the following formula (5),
  • R 5 , R 6 , R 7 , and R ⁇ individually represent a hydrogen atom or an alkyl group having 1-8 carbon atoms, and in which Q is a phenyl ring or a hydrogenated phenyl ring.
  • (C) about 0.1-10% by weight of a photopolymerization initiator, the weight% being related to the total of the composition.
  • Composition IA Illustrating the component (A) for Composition IA, given as specific preferred alkylene groups having 2-6 carbon atoms which are represented by R 1 in formula (1) are the structural units shown by the following formulas (6-1) to (6-8).
  • m is an integer 3-10 and particularly preferably 5.
  • divalent organic groups represented by R 2 or R 3 in formula (3) divalent alkylene groups and arylene groups are preferred.
  • R 2 or R 3 are ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, phenylene, diphenylene, methylenebisphenylene, and the like.
  • the structural units (6 '-2) is particularly preferred, being bisphenol-A or hydrogenated bisphenol-A.
  • n 1-25.
  • the following groups (7-1) to (7-5) are given as specific examples of the ethylenically unsaturated groups contained in the component (A).
  • CH, C—C-0-R iJ - (7-2)
  • R 12 individually represent a hydrogen atom or a methyl group and R 13 is an alkylene group having 2-9 carbon atoms, and preferably alkylene groups having 2-5 carbon atoms, such as ethylene group, propylene group, tetramethylene group, and pentamethylene group.
  • the group (7-1) containing one ethylenically unsaturated group, (7-2) containing one ethylenically unsaturated group, (7-3) containing two ethylenically unsaturated groups, and (7-4) containing three ethylenically unsaturated groups are preferred, with the groups (7-1) and (7-2) being particularly preferred.
  • the structural units (1), (2), (3), (4) and the ethylenically unsaturated group which constitute the component (A) are bonded via at least one bond selected from the group consisting of urethane bond, urea bond, amide bond, ester bond, and ether bond.
  • the number average molecular weight of the component (A) is preferably about 1,000 to about 10,000, and more preferably about 1,500 to about 8,000.
  • the amount of the ethylenically unsaturated group contained in the component (A) is 1-20, preferably 1-10, per molecule. Excellent curability of the composition, and favorable durability and flexibility of the cured products are obtained by keeping the proportion of the ethylenically unsaturated group in the above range.
  • the polymers illustrated above can be used independently or in combination of two or more as the component (A) .
  • the proportion of the component (A) in Composition IA is preferably about 10 to about 75% by weight, and more preferably about 30 to about 70% by weight. Excellent coatability and processability of Composition IA, as well as superior flexibility of the cured products, can be achieved by keeping the proportion of the component (A) in this range.
  • diol (a) containing at least one structural unites selected from the above formulas (1), (2), (3), and (4), and optionally a diol other than the diol (a), with a diisocyanate compound to produce a polymer bonded by urethane bonds and having isocyanate group, and then reacting the isocyanate group of this polymer with a compound having a hydroxyl group and the ethylenically unsaturated group represented by the formulas (7-1) to (7-5) (such a compound is hereinafter referred to as "specific unsaturated compound” (a)), thereby introducing the ethylenically unsaturated group via the urethane bond.
  • a process comprising reacting the diol (a), and optionally a combination of the diol (a) and a diol compound other than the diol (a) or a diamine, with a diisocyanate compound to produce a polymer bonded by urethane bonds, and optionally by urea bonds, and having isocyanate group, and then reacting the isocyanate group of this polymer with the specific unsaturated compound (a), thereby introducing the ethylenically unsaturated group via the urethane bond.
  • a process comprising reacting a diisocyanate compound with the specific unsaturated compound (a) to produce a polymer bonded by urethane bonds and having isocyanate group and ethylenically unsaturated groups, and reacting the isocyanate group of this polymer with the diol (a), and optionally a combination of the diol (a) and at least one compound selected from diol compounds other than the diol (a) and diamines, thereby producing urethane bonds, and optionally urea bonds.
  • a process comprising reacting the diol (a), and optionally a combination of the diol (a) and at least one compound selected from diol compounds other than the diol (a) and diamines, with a diisocynate compound to produce a polymer having at least two functional groups selected from hydroxyl group, primary amino group, and secondary amino group, and then reacting these functional groups with a compound having carboxy group, epoxy group, or acid halide group and also having the ethylenically unsaturated group represented by the formulas (7-1) to (7-5), thereby producing ester bonds or amide bonds.
  • the products produced by these Processes 1 to 4 are urethane acrylate polymers and suitable for use as the component (A) .
  • diols containing the above structural unit (1) are polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, poly-2-methyltetramethylene glycol, ethylene oxide adduct to bisphenol A, butylene oxide adduct to bisphenol A, ethylene oxide adduct to bisphenol F, butylene oxide adduct to bisphenol F, ethylene oxide adduct to hydrogenated bisphenol A, butylene oxide adduct to hydrogenated bisphenol A, ethylene oxide adduct to hydrogenated bisphenol F, butylene oxide adduct to hydrogenated bisphenol F, and polyether diols obtained by the ring-opening copolymerization of two or more types of ionic-polymerizable cyclic compounds.
  • Examples of the ionic-polymerizable cyclic compound used to produce these polyether diols include cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahyd ofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, butadiene monoxide, and isoprene monoxide.
  • cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahyd ofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, butadiene monoxide, and isoprene monoxide.
  • ionic-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and ethylene oxide and butene-1-oxide.
  • the ring-opening copolymers of these two or more ionic-polyme izable cyclic compounds may be randomly bonded.
  • PTMG 1000 and PTMG 2000 are PTMG 1000 and PTMG 2000 (Mitsubishi Chemical); PPG 1000, PPG 2000, EXCENOL 2020, EXCENO 1020 (Asahi Oline); PEG 1000, UNISAFE DC 1100, UNISAFE DA 400, UNISAFE DC 1800 (Nippon Oil and Fats Co., Ltd.); PPTG 2000, PPTG 1000, PTG 400, PTGL 2000 (Hodogaya Chemical Co., Ltd.); and PBG 2000A, PBG 2000B (Dai-ichi Kogyo Seiyaku).
  • diol having the structural unit of formula (2) examples of the diol having the structural unit of formula (2) are polycaprolactone diols obtained by the reaction of ⁇ -caprolactone and a divalent diol, such as ethylene glycol, tetramethylene glycol, 1,6-hexane glycol, neopentylene glycol, or 1,4-butane diol.
  • a divalent diol such as ethylene glycol, tetramethylene glycol, 1,6-hexane glycol, neopentylene glycol, or 1,4-butane diol.
  • polyester diols obtained by the reaction of a polyhydric alcohol, such as ethylene glycol, propylene glycol, tetramethylene glycol, 1 , 6-hexane diol, neopentylene glycol, or 1 , 4-cyclohexane-dimethanol , and a polybasic acid, such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebacic acid, can be given.
  • a polyhydric alcohol such as ethylene glycol, propylene glycol, tetramethylene glycol, 1 , 6-hexane diol, neopentylene glycol, or 1 , 4-cyclohexane-dimethanol
  • a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebacic acid
  • polycarbonate diols and commercially available products such as DN-980, DN-981, DN-982, DN-983, Nipporane N-982 (Nihon Polyurethane), and PC-8000 (PPG of the US) can be given.
  • diol compounds other than the diol (a) used in the Processes 1-4 1, 4-cyclohexanedimethanol, dimethylol compounds of dicyclopentadiene, tricyclodecanedimethanol , ⁇ -methyl-S-valerolactone, polybutadiene with terminal hydroxyl groups, hydrogenated polybutadiene with terminal hydroxyl groups, castor oil-denatured polyol, polydimethylsiloxane with terminal diols, and polydimethylsiloxane carbitol-denatured polyols.
  • ethylene diamine, tetramethylene diamine, hexamethylene diamine, paraphenylene diamine, 4 , 4 '-diaminodiphenylmethane, diamines with hetero atoms, and polyether diamines can be given.
  • diisocyanate used in Processes 1-4 are, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1 , 5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3 '-dimethyl-4 , 4 '-diphenylmethane diisocyanate, 4 , 4 '-diphenylmethane diisocyanate,
  • (meth)acrylate compounds having hydroxyl group are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyoctyl (meth)acrylate, pentaerythritol tri(meth)acrylate, glycerine di (meth)acrylate, dipentaerythritolmonohydroxy penta(meth)acrylate, 1, 4-butanediol mono(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 1 , 6-hexanediol mono(irteth)acrylate, neopentylglycol mono(meth)acrylate, trimethylolpropane di (meth)acrylate, trimethylolethane di ( eth)acrylate, (meth)acrylates represented by the f ol l owing f ormulas ( 8-1 ) or ( 8-2 ) ,
  • CH 2 C- C-0-CH 2 CH 2 - ( 0-CCH 2 CH 2 CH 2 CH 2 CH 2 ) n -OH ( 8-2 )
  • R 13 is a hydrogen atom or a methyl group and n is an integer from 1-5.
  • the component (B) which constitutes a part of composition IA of the present invention functions as a reactive diluent.
  • Either monofunctional or polyfunctional compounds can be used as the component (B).
  • a combination of one or more mono- and polyfunctional components are used.
  • the monofunctional compounds are used as main component when cured materials with a relatively low modulus of elasticity are desired.
  • the modulus of elasticity can be controlled by using polyfunctional compounds in combination with the monofunctional compounds at a suitable ratio. Examples of the monofunctional compounds and the polyfunctional compounds include the following compounds, but are not limited to these, inasmuch as the compounds have a molecular weight of 1,300 or smaller.
  • Monofunctional compounds 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl ( eth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, unde
  • (meth)acrylate ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobomyl (meth)acrylate, bornyl (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N-vinylpyr
  • R 14 is a hydrogen atom or a methyl group
  • R 15 is an alkylene group containing 2 to 6, preferably 2 to 4 carbon atoms
  • R 16 is a hydrogen atom or an alkyl group containing 1 to 12, preferably 1 to 9, carbon atoms
  • q is an integer from 0 to 12, and preferably from 1 to 8.
  • R 14 is the same as the R 14 of formula (9) ;
  • R 17 is an alkylene group containing 2 to 8, preferably 2 to 5, carbon atoms; and
  • r is an integer from 1 to 8 , and preferably from 1 to 4.
  • R 14 and R 17 are the same as the R 14 , R 17 in formula (11) ; s is an integer of 1 to 15; and R 18 are individually a hydrogen atom or a methyl group.
  • Commercially available monofunctional compounds are for example: ARONIX M102, Mill, M113, M114, M117 (Toagosei Chemical Industry Co. , Ltd. ) , KAYARAD TC110S, R629, R644 (Nippon Kayaku Co. , Ltd. ) , and V# 3700 (Osaka Organic Chemical Industry, Ltd. ).
  • polyfunctional compounds for example can be used: tr imethylolpropane tr i (meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di (meth)acrylate, tetraethylene glycol di (meth)acrylate, polyethylene glycol di (meth)acrylate, 1 , 4-butanediol di (meth)acrylate, 1 , 6-hexanediol di (meth)acrylate, neopentyl glycol di (meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris (2-hydroxyethyl ) isocyanurate tri(meth)acr late, tris (2-hydroxyethyl ) isocyanurate di (meth)acr late, tricyclodecanedimethanol di (meth)acrylate, and epoxy (meth)acrylate which is an addition compound of (meth)acrylate to dig
  • Composition IA contains one or more N-vinyllactams such as N-vinylpyrrolidone or N-vinyl- ⁇ -caprolactam. When used, these N-vinyllactams are incorporated in Composition IA in an amount of 3-20% by weight, and preferably 3-15% by weight.
  • Composition IA contain a monomer having an alicyclic structure.
  • Isobomyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecanedimethanol di (meth)acrylate, and the like can be given as examples of the monomer having an alicyclic structure. Of these, isobomyl (meth)acrylate and tricyclodecanedimethanol di (meth)acrylate are particularly preferred.
  • the component (B) described above in detail is preferably incorporated in Composition IA in an amount of about 20 to about 60% by weight, and preferably about 25 to about 50% by weight.
  • Either a radical photopolymerization initiator and an ionic photopolymerization initiator may be used as the component (C) which makes up the Composition IA. Radical photopolymerization initiators are preferred.
  • radical photopolymerization initiators are 1-hydroxycyclohexyl phenyl ketone, 2 ,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole,
  • radical photopolymerization initiators are Irgacure 184, 369, 651, 500, 907 CGI1700, CGI1750, CGI1850, CG24-61 (Ciba Geigy), Lucirin LR8728 (BASF), Darocur 1116, 1173 (Ciba Geigy), and Uvecryl P36 (UCB).
  • 2, 5-diethoxy-4-(p-tol lmercapto)benzene diazonium PF6-, 2 , 4 , 6-trochlorobenzene diazonium PF6-, 4-dimethylaminonaphthalene diazonium PF6-, and cyclopentadienylpherocenium PF6- can be given.
  • a photo-sensitizer may be used together with the photopolymerization initiator, component (C).
  • photo-sensitizer examples include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylamino-benzoate, ethyl 4-dimethylamino-benzoate, isoamyl
  • the component (C) may be incorporated in Composition IA in an amount of about 0.1-10% by weight, particularly preferably about 0.5-7% by weight.
  • the photo-sensitizer is preferably added in an amount of about 0.01-10 parts by weight for 100 parts by weight of the photopolymerization initiator.
  • polymers or oligomers can be added to Composition IA.
  • Such polymers or oligomers include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivatives, styrene/butadiene/styrene block copolymer, styrene/ethylene/butene/styrene block copolymer , styrene/isoprene/styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine-containing oligomer, silicone oligomer, polysulfide oligomer, and the like.
  • reactive oligomers prepared by copolymerizing styrene compounds, (meth)acryl compounds, (meth)acryl compounds with an epoxy group, and the like, and introducing an acryloyl group into the copolymer (e.g. AP-2150, B-3000 to B-3006 (Shin-Nakamura Chemical Co.)) may be incorporated in the composition.
  • an acryloyl group e.g. AP-2150, B-3000 to B-3006 (Shin-Nakamura Chemical Co.)
  • Composition IA may be formulated with various components, as required, such as antioxidants, UV absorbers, photo-stabilizers, silane coupling agents, aging preventives, heat polymerization inhibitors, leveling agents, coloring matters, surface active agents, preservatives, plasticizers, lubricants, solvents, fillers, wettability improvers, and coated surface improvers.
  • antioxidants such as UV absorbers, photo-stabilizers, silane coupling agents, aging preventives, heat polymerization inhibitors, leveling agents, coloring matters, surface active agents, preservatives, plasticizers, lubricants, solvents, fillers, wettability improvers, and coated surface improvers.
  • antioxidants which can be used are Irganox 1010, 1035, 1076, 1222 (Ciba Geigy), and the like.
  • UV absorbers Tinuvin-P, 234, 320, 326, 327, 328, 213 (Ciba Geigy), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (Sumitomo Chemical Industries Co., Ltd.), and the like are given as examples.
  • photo-stabilizers which can be added include Tinuvin 292, 144, 622LD (Ciba Geigy), and Sanol LS770, LS765, LS292, LS2626, LS1114, LS744 (Sankyo Co.).
  • silane coupling agents which can be given are ⁇ -aminopropyltriethoxy silane, ⁇ -mercaptopropyltrimethoxy silane, ⁇ -methacryloxypropyl-trimethoxy silane, and commercially available products such as SH6062, SZ6030 (Toray-Dow Corning Silicone Co.) and KBE903, KBM803
  • aging preventives include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (Sumitomo Chemical Co.).
  • leveling agent dimethylpolysiloxane-polycarbinol graft polymers and commercially available products such as SH190, SH28PA (Toray-Dow Corning Silicone Co.) are given.
  • Composition IA As a typical example of Composition IA which has been described above in detail, a series of products commercially available under the trademark of Desolite R3000 (Japan Synthetic Rubber Co., Ltd.) are given.
  • composition II the photocurable coloring composition
  • Composition IIB the composition comprising the following Component (A'), and/or Component (B'), Component (C'), and Component (D')
  • Component IIB the composition comprising the following Component (A'), and/or Component (B'), Component (C'), and Component (D')
  • Composition IIB the composition comprising the following Component (A'), and/or Component (B'), Component (C'), and Component (D')
  • (B') A reactive diluent, preferably at least one of the multifunctional reactive diluents, as described above.
  • the urethane acrylate polymer (A') belongs to the Component (A) of Composition IA.
  • the polymers for the Component (A) as well as the processes for manufacturing such polymers have already been illustrated in detail.
  • Particularly preferred urethane acrylate polymers are those obtained by the reaction of (a) alkylene oxide adduct to bisphenol A or bisphenol F, (b) a diisocyanate, and (c) a (meth)acrylate containing a hydroxyl group.
  • This type of urethane acrylate polymer is commercially available under the trademarks, for example, of NK Ester U-1301A, U-701A, U-401A, U-601BA, and U-1001BA (manufactured by
  • acrylate polymers as component (A') are e.g. acrylated epoxies.
  • the Component (A') is preferably incorporated in Composition IIB in an amount of about 5 to about 80% by weight, and particularly preferably about 5 to about 70% by weight.
  • component (B) The same reactive diluent as used for composition IA as component (B) can be used as component (B') for Composition IIB. In particular it is useful to have at least one multifunctional reactive diluent present in the coloring composition IIB.
  • the component (B') is used preferably in an amount of 5 to about 80 wt.%, more in particular of about 5 to about 60% by weight.
  • Either component (A') or component (B') should be present in the coloring composition.
  • the amount of (A') plus (B') is at least about 50 wt.% of the total coloring composition.
  • the same photopolymerization initiators as used for Composition IA as Component (C) can be used as Component (C') for Composition IIB.
  • the photo-sensitizers which are mentioned in connection with Composition IA can also be used together with the photopolymerization initiators in Composition IIB.
  • the Component (C') is used in an amount of about 0.1-20% by weight, particularly preferably about 0.5-10% by weight, in Composition IIB.
  • the photo-sensitizer is preferably added in an amount of 0.01-15 parts by weight for 100 parts by weight of Component (C').
  • a mixture of more than one photoinitiator and/or sensitizer is used.
  • Component (D') used in Composition IIB examples include, but not limited to, carbon black, titanium oxide, zinc oxide, insoluble azo pigments, condensed azo pigments, and pigments having a polycyclic structure such as Phthalocyanine Blue.
  • the Component (D') is used in an amount of about 0.1-50% by weight, particularly preferably about 1-10% by weight, in Composition IIB.
  • thermoplastic resins made from an acrylate monomers or polysacharides. These resins are used in an amount of 0-30% by weight, preferably 0-20% by weight, in Composition IIB.
  • composition (IIB) The photocurable coloring compositions illustrated above are commercially available under the trademarks, for example, of UV-Ink, Best Cure-F series (manufactured by T&K TOKA Co.). Quartz fibers, glass plates, and the like are included in examples of the material on which the cured coating with color is formed by the process of the present invention.
  • the reaction was terminated when the residual amount of isocyanate was reduced to 0.1 wt% or less, to obtain a urethane acrylate (a-1) with a number average molecular weight of 1,060.
  • the resulting reaction product was reacted with 9.17 g of polyethylene oxide addition diol to bisphenol A (a number average molecular weight: 400) at 20-50°C and then with 47.65 g of polytetramethylene glycol having a number average molecular weight of
  • Composition (I-a) (a photocurable resin composition) was prepared by blending 60 g of urethane acrylate (a-1), 18.1 g of lauryl acrylate, 8.5 g of N-vinyl pyrrolidone, 9.6 g of SA1002 (Mitsubishi Chemical Co.), 3.0 g of Irgacure 184 (Ciba Geigy), 0.3 g of Irganox 1035 (Ciba Geigy), 0.1 g of SH190 (Toray-Dow Corning Silicone Co.), 0.06 g of SH28PA (Toray-Dow Corning Silicone Co.), and 0.3 g of diethylamine.
  • composition (I-b) (a photocurable resin composition) was prepared by blending 58.5 g of urethane acrylate (a-2), 7.8 g of isobomyl acrylate,
  • N-vinyl pyrrolidone 9.1 g of N-vinyl pyrrolidone, 12.2 g of Viscoat 700 (an ethoxylated-bisphenol-A-diacrylate of Osaka Organic Chemical Industry, Ltd.), 1.5 g of
  • Example 3-5 Preparation of Composition II> The components shown in Table 1 were blended at proportions indicated in Table 1 to produce photocurable coloring compositions (Composition II).
  • CH 2 CHCO- ( CH 2 ) 2 -OCNH- ( CH 2 ) 6 NHC- ( OCH 2 CH 2 ) 15
  • Coloring agent (1) Phthalocyanine Blue ZCA104 (trademark, manufactured by Dainichiseika Colour & Chemicals Manufacturing. Co.).
  • Coloring agent (2) Insoluble azo pigment,
  • Kamine F5B (trademark, manufactured by Sanyo Shikiso Co. )
  • Composition (I-a) was coated on a glass plate to a thickness of 200 ⁇ m and cured by irradiation with light at a dose of 500 mJ/cm 2 from a metal halide lamp in air, to obtain a cured coating.
  • the glass plate with the cured coating prepared in (Procedure 1) above was allowed to stand in a dark chamber at 23°C ⁇ 2°C for 10 days, followed by irradiation with light at a dose of 100 mJ/cm 2 from a metal halide lamp in air.
  • Composition II obtained in Example 3 was coated on the surface of the coating obtained in (Procedure 2) above to a thickness of 10 ⁇ m. This coating was cured by irradiation with light at a dose of 500 mJ/cm 2 from a metal halide lamp in a nitrogen atmosphere, to obtain a cured coating. A force (g/cm) to peel off the colored coating from the underlying coating was measured by the 90° peeling test according to JIS Z0237 at a peeling speed of 50 mm/min. This measurement was carried out using the double-layered coating sample obtained in (Procedure 3) above and a sample obtained by dipping this sample in hot water at 80°C for one week and drying it. The results are shown in Table 2.
  • Test Example 2 A double layered coating sample was prepared in the same manner as in Test Example 1, except that Composition I-b was used instead of Composition I-a in the Procedure 1; the irradiation of the Procedure 2 was carried out in a nitrogen atmosphere containing 0.2% oxygen; and Composition II obtained in Example 4 was used in the Procedure 3. The peeling strength was measured in the same manner as in Test Example 1. The results are shown in Table 2.
  • Test Example 3 A double layered coating sample was prepared in the same manner as in Test Example 1, except that the irradiation of the Procedure 2 was carried out in a nitrogen atmosphere containing 2% oxygen and Composition II obtained in Example 5 was used in the Procedure 3. The peeling strength was measured in the same manner as in Test Example 1. The results are shown in Table 2.
  • a double layered coating sample was prepared in the same manner as in Test Example 1, except that lights having a wavelength of 400 nm and shorter were cut out by causing the light from the metal halide lamp to pass through a spectroscopic filter in the Procedure 2.
  • the peeling strength was measured in the same manner as in Test Example 1. The results are shown in Table 2.
  • Comparative Test Example 2 A double layered coating sample was prepared in the same manner as in Test Example 1, except that the Procedure 2 was omitted. The peeling strength was measured in the same manner as in Test Example 1. The results are shown in Table 2.
  • the cured coating with color produced by the process of the present invention can strongly adhere with good reproducibility to a radiation-cured coating.
  • the adhesion is not affected by exposure to severe conditions such as dipping in hot water.
  • this cured coating with color is so strongly adhered to the secondary coating that there are no risks for the colored coating to be released from each optical fiber when optical fiber unit is disassembled. This makes it easy to identify an optical fiber from other optical fibers.

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  • Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Cette invention concerne un procédé permettant de faire fortement adhérer une couche colorée à la surface d'un revêtement secondaire qui a été appliqué à de la fibre optique de quartz. Ledit procédé consiste à irradier la surface du revêtement secondaire durci avec un rayonnement lumineux de longueur d'onde comprise entre 200 et 450 nm, à une dose comprise entre 50 et 1000 mJ/cm2 et à former le revêtement durci coloré à la surface du revêtement secondaire.
PCT/NL1996/000460 1995-11-20 1996-11-20 Procede de formation d'un revetement durci et colore WO1997019029A1 (fr)

Priority Applications (1)

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AU75906/96A AU7590696A (en) 1995-11-20 1996-11-20 Process for forming a cured coating with a color

Applications Claiming Priority (2)

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JP7/301169 1995-11-20
JP7301169A JPH09142889A (ja) 1995-11-20 1995-11-20 着色硬化塗膜の形成方法

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WO1998050317A1 (fr) * 1997-05-06 1998-11-12 Dsm N.V. Composition d'encre durcissable par exposition a un rayonnement
EP0890859A3 (fr) * 1997-07-07 1999-10-13 Dsm N.V. Composition à fibres optiques
WO1999061535A1 (fr) * 1998-05-28 1999-12-02 Dsm N.V. Composition d'encre polymerisable par rayonnement pour revetement de fibres de verre optiques
US6085010A (en) * 1997-06-11 2000-07-04 Dsm N.V. Optical glass fiber ribbon assemblies and radiation-curable compositions for use in forming ribbon assemblies
US6130980A (en) * 1997-05-06 2000-10-10 Dsm N.V. Ribbon assemblies and ink coating compositions for use in forming the ribbon assemblies
US6197422B1 (en) 1997-05-06 2001-03-06 Dsm, N.V. Ribbon assemblies and radiation-curable ink compositions for use in forming the ribbon assemblies
WO2001064596A1 (fr) * 2000-03-03 2001-09-07 Pirelli Cavi E Sistemi S.P.A. Fibre optique a revetement colore
US6301415B1 (en) 1997-08-14 2001-10-09 Dsm N.V Optical glass fiber ribbon assemblies, matrix forming compositions radiation-curable compositions
US6391936B1 (en) 1997-12-22 2002-05-21 Dsm N.V. Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies
US6498883B1 (en) 2001-04-05 2002-12-24 Borden Chemical, Inc. Optical fiber ribbon with pigmented matrix material and processes for making same
EP1408017A3 (fr) * 1997-05-06 2006-01-11 DSM IP Assets B.V. Compositions d'encre durcissant
US20220363913A1 (en) * 2020-09-25 2022-11-17 Sumitomo Electric Industries, Ltd. Resin composition, method for producing resin composition, optical fiber, and method for producing optical fiber

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
US6018605A (en) * 1997-12-31 2000-01-25 Siecor Operations Photoinitiator--tuned optical fiber and optical fiber ribbon and method of making the same
JP4947617B2 (ja) * 2005-12-15 2012-06-06 古河電気工業株式会社 光ファイバ心線および光ファイバテープ心線
WO2024135207A1 (fr) * 2022-12-21 2024-06-27 住友電気工業株式会社 Composition de résine pour revêtement coloré de fibres optiques, fibres optiques, et ruban de fibres optiques

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1408017A3 (fr) * 1997-05-06 2006-01-11 DSM IP Assets B.V. Compositions d'encre durcissant
WO1998050317A1 (fr) * 1997-05-06 1998-11-12 Dsm N.V. Composition d'encre durcissable par exposition a un rayonnement
US6130980A (en) * 1997-05-06 2000-10-10 Dsm N.V. Ribbon assemblies and ink coating compositions for use in forming the ribbon assemblies
US6197422B1 (en) 1997-05-06 2001-03-06 Dsm, N.V. Ribbon assemblies and radiation-curable ink compositions for use in forming the ribbon assemblies
US6085010A (en) * 1997-06-11 2000-07-04 Dsm N.V. Optical glass fiber ribbon assemblies and radiation-curable compositions for use in forming ribbon assemblies
EP0890859A3 (fr) * 1997-07-07 1999-10-13 Dsm N.V. Composition à fibres optiques
US6301415B1 (en) 1997-08-14 2001-10-09 Dsm N.V Optical glass fiber ribbon assemblies, matrix forming compositions radiation-curable compositions
US6391936B1 (en) 1997-12-22 2002-05-21 Dsm N.V. Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies
US6040357A (en) * 1998-05-28 2000-03-21 Dsm N.V. Method of making a radiation-curable ink composition, radiation-curable ink composition and ribbon assembly
WO1999061535A1 (fr) * 1998-05-28 1999-12-02 Dsm N.V. Composition d'encre polymerisable par rayonnement pour revetement de fibres de verre optiques
WO2001064596A1 (fr) * 2000-03-03 2001-09-07 Pirelli Cavi E Sistemi S.P.A. Fibre optique a revetement colore
US6498883B1 (en) 2001-04-05 2002-12-24 Borden Chemical, Inc. Optical fiber ribbon with pigmented matrix material and processes for making same
US20220363913A1 (en) * 2020-09-25 2022-11-17 Sumitomo Electric Industries, Ltd. Resin composition, method for producing resin composition, optical fiber, and method for producing optical fiber

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JPH09142889A (ja) 1997-06-03

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