• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    An optical fiber comprises an optical transmission medium having a core and a sheath; a primary resin layer disposed in contact with the optical transmission medium to cover the optical transmission medium; and a secondary resin layer overlying the primary resin layer, wherein the primary resin layer comprises a cured product of an ultraviolet light curable resin composition comprising a urethane (meth) acrylate oligomer, a monomer and a photopolymerization initiator, and a compound containing phosphorus and tin as constituent atoms; and a Young's modulus of the primary resin layer is 0.5 MPa or less than 23 ° C.
    公开号:FR3058410A1
    申请号:FR1760500
    申请日:2017-11-08
    公开日:2018-05-11
    发明作者:Yuya Homma；Kazuyuki Sohma；Kensaku Shimada
    申请人:Sumitomo Electric Industries Ltd；
    IPC主号:
    专利说明:

    TECHNICAL FIELD The present invention relates to optical fibers.
    BACKGROUND [0002] Optical fibers generally include layers of coating resin to protect glass fibers which are optical transmission media. JP 2014-132075 A and JP 2014-95923 A, and WO 2014/168201 A1, for example, describe resin compositions for coating optical fibers containing urethane (meth) acrylate oligomers.
    SUMMARY Resistance to lateral pressure has been required for optical fibers in order to minimize an increase in the transmission loss induced by a micro curvature generated when lateral pressure is applied to optical fibers. In addition, in the case where the coating resin layer has a primary resin layer covering an optical transmission medium and a secondary resin layer covering the primary resin layer, a reduction of the Young's modulus of the primary resin layer is required to improve resistance to lateral pressure.
    The organotin compound, which is a catalyst for synthesizing an urethane (meth) acrylate oligomer, can be mixed with the resin composition used to form the coating resin layer. For this reason, a slight amount tin derived from the organotin compound is contained in the coating resin layer formed by curing the resin composition. In the event that an organotin compound is contained in the coating resin layer, it also acts as a hydrolysis catalyst for the urethane bond and the ester bond in a hygrothermal environment, and it facilitates the progression of deterioration. the coating resin layer. Since the crosslinking density of the cured resin composition in a primary resin layer having a low Young's modulus, which has recently been desired when considering resistance to lateral pressure, is low, the cured resin composition is susceptible attacks by moisture content. Attacks by moisture content can cause hydrolysis and irregular splitting of the crosslinking of the primary resin, thereby producing concentrated stress points. When defects (voids) in the resin are produced in these parts, the voids increase in size at low temperatures causing micro curvatures which appear in the optical transmission medium. The loss of transmission of the optical fiber thus tends to increase.
    An object of the present invention is then to provide an optical fiber having a low Young's modulus leading to high resistance to lateral pressure, allowing the prevention of the production of voids even if the optical fiber is left in an environment. hygrothermal over a long period, and minimizing an increase in transmission loss at low temperature.
    The optical fiber according to one aspect of the present invention comprises an optical transmission medium having a core and a sheath, a layer of primary resin disposed in contact with the optical transmission medium to cover the optical transmission medium, and a secondary resin layer overlying the primary resin layer, wherein the primary resin layer comprises a cured product of a UV curable resin composition comprising an urethane (meth) acrylate oligomer, a monomer and an initiator photopolymerization, and a compound containing phosphorus and tin as constituent atoms; and a Young's modulus of the primary resin layer is 0.5 MPa or less at 23 ° C.
    According to the present invention, an optical fiber having a low Young's modulus leading to high resistance to lateral pressure, allowing the prevention of the production of voids even if the optical fiber is left in a hygrothermal environment for a long time , and minimizing an increase in transmission loss at low temperatures can be provided.
    BRIEF DESCRIPTION OF THE DRAWINGS [0008] FIG. 1 is a schematic transverse view illustrating an example of the optical fiber according to the present embodiment. FIG. 2A is a diagram illustrating a configuration of a metal grid material used in a grid side pressure test. FIG. 2B is a partially enlarged view of a portion in FIG. 2A.
    DETAILED DESCRIPTION [Description of an embodiment according to the present invention] The content of the embodiment according to the present invention will be detailed and described first. The optical fiber according to one aspect of the present invention comprises an optical transmission medium having a core and a sheath, a primary resin layer disposed in contact with the optical transmission medium to cover the optical transmission medium, and a resin layer secondary covering the primary resin layer, wherein the primary resin layer comprises a cured product of an ultraviolet light curable resin composition (also referred to hereinafter as a resin composition) comprising a (meth) acrylate oligomer urethane, a monomer and a photopolymerization initiator, and a compound containing phosphorus and tin as constituent atoms; and a Young's modulus of the primary resin layer is 0.5 MPa or less than 23 ° C.
    Tin (Sn) in the compound containing phosphorus and tin as constituent atoms is derived from an organotin compound used as a catalyst when the urethane (meth) acrylate oligomer is synthesized . The organotin compound is contained in the resin composition.
    While the organotin compound is useful as a catalyst when the urethane (meth) acrylate oligomer is synthesized, it also has an action to promote urethane bond hydrolysis and ester bonding in a hygrothermal environment. . On the contrary, the present inventors have found that by converting the organotin compound in the primary resin layer into a compound containing a phosphorus atom and a tin atom in the same molecule, the activity of the organotin compound can be lowered to avoid hydrolysis even after the optical fiber is stored in a hygrothermal environment for a long time, and then no vacuum is produced in the resin layer. The present inventors have thus produced the present invention.
    The photopolymerization initiator comprises 2,4,6trimethylbenzoyldiphenylphosphine oxide. 2,4,6-Trimethylbenzoyldiphenylphosphine oxide leads to excellent fast curing properties of resins, and provides as a side product after UV irradiation of diphenylphosphinic acid, which can react with the organotin compound to lower by -the activity of the organotin compound.
    The compound containing phosphorus and tin can be a reaction product between at least one phosphorus compound chosen from the group consisting of a compound represented by formula (la), a compound represented by formula (lb), and a compound represented by formula (Ic); and an organotin compound. The phosphorus compounds below can react quickly with the organotin compound to lower the activity of the organotin compound:
    R 1 -Ρ - ΟΗ
    R 3 -Ρ — ΟΗ
    R 4 --ρ — ΟΗ
    R 2
    ΟΗ (1 a)
    C1 b) (1 c) where R 1 , R 2 , R 3 , and R 4 each independently represent an alkyl group, an alkenyl group, or an aryl group.
    The phosphorus compound can comprise at least one chosen from the group consisting of diphenylphosphinic racide, phenylphosphinic acid, and phenylphosphonic acid since the activity of the organotin compound is easily lowered by their steric hindrance due to a phenyl group.
    The organotin compound can comprise at least one chosen from the group consisting of dibutyltin dilaurate and dibutyltin diacetate with regard to the availability and the catalyst properties when the urethane (meth) acrylate oligomer is synthesized. The difference between a glass transition temperature of the primary resin layer and a glass transition temperature of the secondary resin layer can be 150 ° C or lower. The low temperature properties of the optical fiber after thermal cycles can thereby be improved.
    Young's modulus of the primary resin layer may be 0.25 MPa or less than 23 ° C. A higher resistance to the lateral pressure of the optical fiber can thereby be ensured.
    The resin composition curable by ultraviolet light may further comprise an amine compound. The reaction between the phosphorus compound and the organotin compound can thereby be promoted.
    [Detailed description of an embodiment according to the present invention]
    Specific examples of optical fiber according to an embodiment of the present invention will be described below with reference to the drawings. The present invention will not be limited to these examples but is defined by the claims and intends to include all modifications in the spirit and scope of the claims equivalence. In the following description, identical reference signs will be given to identical components in the description of the drawings, and the duplication of description will be omitted.
    (Optical fiber)
    FIG. 1 is a schematic transverse view illustrating an example of the optical fiber according to an embodiment of the present invention. An optical fiber 10 comprises an optical transmission medium 13 having a core 11 and a sheath 12, and a coating resin layer 16 having a primary resin layer 14 and a secondary resin layer 15, arranged on the external periphery of the medium optical transmission 13.
    The sheath 12 surrounds the core 11. The core 11 and the sheath 12 mainly contain glass, such as silica glass; for example, a silica to which germanium is added can be used for the core 11, and pure silica or a silica to which fluorine is added can be used for the sheath 12.
    In FIG. 1, the external diameter (D2) of the optical transmission medium 13 is for example around 125 μm. The diameter (Dl) of the core 11 forming the optical transmission medium 13 is approximately 7 to 15 μm. The coating resin layer 16 has at least one bilayer structure comprising the primary resin layer 14 and the secondary resin layer 15. The total thickness of the coating resin layer 16 is usually about 60 µm; the thicknesses of the primary resin layer 14 and of the secondary resin layer 15 are substantially identical and the thickness of each layer is 20 to 40 μm. The thickness of the primary resin layer 14 may for example be 35 µm and the thickness of the secondary resin layer 15 may be 25 µm. In the case where very many optical fibers are bundled to make a cable, the coating diameter of the optical fiber is preferably thin. In this case, the total thickness of the coating resin layer 16 is preferably 30 to 40 µm. Each of the thickness of the primary resin layer and the thickness of the secondary resin layer can be 10 to 30 µm. The two are preferably almost identical.
    Young's modulus of the primary resin layer is 0.5 MPa or less at 23 ° C, preferably 0.3 MPa or less, more preferably 0.25 MPa or less. The lower limit value of the Young's modulus of the primary resin layer is not particularly limited, and is around 0.05 MPa. The Young's modulus of the primary resin layer can be measured by a pull-out modulus test at 23 ° C.
    On the other hand, a higher optical signal to noise ratio (OSNR) is required in the optical fiber to increase the channel capacity per core of a glass fiber by digital coherent communication techniques including a multi technique. -modulation. Examples of a method for improving the OSNR include a reduction in non-linearity. For the reduction of non-linearity, the effective cross section of the fiberglass core is increased as much as possible and a small loss of transmission is necessary. However, the first, that is to say an increase in the effective cross-section of the core, indicates that the optical fiber becomes brittle against lateral pressure. In particular, in the case where the effective cross section of the core exceeds 150 μm 2 , it is preferable that the primary resin layer has a low Young's modulus of 0.25 MPa or less.
    The primary resin layer 14 can be formed by curing an ultraviolet light curable resin composition comprising an urethane (meth) acrylate oligomer, a monomer, and a photopolymerization initiator.
    The term (meth) acrylate here indicates the acrylate or its corresponding methacrylate. The same is true for the term (meth) acrylic acid.
    Examples of the urethane (meth) acrylate oligomer include oligomers obtained by reaction of a polyol compound, a polyisocyanate compound, and a group-containing (meth) acrylate compound hydroxyl.
    Examples of the polyol compound include polytetramethylene glycol, polypropylene glycol, and an addition diol of bisphenol A-ethylene oxide. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate. Examples of the hydroxyl group containing (meth) acrylate compound include 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 1,6hexanediol monoacrylate, pentaerythritol triacrylate, 2hydroxypropyl acrylate, and tripropylene glycol diacrylate.
    An organotin compound is used as a catalyst during the synthesis of the urethane (meth) acrylate oligomer. Examples of the organotin compound include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (isooctylmercaptoacetate), and dibutyltin oxide. From a catalyst availability and performance point of view, it is preferable to use dibutyltin dilaurate or dibutyltin diacetate as the catalyst.
    A lower alcohol having 5 carbon atoms or less can be used during the synthesis of the urethane (meth) acrylate oligomer. Examples of the lower alcohol having 5 or less carbon atoms used during the synthesis of the urethane (meth) acrylate oligomer include methanol, ethanol, 1-propanol,
    2- propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,
    3- methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, and 2,2-dimethyl-1-propanol.
    The preparation of the urethane (meth) acrylate oligomer will be described below with reference to a specific example. If, for example, polypropylene glycol is used as the polyol, isophorone diisocyanate as the polyisocyanate, 2-hydroxyethyl acrylate as the (meth) acrylate containing a hydroxyl group, and methanol is used as the alcohol, it is possible to obtain an urethane (meth) acrylate oligomer containing three reaction products represented below:
    (1) HI- (PPG-I) nH (2) HI- (PPG-I) n-Me (3) Me-I- (PPG-I) n-Me where H represents the 2- acrylate residue hydroxyethyl, I represents the residue of isophorone diisocyanate, PPG represents the residue of polypropylene glycol, Me represents the residue of methanol, and n represents an integer of 1 or greater.
    The reaction product (1) is an oligomer reactive at both ends and the crosslinking density of the cured resin composition is therefore increased; however, the reaction product (2) is a reactive oligomer at one termination; the reaction product (2) therefore has the effect of reducing the crosslinking density of the cured resin composition, and can reduce the Young's modulus. The reaction product (3) is a non-reactive oligomer with two endings which does not cause curing with ultraviolet light; it is therefore preferable that the preparation is carried out so that the reaction product (3) is minimized. An alcohol other than methanol can be used to prepare a non-reactive oligomer at one end or a non-reactive oligomer at both ends.
    When the urethane (meth) acrylate oligomer is synthesized, one can use a silane coupling agent having a functional group reactive with the isocyanate group. Examples of the silane coupling agent having a functional group reactive with the isocyanate group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane,
    3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. If the polyol compound reacts with the isocyanate compound, the hydroxyl group-containing (meth) acrylate compound and the silane coupling agent are used in combination in the state where an isocyanate group is present on both terminations , and react with the isocyanate group, a reactive oligomer with two endings and in addition an oligomer for adding silane coupling agent to one end can be synthesized. As a result, as the oligomer can react with glass, the adhesion between the optical transmission medium 13 and the primary resin layer 14 can be promoted.
    One can use, as monomer, a monofunctional monomer having a polymerizable group, or a polyfunctional monomer having two or more polymerizable groups. These monomers can be used in the form of a mixture thereof. Examples of the monofunctional monomer include (meth) acrylate monomers, such as (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) n-butyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate , (meth) acrylate, (meth) isoamyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) n-octyl acrylate, (meth) isooctyl acrylate, (meth) isodecyl acrylate , lauryl (meth) acrylate, phenoxyethyl (meth) acrylate, (tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl meth), polyethylene glycol nonylphenol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and isobornyl (meth) acrylate; monomers containing a carboxyl group, such as (meth) acrylic acid, dimers of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and d (meth) acrylate 'œ-carboxypolycaprolactone; (meth) acrylates containing a heterocycle, such as 3- (3-pyridyl) propyl (meth) acrylate, N-acryloylmorpholine, N-vinylpyrrolidone,
    N-vinylcaprolactam, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine; maleimide monomers, such as maleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; N-substituted amide monomers, such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide,
    N, N-diethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methylolpropane (meth) acrylamide; aminoalkyl (meth) acrylate monomers, such as aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, Ν, Ν-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; and succinimide monomers, such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyoctamethylene succinimide.
    Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth ) tripropylene glycol acrylate, addition product of bisphenol A alkylene oxide acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, di (meth ) 1,4-butanediol acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, di (meth) acrylate 1,14-tetradecanediol, 1,16-hexadecanediol di (meth) acrylate, 1,20-eicosanediol di (meth) acrylate, isopentyl diol di (meth) acrylate, 3ethyl-l di (meth) acrylate , 8-octanediol, EO adducts of bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropanepolyethoxy tri (meth) acrylate, tri (meth) acrylate trim ethylolpropanepolypropoxy, trimethylolpropanepolyethoxypolypropoxy tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, pentaerythritiol tri (meth) acrylate, pentaerythritolpolyethoxy tetra (methoxy acrylate), tetra (methoxy) acrylate pentaerythritol, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythriol hexa (meth) acrylate, and isocyanurate modified tris [(meth) acryloyloxyethyl].
    The photopolymerization initiator can be appropriately chosen from known radical photopolymerization initiators. Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4 oxide, 4-trimethylpentylphosphine, 2,4,4-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropan-l-one (Irgacure 907, manufactured by BASF SE), oxide of 2, 4.6 trimethylbenzoyldiphenylphosphine (Irgacure TPO, manufactured by BASF SE), and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819, manufactured by BASF SE).
    These photopolymerization initiators can be used in the form of a mixture of these, and the photopolymerization initiator preferably comprises at least 2,4,6-trimethylbenzoyldiphenylphosphine oxide. 2,4,6-Trimethylbenzoyldiphenylphosphine oxide leads to excellent rapid hardening properties of resins, and provides as a side product after UV irradiation of diphenylphosphinic acid, which can react with the organotin compound to lower -the activity of the organotin compound.
    The compound containing phosphorus and tin is preferably a reaction product between at least one phosphorus compound chosen from the group consisting of a compound represented by the formula (la), a compound represented by the formula (lb), and a compound represented by the formula (Ie) cited above; and an organotin compound.
    R 1 , R 2 , R 3 , and R 4 each independently represent an alkyl group, an alkenyl group, or an aryl group. The alkyl group can be a linear, branched, or cyclic alkyl group having from 1 to 30 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, a 2-ethylhexyl group, a 1,1,3,3-tetramethylbutyl group, and a cyclohexyl group. Examples of the alkenyl group include a vinyl group. Examples of the aryl group include a phenyl group.
    At least one hydrogen atom constituting the alkyl group, the alkenyl group, or the aryl group may be replaced by a halogen atom, an alkoxy group, or a carboxyl group.
    Examples of the compound represented by formula (la) include dimethylphosphinic acid, diphenylphosphinic acid, bis (1,1,3,3-tetramethylbutyl) phosphinic acid, and 2-phenylphosphinopropanoic acid. Diphenylphosphinic acid is preferable as the compound represented by formula (la) since the activity of the organotin compound can be lowered by its steric hindrance due to phenyl groups.
    Examples of the compound represented by formula (lb) include ethylphosphonic acid, vinylphosphonic acid, n-butylphosphonic acid, 2-ethylhexylphosphonic acid, 3-bromopropylphosphonic acid, 3-methoxybutylphosphonic acid, phenylphosphonic acid, and 4- methoxyphenylphosphonic. Phenylphosphonic acid is preferable as the compound represented by the formula (lb) since the activity of the organotin compound can be lowered by its steric hindrance due to a phenyl group.
    Examples of the compound represented by formula (Ie) include methylphosphinic acid and phenylphosphinic acid. Phenylphosphinic acid is preferable for the compound represented by the formula (Ic) because the activity of the organotin compound can be lowered by its steric hindrance due to a phenyl group.
    The phosphorus compound can be added to the resin composition to form the primary resin layer, or can be produced by irradiating the resin composition with ultraviolet light. In the latter case, diphenylphosphinic acid can for example be produced using a resin composition including 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator and by irradiating the resin composition with light ultraviolet.
    Examples of the compound containing phosphorus and tin include compounds represented by formula (2) but are not particularly limited to these. The compound represented by formula (2) is an example of the reaction product between a compound represented by formula (la) and an organotin compound:
    OR 5 O
    R 1 - P — O — Sri - O — P— R 1 ( 2 )
    R 2 R 6 R 2 where R 1 and R 2 each independently represent an alkyl group, an alkenyl group, or an aryl group, and R 5 and R 5 each independently represent an alkyl group.
    The resin composition for forming the primary resin layer may further comprise an amine compound. When the amine compound is contained, the reaction between the phosphorus compound and the organotin compound can be promoted. Examples of the amine compound include triethylamine, triphenylamine, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate.
    The resin composition may further comprise a silane coupling agent, a photo-acid generator, a leveling agent, an anti-foaming agent, or an antioxidant.
    The silane coupling agent is not particularly limited as long as it does not prevent the hardening of the resin composition curable with ultraviolet light, and different silane coupling agents can be used comprising silane coupling agents known and used in the public. Examples of the silane coupling agent include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ^ -methoxyethoxy) silane, 3- (3,4-epoxycyclohexyl) -ethyltrimethoxyethylimethylane dimethylethiethylane ne, 3-acryloxypropyltrimethoxysi la ne, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxys ilane, N- (p-aminoethyl) -yaminopropyltrimethy-amyl-propylimyl-propane -chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, bis- [3- (triethoxysilyl) propyl] tetrasulfide, bis- [3- (triethoxysilyl) propyl] disulfide, γ-trimethimethylpropyl trimethyl sulfide, trimethimethyl carboxy The adhesion between the optical transmission medium 13 and the primary resin layer 14 can be controlled or the dynamic fatigue properties can be improved by using the silane coupling agent.
    One can use, as photo-acid generator, an onium salt having a structure represented by A + B. Examples of the photo-acid generator include sulfonium salts, such as UVACURE 1590 (manufactured by DAICEL -CYTEC Company, Ltd.), and CPI-100P and 110P (manufactured by San-Apro Ltd.); and iodonium salts, such as IRGACURE 250 (manufactured by BASF SE), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (manufactured by Rhodia Japan, Ltd.).
    The secondary resin layer 15 may for example be formed by curing an ultraviolet light curable resin composition comprising an urethane (meth) acrylate oligomer, a monomer, and a photopolymerization initiator. The urethane (meth) acrylate oligomer, the monomer, and the photopolymerization initiator can be appropriately selected from those listed in the resin composition forming the primary resin layer. The resin composition forming the secondary resin layer has a different composition from that of the resin composition forming the primary resin layer.
    Young's modulus of the secondary resin layer is preferably from 500 to 1,400 MPa at 23 ° C, even better from 800 to 1,200 MPa. If the Young's modulus of the secondary resin layer is 500 MPa or higher, the resistance to lateral pressure is easily improved; if the Young's modulus of the secondary resin layer is 1,400 MPa or less, the secondary resin layer has an appropriate elongation at break; the secondary resin layer is therefore difficult to break during removal of the coating, and has high coating removal properties.
    The difference between the glass transition temperature of the primary resin layer and the glass transition temperature of the secondary resin layer is preferably 150 ° C or lower, and is even better in the range of 120 ° C to 150 ° C. When the difference in glass transition temperatures is 150 ° C or lower, the properties at low temperature after thermal shock (thermal cycles) are improved.
    A colored layer, which serves as an ink layer, can be formed on the external surface of the secondary resin layer 15 constituting the coating resin layer 16 in order to distinguish the optical fibers. The secondary resin layer 15 can otherwise be formed in order to also serve as a colored layer.
    The optical fiber according to this embodiment can be subjected to a heat treatment at a temperature of 40 ° C to 85 ° C for about 12 to 72 hours. Heat treatment can promote the reaction between the phosphorus compound and the organotin compound. The optical fiber according to the present embodiment can be treated in an atmosphere containing D 2 (deuterium) in order to eliminate defects in the optical transmission medium, and by doing so, the heat treatment can be carried out simultaneously.
    EXAMPLES The results of the evaluation tests using the Examples and Comparative Examples according to the present invention will be presented below and the present invention will be described in more detail. The present invention will not be limited to these examples.
    (Urethane (meth) acrylate oligomer)
    A urethane acrylate oligomer was synthesized using polypropylene glycol having a molecular weight of 4000 as the polyol, isophorone diisocyanate as the polyisocyanate, 2-hydroxyethyl acrylate as the (meth) acrylate. containing a hydroxyl group, and dibutyltin diacetate as catalyst.
    A urethane acrylate oligomer B was prepared by synthesis using polypropylene glycol having a molecular weight of 4,000 as polyol, isophorone diisocyanate as polyisocyanate, 2-hydroxyethyl acrylate as ( meth) acrylate containing a hydroxyl group, methanol as alcohol, and dibutyltin dilaurate as catalyst.
    A urethane C acrylate oligomer was prepared by synthesis using polypropylene glycol having a molecular weight of 1000 as polyol, isophorone diisocyanate as polyisocyanate, 2-hydroxyethyl acrylate as ( meth) acrylate containing a hydroxyl group, and dibutyltin dilaurate as catalyst.
    (Resin composition for primary coating layer)
    Resin compositions were prepared each time for a primary resin layer having the compositions (parts by mass) shown in Tables 1 and 2.
    (Resin composition for secondary resin layer)
    Resin compositions were prepared each time for a secondary resin layer having the compositions (parts by mass) shown in Table 1 and in Table 2.
    [Preparation of optical fiber 10]
    A primary resin layer 14 having a thickness of 35 µm was formed using a resin composition for a primary resin layer on the outer periphery of an optical transmission medium 13 including a core and a sheath, and having a diameter external (D2) of 125 pm and an effective transverse surface of the core of 150 pm 2 ; and furthermore a secondary resin layer 15 having a thickness of 25 µm was formed on the outer periphery using the resin composition for a secondary resin layer to prepare an optical fiber 10. In addition, the optical fiber was subjected 10 to a heat treatment under the conditions shown in Table 1 or Table 2.
    [Evaluation of optical fiber 10]
    The resulting optical fibers were subjected to the following evaluation tests. The results are shown in Tables 1 and 2.
    (Elementary analysis)
    The prepared optical fiber was immersed in methyl ethyl ketone for treatment at 60 ° C for 14 hours, thereby extracting non-crosslinked constituents. The methyl ethyl ketone was then removed by an evaporator, and the residue was dissolved in methanol. The insoluble material produced at that time was filtered, and subjected to ICP emission spectrometry to confirm whether phosphorus atoms and tin atoms were detected therein. In all of Examples 11-11, insoluble material was produced, in which phosphorus and tin atoms were detected. In Comparative Examples 1 and 2, no compound including a phosphorus atom was contained, and therefore no insoluble material was produced in the initial evaluation. In Comparative Example 3, as in Examples 11 there, insoluble material was produced, in which phosphorus atoms and tin atoms were detected.
    (Young's modulus of the primary resin layer)
    The Young's modulus of the primary resin layer was measured by a pull-out modulus test at 23 ° C. A coating resin layer 16 of the optical fiber 10 was specifically cut with a razor to cut the coating resin layer 16, and the coating resin layer 16 was fixed (primary resin layer 14 and resin layer secondary 15) and the optical transmission medium 13 was removed. The stress of the primary resin layer 14 was determined from the amount of elastic deformation of the primary resin layer 14 before the optical transmission medium 13 a been torn off and the tearing force of the optical transmission medium 13.
    (Glass transition temperature (Tg))
    The determination of Tg was carried out as follows. The optical fiber 10 was first immersed in ethanol, and the coating resin layer 16 (the primary resin layer 14 and the secondary resin layer 15) was removed in a tubular form. The coating resin layer 16 was then dried under vacuum to remove the ethanol therefrom, and a measurement of dynamic viscoelasticity of the resultant was carried out under the conditions of a rate of temperature rise of 5 ° C. / min and a frequency of 11 Hz. We considered the temperature values of the two peak peaks of tan δ measured as Tg of the primary resin layer 14 and Tg of the secondary resin layer 15, and we considered the difference between the temperature values of the peaks as the difference between Tg of the primary resin layer 14 and Tg of the secondary resin layer 15.
    (Resistance to lateral pressure)
    The resistance to lateral pressure of the optical fiber was evaluated by a lateral pressure test. FIG. 2A is a diagram illustrating the configuration of a metal grid material 30 used in the side pressure test, and FIG. 2B is a partially enlarged view of the portion in FIG. 2A. As illustrated in FIG. 2A and 2B, the metal grid material 30 has a grid shape made up of several metal cables extending horizontally and orthogonally. The diameter φΐ of the orthogonal cable and the diameter φ2 of the horizontal cable are 50 μm, the pitch P between central lines of orthogonal cables and that between central lines of horizontal lines are 150 μm. The projection length LI of the orthogonal cable is 100 µm, and the projection length L2 of the horizontal cable is 100 µm.
    The lateral pressure test was carried out by determining the difference between the loss of light signal transmission at a wavelength of 1550 nm when the optical fiber was wound around a coil (body diameter: 280 mm) having the metal grid material 30 illustrated in FIG. 2A and 2B wrapped around the body and loss of transmission when the optical fiber was loosely formed into a bundle without being wrapped around the spool. The optical fiber was noted by A when the difference in transmission loss was less than 0.6 dB / km, by B when the difference was 0.6 dB / km or more and less than 1.0 dB / km, and by C when the difference was 1.0 dB / km or more; an assessment greater than or equal to B was considered acceptable.
    (Properties at low temperature after hygrothermal deterioration)
    In optical fibers deteriorated at 85 ° C and 85% RH for 180 days, the light signal transmission properties having a wavelength of 1550 nm were measured under two temperature conditions of 23 ° C and -40 ° C to determine the transmission loss at 23 ° C and that at -40 ° C. Optical fiber was noted by A if the difference in transmission loss obtained by subtracting the transmission loss at 23 ° C from the transmission loss at -40 ° C was less than 0 dB / km (the transmission loss at -40 ° C is lower), by B if the difference was 0 dB / km or more and less than 0.01 dB / km, and by C if the difference was 0.01 dB / km or more. An assessment greater than or equal to B was considered acceptable.
    (Thermal cycle test)
    In the optical fibers, which were subjected to 50 thermal cycles between -40 ° C. and 23 ° C. (maintenance at each temperature for 1 hour; transition time of 60 min), the properties of light signal transmission having been measured. a wavelength of 1,550 nm under two temperature conditions of 23 ° C and -40 ° C to determine the transmission loss at 23 ° C and that at -40 ° C. Optical fiber was noted by A if the difference in transmission loss obtained by subtracting the transmission loss at 23 ° C from the transmission loss at -40 ° C was less than 0 dB / km (the transmission loss at -40 ° C is lower), by B if the difference was 0 dB / km or more and less than 0.01 dB / km, and by C if the difference was 0.01 dB / km or more. An assessment greater than or equal to B was considered acceptable.
    [Table 1]
    Examples 1 2 3 4 5 6 7 Resin composition for primary resin layer Urethane A acrylate oligomer 70.5 - - - - - - Urethane B acrylate oligomer - 68.5 69.5 70.5 71 70.5 71 Isobornyl acrylate 10 10 10 10 10 10 10 N-vi nylca prolacta me 10 10 10 10 10 10 10 Nonylphenoxypolyethylene acrylateglycol 6 6 6 6 6 6 6 1,6-hexanediol diacrylate 1 3 2 1 0.5 1 1 Irgacure TPO 1 1 1 1 1 1 1 Diethylamine 0.5 0.5 0.5 0.5 0.5 0.5 - Mercaptopropyltrimethoxysilane 1 1 1 1 1 1 1 Resin composition for secondary resin layer Urethane C acrylate oligomer 60 60 60 60 60 60 60 Isobornyl acrylate 19 19 19 19 19 19 19 Trimethylolpropane triacrylate 20 20 20 20 20 20 20 Irgacure TPO 1 1 1 1 1 1 1 Difference in Tg (° C) 148 146 146 145 145 145 145 Treatmentthermal Temperature (° C) 40 40 40 40 40 85 40 Duration (h) 12 12 12 12 12 72 12 Compound containing phosphorusand tin Yes Yes Yes Yes Yes Yes Yes Young's modulus of the layerprimary resin (MPa) 0.50 0.28 0.23 0.11 0.07 0.11 0.11 Resistance to lateral pressure B B AT AT AT AT AT Low temperature properties after hygrothermal deterioration AT AT AT AT AT AT B Thermal cycle test AT AT AT AT AT AT AT
    [Table 2]
    Examples ExamplesComparatives 8 9 10 11 1 2 3 Resin composition for primary resin layer Urethane A acrylate oligomer - - - 70.5 - - 70 Urethane B acrylate oligomer 69.5 69.5 69.5 - 70 70 - Isobornyl acrylate 10 10 10 10 10 10 10 N-vinylcaprolactam 10 10 10 10 10 10 10 Nonylphenoxypolyethylene glycol acrylate 6 6 6 6 6 6 6 1,6-hexanediol diacrylate 1 1 1 1 1 1 2 Irgacure TPO - - - 1 - - 1 Irgacure 907 2 2 - - 2 - - Irgacure 184 - - 2 - - 3 - Diphenylphosphinic acid 0.5 - - - - - - Phenylphosphinic acid - 0.5 - - - - - Phenylphosphonic acid - - 0.5 - - - - Diethylamine - - - 0.5 - - - Mercaptopropyltrimethoxysilane 1 1 1 1 1 1 1 Resin composition for secondary resin layer Urethane C acrylate oligomer 60 60 60 50 60 60 60 Isobornyl acrylate 19 19 19 19 19 19 19 Trimethylolpropane triacrylate 20 20 20 20 20 20 20 Irgacure TPO 1 1 1 1 1 1 1 Difference in Tg (° C) 145 145 145 155 145 145 148 Treatmentthermal Temperature (° C) 40 40 40 40 40 40 40 Duration (h) 12 12 12 12 12 12 12 Compound containing phosphorus and tin Yes Yes Yes Yes no no Yes Young's modulus of the primary resin layer (MPa) 0.13 0.13 0.12 0.50 0.13 0.12 0.53 Resistance to lateral pressure AT AT AT B AT AT VS Low temperature properties after hygrothermal deterioration B B B AT VS VS B Thermal cycle test AT AT AT VS AT AT AT
    It was possible to verify that the optical fibers prepared in the examples exhibited resistance to lateral pressure and superior low temperature properties after hygrothermal deterioration. It was also possible to verify, when the difference between the glass transition temperature of the primary resin layer and the glass transition temperature of the secondary resin layer is 150 ° C or lower, that the properties at low temperature after cycles thermal are better.
    权利要求:
    Claims (8)
    [1" id="c-fr-0001]
    1. Optical fiber including:
    an optical transmission medium having a core and a sheath; a primary resin layer disposed in contact with the optical transmission medium to cover the optical transmission medium; and a secondary resin layer covering the primary resin layer, characterized in that the primary resin layer comprises a cured product of an ultraviolet light curable resin composition comprising an urethane (meth) acrylate oligomer, a monomer, and a photopolymerization initiator, and a compound containing phosphorus and tin as constituent atoms; and a Young's modulus of the primary resin layer is 0.5 MPa or less than 23 ° C.
    [2" id="c-fr-0002]
    2. Optical fiber according to claim 1, characterized in that the photopolymerization initiator comprises 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
    [3" id="c-fr-0003]
    3. Optical fiber according to claim 1 or 2, characterized in that the compound containing phosphorus and tin is a reaction product between at least one phosphorus compound chosen from the group consisting of a compound represented by the formula (la), a compound represented by the formula (lb), and a compound represented by the formula (le); and an organotin compound:
    Ο
    R 1 —P — OH
    R 2 (1 a)
    O
    R 3 - P - OH
    I
    OH d b)
    O
    R 4 -P-OH
    I
    H (1 c) where R 1 , R 2 , R 3 , and R 4 each independently represent an alkyl group, an alkenyl group, or an aryl group.
    [4" id="c-fr-0004]
    4. Optical fiber according to claim 3, characterized in that the phosphorus compound comprises at least one chosen from the group consisting of diphenylphosphinic acid, phenylphosphinic acid, and phenylphosphonic acid.
    [5" id="c-fr-0005]
    5. Optical fiber according to claim 3 or 4, characterized in that the organotin compound comprises at least one chosen from the group consisting of dibutyltin dilaurate and dibutyltin diacetate.
    [6" id="c-fr-0006]
    6. Optical fiber according to any one of claims 1 to 5, characterized in that a difference between a glass transition temperature of the primary resin layer and a glass transition temperature of the secondary resin layer is 150 ° C or lower.
    [7" id="c-fr-0007]
    7. Optical fiber according to any one of claims 1 to 6, characterized in that the Young's modulus of the primary resin layer is 0.25 MPa or less than 23 ° C.
    [8" id="c-fr-0008]
    8. Optical fiber according to any one of claims 1 to 7, characterized in that the resin composition curable by ultraviolet light further comprises an amine compound.
    ο
    2/2
    CM • 5>
    u.
    s • S »
    u.
    PROJECTION LENGTH OF
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3058410A1|2018-05-11|OPTICAL FIBER
    FR3070389A1|2019-03-01|COMPOSITION OF RESIN LAYERS SUITABLE FOR THE PRODUCTION OF OPTICAL FIBER IN HYGROTHERMIC MEDIA
    CN107614639A|2018-01-19|Adhesive sheet
    FR2992431A1|2013-12-27|OPTICAL FIBER COATED
    WO2017094302A1|2017-06-08|Optical fiber tape, method for manufacturing optical fiber tape, and ultraviolet curable resin composition used to form connection portions of intermittently fixed optical fiber tape
    FR3024873B1|2019-08-09|OPTICAL FIBER AND PROCESS FOR PRODUCING THE SAME
    CN108165190A|2018-06-15|Adherence composition, battery adhesive sheet and lithium ion battery
    CN1279217A|2001-01-10|Coated optical fiber with increased modulus and thermal strippability
    US20190064433A1|2019-02-28|Optical fiber
    FR3057074A1|2018-04-06|OPTICAL FIBER
    CN108165189A|2018-06-15|Adherence composition, battery adhesive sheet and lithium ion battery
    JPWO2020040223A1|2021-08-26|Optical fiber
    FR3058411A1|2018-05-11|OPTICAL FIBER
    CN1926458A|2007-03-07|Optical fibre comprising a strippable coating and method of stripping one such fibre
    JP6873056B2|2021-05-19|Recoating optical fiber and optical fiber recoating method
    RU2559519C2|2015-08-10|Optical fibre core
    FR3074922A1|2019-06-14|OPTICAL FIBER SPLICING STRUCTURE
    WO2019151453A1|2019-08-08|Uv-curable resin composition and optical fiber
    WO2020250594A1|2020-12-17|Resin composition, optical fiber, and method for manufacturing optical fiber
    JP2005338240A|2005-12-08|Active energy ray-curing resin composition and single coated optical fiber using same
    JP2003329860A|2003-11-19|Optical fiber
    CN114127605A|2022-03-01|Optical fiber ribbon and optical fiber cable
    JP2009175223A|2009-08-06|Optical fiber ribbon for equipment wiring and optical fiber ribbon for equipment wiring with connector
    JP2004004481A|2004-01-08|Glass optical fiber strand for fiber grating
    CN112789306A|2021-05-11|Resin composition and optical fiber
    同族专利:
    公开号 | 公开日
    CN108072931A|2018-05-25|
    RU2017138532A3|2021-03-19|
    RU2756680C2|2021-10-04|
    GB2558989A|2018-07-25|
    KR20180051420A|2018-05-16|
    FR3058410B1|2021-07-02|
    JP2018077303A|2018-05-17|
    GB201718395D0|2017-12-20|
    RU2017138532A|2019-05-07|
    US10048436B2|2018-08-14|
    US20180128970A1|2018-05-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4690501A|1985-07-08|1987-09-01|Desoto, Inc.|Ultraviolet curable optical glass fiber coatings from acrylate terminated, end-branched polyurethane polyurea oligomers|
    US5219896A|1989-09-06|1993-06-15|Stamicarbon, B.V.|Primary coatings for optical glass fibers including poly acrylates|
    CN1047104A|1990-04-17|1990-11-21|湖北省化学研究所|Ultraviolet rapid solidified tri compound single layer optical fiber paint|
    GB9121655D0|1991-10-11|1991-11-27|Ici Plc|Optical fibre coating|
    US5483612A|1994-10-17|1996-01-09|Corning Incorporated|Increased capacity optical waveguide|
    US6579618B1|1997-08-15|2003-06-17|Dsm N.V.|Coated optical fiber and radiation curable resin composition|
    JP2000302829A|1999-04-23|2000-10-31|Jsr Corp|Liquid curable resin composition and cured substance thereof|
    US6528553B1|1999-07-20|2003-03-04|Dsm N.V.|Radiation curable resin composition|
    US6470128B1|2001-03-30|2002-10-22|Alcatel|UV-curable coating composition for optical fiber for a fast cure and with improved adhesion to glass|
    US6849333B2|2001-05-18|2005-02-01|Corning Incorporated|Optical fiber with an improved primary coating composition|
    JP2004211057A|2002-12-16|2004-07-29|Jsr Corp|Radiation curing resin composition|
    JP4490798B2|2004-08-30|2010-06-30|Ｊｓｒ株式会社|Liquid curable resin composition for optical fiber up jacket|
    CN101268157A|2004-08-30|2008-09-17|帝斯曼知识产权资产管理有限公司|Curable liquid resin optical fiber up jacket composition|
    JP2006249264A|2005-03-11|2006-09-21|Jsr Corp|Liquid curable resin composition|
    WO2008076299A1|2006-12-14|2008-06-26|Dsm Ip Assets B.V.|D1363 bt radiation curable primary coatings on optical fiber|
    JP2010509643A|2006-12-14|2010-03-25|ディーエスエムアイピーアセッツビー．ブイ．|Radiation curable primary coating for D1365BJ optical fiber|
    US8406596B2|2009-08-12|2013-03-26|Corning Incorporated|Optical fiber containing multi-layered coating system|
    JP5493157B2|2009-10-09|2014-05-14|ディーエスエムアイピーアセッツビー．ブイ．|Method for formulating radiation curable supercoating for D1451 optical fiber|
    RU2604227C2|2009-10-09|2016-12-10|ДСМ Ай Пи ЭССЕТС Б.В.|D1452 gb radiation-curable coating for optical fibre|
    EP2559718B1|2010-04-14|2018-09-05|Mitsubishi Chemical Corporation|Polycarbonate diol, process for producing same, and polyurethane and actinic-energy-ray-curable polymer composition both formed using same|
    JP2012008221A|2010-06-22|2012-01-12|Hitachi Chem Co Ltd|Light waveguide clad resin composition, light waveguide clad resin film and light waveguide using the same|
    JP5027318B2|2011-02-04|2012-09-19|古河電気工業株式会社|Optical fiber core|
    CN104884499B|2012-12-26|2018-05-29|三菱化学株式会社|Polyurethane obtained from polycarbonate glycol and use polycarbonate glycol|
    JP6347397B2|2012-12-26|2018-06-27|三菱ケミカル株式会社|Polycarbonate diol and polyurethane using the same|
    CN104245617B|2013-04-12|2017-03-08|住友电气工业株式会社|Coated fiber|
    US9810838B2|2013-09-12|2017-11-07|Corning Incorporated|Fiber coatings with low young's modulus and high tear strength|
    US9488774B2|2014-04-01|2016-11-08|Corning Incorporated|Primary optical fiber coating composition containing non-radiation curable component|
    WO2017065274A1|2015-10-14|2017-04-20|住友電気工業株式会社|Optical fiber strand|JP2019045517A|2017-08-29|2019-03-22|住友電気工業株式会社|Optical fiber|
    WO2019212800A1|2018-04-30|2019-11-07|Corning Incorporated|Small outer diameter low attenuation optical fiber|
    US11181686B2|2018-04-30|2021-11-23|Corning Incorporated|Small diameter low attenuation optical fiber|
    CN112400127A|2018-04-30|2021-02-23|康宁股份有限公司|Small diameter low attenuation optical fiber|
    WO2021091746A1|2019-11-04|2021-05-14|Corning Incorporated|Fiber coatings with low pullout force|
    JPWO2019221248A1|2018-05-16|2021-07-15|住友電気工業株式会社|Optical fiber|
    EP3825290A1|2018-08-31|2021-05-26|Japan Fine Coatings Co., Ltd.|Radiation curable resin composition|
    WO2020255835A1|2019-06-19|2020-12-24|住友電気工業株式会社|Optical fiber|
    US11194107B2|2019-08-20|2021-12-07|Corning Incorporated|High-density FAUs and optical interconnection devices employing small diameter low attenuation optical fiber|
    WO2021091527A1|2019-11-04|2021-05-14|Corning Incorporated|Optical fibers with thin coatings|
    WO2021146077A1|2020-01-17|2021-07-22|Corning Incorporated|Reduced coating diameter chlorine-doped silica optical fibers with low loss and microbend sensitivity|
    法律状态:
    2018-10-24| PLFP| Fee payment|Year of fee payment: 2 |
    2019-09-30| PLFP| Fee payment|Year of fee payment: 3 |
    2019-10-18| PLSC| Search report ready|Effective date: 20191018 |
    2020-10-01| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-01| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2016218039A|JP2018077303A|2016-11-08|2016-11-08|Coated optical fiber|
    JP2016218039|2016-11-08|
    [返回顶部]