Resin composition, optical fiber, and method for manufacturing optical fiber

Abstract

This resin composition for primary cladding of an optical fiber comprises a photopolymerizable compound and a photoinitiator, wherein the photopolymerizable compound contains a urethane oligomer and an N-vinyl compound represented by formula (I). In the formula, R represents a C1-C5 alkyl group.

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition for a primary coating of an optical fiber, an optical fiber, and a method for manufacturing an optical fiber. This application claims priority to Japanese Application No. 2020-168366, filed on October 5, 2020, and incorporates by reference all of the contents of said Japanese application. [Background technology]

[0002] Generally, optical fibers are provided with a coating resin layer for protecting a glass fiber, which is an optical transmission medium. The coating resin layer is composed of, for example, two layers: a primary resin layer in contact with the glass fiber, and a secondary resin layer formed on the outer surface of the primary resin layer. As resin compositions for primary coatings of optical fibers, for example, resin compositions for primary resin layers described in Patent Documents 1 to 6 are known. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-197163 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-111674 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-136783 [Patent Document 4] Special Publication No. 2013-501125 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-114208 [Patent Document 6] Japanese Patent Application Laid-Open No. 2017-141125 Summary of the Invention

[0004] A resin composition for a primary coating of an optical fiber according to one embodiment of the present disclosure contains a photopolymerizable compound and a photopolymerization initiator, and the photopolymerizable compound includes a urethane oligomer and an N-vinyl compound represented by formula (I) described below.

[0005] An optical fiber according to one aspect of the present disclosure comprises a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and coats the glass fiber, and a secondary resin layer that coats the primary resin layer, wherein the primary resin layer contains a cured product of the resin composition.

[0006] A method for manufacturing an optical fiber according to one aspect of the present disclosure includes a coating step of coating the resin composition on the outer periphery of a glass fiber including a core and a cladding, and a curing step of curing the resin composition by irradiating it with ultraviolet light after the coating step. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] [Problem to be solved by this disclosure] The resin composition for the primary coating tends to have a slower curing rate than the resin composition for the secondary coating, and therefore, in order to improve the productivity of optical fibers, it is necessary to improve the curing rate of the resin composition for the primary coating. Furthermore, if the resin composition for the primary coating is not cured sufficiently, defects such as voids may occur in the formed primary resin layer, or peeling may occur between the glass fiber and the primary resin layer, which is likely to lead to an increase in transmission loss, particularly at low temperatures.

[0009] An object of the present disclosure is to provide a resin composition that has a fast curing rate and is capable of forming a resin layer suitable for a primary coating of an optical fiber, and an optical fiber that is excellent in productivity.

[0010] [Effects of this disclosure] According to the present disclosure, it is possible to provide a resin composition that has a fast curing rate and is capable of forming a resin layer suitable for a primary coating of an optical fiber, and an optical fiber that is excellent in productivity.

[0011] [Description of the embodiments of the present disclosure] First, the contents of the embodiments of the present disclosure will be listed and explained. A resin composition for a primary coating of an optical fiber according to one aspect of the present disclosure contains a photopolymerizable compound and a photopolymerization initiator, and the photopolymerizable compound contains a urethane oligomer and an N-vinyl compound represented by formula (I) described below.

[0012] Such a resin composition has a high curing rate and can suppress defects in the formed primary resin layer and peeling between the glass fiber and the primary resin layer. Therefore, a resin layer suitable for the primary coating of an optical fiber can be formed, thereby improving the productivity of the optical fiber. An optical fiber having a primary resin layer formed using such a resin composition can suppress an increase in transmission loss at low temperatures.

[0013] From the viewpoint of further improving the curing rate of the resin composition, the N-vinyl compound represented by formula (I) may contain N-vinylmethyloxazolidinone.

[0014] From the viewpoint of further improving the curing rate of the resin composition and appropriately adjusting the viscosity of the resin composition, the content of the N-vinyl compound represented by formula (I) may be 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition.

[0015] From the viewpoint of further improving the curing rate of the resin composition, the urethane oligomer may have at least one photopolymerizable group selected from the group consisting of a (meth)acrylamide group and a (meth)acryloyloxy group at at least one end of the urethane bond.

[0016] From the viewpoint of adjusting the Young's modulus of the primary resin layer, the photopolymerizable compound may further contain a (meth)acrylic acid ester.

[0017] From the viewpoint of adjusting the Young's modulus of the primary resin layer, the number average molecular weight of the urethane oligomer may be 5,000 or more and 40,000 or less.

[0018] An optical fiber according to one aspect of the present disclosure includes a glass fiber including a core and a cladding, a primary resin layer in contact with and coating the glass fiber, and a secondary resin layer coating the primary resin layer, the primary resin layer containing a cured product of the resin composition. Such an optical fiber can suppress defects in the primary resin layer and peeling between the glass fiber and the primary resin layer, thereby suppressing an increase in transmission loss at low temperatures and exhibiting excellent productivity.

[0019] An optical fiber manufacturing method according to an aspect of the present disclosure includes a coating step of coating the resin composition on the outer periphery of a glass fiber including a core and a cladding, and a curing step of curing the resin composition by irradiating it with ultraviolet light after the coating step. Such an optical fiber manufacturing method can produce optical fibers with excellent productivity.

[0020] [Details of the embodiments of the present disclosure] Specific examples of the resin composition and optical fiber according to the present embodiment will be described with reference to the drawings as necessary. The present disclosure is not limited to these examples, but is defined by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims. In the following description, the same elements in the drawings will be denoted by the same reference numerals, and redundant explanations will be omitted. In this specification, a (meth)acrylamide group refers to an acrylamide group or a corresponding methacrylamide group. The same applies to other similar expressions such as (meth)acrylate.

[0021] (Resin composition) The resin composition according to this embodiment contains a photopolymerizable compound and a photopolymerization initiator, and the photopolymerizable compound contains a urethane oligomer and an N-vinyl compound represented by formula (I) described below.

[0022] The urethane oligomer according to the present embodiment is not particularly limited as long as it is a urethane oligomer that can be used as a photopolymerizable compound in a resin composition for a primary coating. From the viewpoint of further improving the curing speed of the resin composition, the urethane oligomer preferably has at least one photopolymerizable group selected from the group consisting of a (meth)acrylamide group and a (meth)acryloyloxy group at at least one end of the urethane bond. From the viewpoint of adjusting the Young's modulus of the primary resin layer, the urethane oligomer may further have at least one group selected from the group consisting of a group based on a monohydric alcohol and a group based on an active hydrogen-containing silane compound at the end of the urethane bond.

[0023] Examples of the urethane oligomer include urethane oligomers having (meth)acrylamide groups at both ends of the urethane bond, urethane oligomers having (meth)acryloyloxy groups at both ends of the urethane bond, urethane oligomers having a (meth)acrylamide group at one end of the urethane bond and a (meth)acryloyloxy group at the other end, urethane oligomers having a (meth)acrylamide group or a (meth)acryloyloxy group at one end of the urethane bond and a group based on a monohydric alcohol or a group based on an active hydrogen-containing silane compound at the other end, and combinations thereof.

[0024] The urethane oligomer may be, for example, a reaction product of a polyol, a diisocyanate, one or more compounds selected from the group consisting of N-hydroxyalkyl(meth)acrylamides and hydroxyl group-containing (meth)acrylates, and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds. For example, a urethane oligomer having (meth)acrylamide groups at both ends of the urethane bond may be a reaction product of a polyol, a diisocyanate, and an N-hydroxyalkyl(meth)acrylamide. A urethane oligomer having (meth)acryloyloxy groups at both ends of the urethane bond may be a reaction product of a polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate.

[0025] Examples of polyols include polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, polybutadiene polyols, and bisphenol A-ethylene oxide addition diols. Examples of polyether polyols include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol. These polyols may be used alone or in combination of two or more. From the viewpoint of easily adjusting the Young's modulus and elongation at break of the primary resin layer, it is preferable to use at least one polyol selected from the group consisting of polypropylene glycol, polytetramethylene ether glycol, and polycarbonate polyol.

[0026] In order to obtain a Young's modulus suitable for the primary resin layer, the number average molecular weight (Mn) of the polyol is preferably 2,000 or more and 20,000 or less, more preferably 2,400 or more and 19,000 or less, and even more preferably 2,800 or more and 18,000 or less.

[0027] Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 1,5-naphthalene diisocyanate, norbornene diisocyanate, 1,5-pentamethylene diisocyanate, tetramethylxylylene diisocyanate, and trimethylhexamethylene diisocyanate. These diisocyanates may be used alone or in combination of two or more.

[0028] Examples of N-hydroxyalkyl(meth)acrylamides include N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and N,N-dimethylol(meth)acrylamide. These N-hydroxyalkyl(meth)acrylamides may be used alone or in combination of two or more. From the viewpoint of further improving the curing rate of the resin composition, it is preferable to use N-hydroxyethylacrylamide as the N-hydroxyalkyl(meth)acrylamide.

[0029] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-hydroxy-O-phenylphenolpropyl (meth)acrylate, 2-hydroxy-3-methacrylpropyl acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more. It is preferable to use at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate as the hydroxyl group-containing (meth)acrylate.

[0030] Examples of monohydric alcohols 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, and 3-methyl-2-butanol. These monohydric alcohols may be used alone or in combination of two or more. By introducing a group based on a monohydric alcohol to the end of the urethane bond, the urethane oligomer can reduce the proportion of terminal (meth)acrylamide groups and (meth)acryloyloxy groups, which are photopolymerizable groups, and thereby reduce the Young's modulus of the primary resin layer.

[0031] Examples of active hydrogen-containing silane compounds include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These active hydrogen-containing silane compounds may be used alone or in combination of two or more. By introducing a group based on the active hydrogen-containing silane compound into the terminal of the urethane bond, the urethane oligomer reduces the number of terminal (meth)acrylamide groups and (meth)acryloyloxy groups, which are photopolymerizable groups. This reduces the Young's modulus of the primary resin layer and improves the adhesion between the primary resin layer and the glass fiber.

[0032] Examples of methods for synthesizing urethane oligomers include a method of reacting a polyol with a diisocyanate, followed by reaction with one or more compounds selected from the group consisting of N-hydroxyalkyl (meth)acrylamides and hydroxyl group-containing (meth)acrylates (and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds); a method of reacting a diisocyanate with one or more compounds selected from the group consisting of N-hydroxyalkyl (meth)acrylamides and hydroxyl group-containing (meth)acrylates (and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds), followed by reaction with a polyol; and a method of simultaneously reacting a polyol, a diisocyanate, and one or more compounds selected from the group consisting of N-hydroxyalkyl (meth)acrylamides and hydroxyl group-containing (meth)acrylates (and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds).

[0033] When a bifunctional polyol is used, a preferred method is to react the hydroxyl group (OH) of the polyol with the isocyanate group (NCO) of the diisocyanate, followed by reaction with one or more compounds selected from the group consisting of N-hydroxyalkyl (meth)acrylamides and hydroxyl group-containing (meth)acrylates (and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds).When a trifunctional or higher polyol is used, a preferred method is to react the diisocyanate with one or more compounds selected from the group consisting of N-hydroxyalkyl (meth)acrylamides and hydroxyl group-containing (meth)acrylates (and, if necessary, one or more compounds selected from the group consisting of monohydric alcohols and active hydrogen-containing silane compounds), followed by reaction with the polyol.

[0034] The preparation of a urethane oligomer will be described below with a specific example, in which polypropylene glycol is used as the polyol, 2,4-tolylene diisocyanate as the diisocyanate, N-hydroxyethyl acrylamide as the N-hydroxyalkyl (meth)acrylamide, 2-hydroxyethyl acrylate as the hydroxyl group-containing (meth)acrylate, methanol as the monohydric alcohol, and 3-mercaptopropyltrimethoxysilane as the active hydrogen-containing silane compound.

[0035] First, polypropylene glycol and 2,4-tolylene diisocyanate are reacted to synthesize an NCO-terminated prepolymer. Next, the NCO-terminated prepolymer is reacted with N-hydroxyethyl acrylamide, 2-hydroxyethyl acrylate, methanol, and 3-mercaptopropyltrimethoxysilane to synthesize a urethane oligomer. The synthesized urethane oligomer can be represented as a mixture of the following formulas (1) to (7). Am-(UIUP)nUIU-Am (1) Am-(UIUP)nUIU-Ac (2) Ac-(UIUP)nUIU-Ac (3) Am-(UIUP)nUIUM (4) Am-(UIUP)nUIU-SC (5) Ac-(UIUP)nUIUM (6) Ac-(UIUP)nUIU-SC (7)

[0036] Here, Am represents a residue of N-hydroxyethyl acrylamide, Ac represents a residue of 2-hydroxyethyl acrylate, M represents a residue of methanol, SC represents a residue of 3-mercaptopropyltrimethoxysilane, U represents a (thio)urethane bond, I represents a residue of 2,4-tolylene diisocyanate, P represents a residue of polypropylene glycol, and n is an integer of 1 or more.

[0037] The reaction products during the synthesis of urethane oligomers may contain the following formulae (8) to (14) as by-products. Formulae (8) to (14) are called adducts, and function as a type of monomer. Am-UIU-Am (8) Am-UIU-Ac (9) Ac-UIU-Ac (10) Am-UIUM (11) Am-UIU-SC (12) Ac-UIUM (13) Ac-UIU-SC (14)

[0038] The reaction products during the synthesis of urethane oligomers may contain by-products represented by the following formulas (15) to (20). Since the formulas (15) to (20) do not have a photopolymerizable group, it is desirable that they are not produced. M-(UIUP)nUIUM (15) SC-(UIUP)nUIU-SC (16) M-(UIUP)nUIU-SC (17) MUIUM (18) MUIU-SC (19) SC-UIU-SC (20)

[0039] When preparing the urethane oligomer, the addition of methanol and 3-mercaptopropyltrimethoxysilane is optional. If methanol and 3-mercaptopropyltrimethoxysilane are not added, a mixture of formulas (1) to (3) is produced as the main component, and a mixture of formulas (8) to (10) is produced as a by-product.

[0040] The molar ratio of NCO to OH (NCO / OH) when reacting a polyol with a diisocyanate is preferably 1.1 to 4.0, more preferably 1.2 to 3.5, and even more preferably 1.4 to 3.0. The molar ratio of N-hydroxyalkyl(meth)acrylamide to NCO of the NCO-terminated prepolymer is preferably 0.1 to 1.15, more preferably 0.2 to 1.10. The molar ratio of hydroxyl-containing (meth)acrylate to NCO of the NCO-terminated prepolymer is preferably 0.1 to 1.15, more preferably 0.2 to 1.10. The molar ratio of the sum of N-hydroxyalkyl(meth)acrylamide, hydroxyl-containing (meth)acrylate, monohydric alcohol, and active hydrogen-containing silane compound to NCO of the NCO-terminated prepolymer is preferably 1.00 to 1.15, more preferably 1.03 to 1.10. The molar ratio of the total of the monohydric alcohol and the active hydrogen-containing silane compound to the NCO of the NCO-terminated prepolymer is preferably 0 or more and 0.5 or less.

[0041] Examples of catalysts used in synthesizing urethane oligomers include organotin compounds and amine compounds. Examples of organotin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(isooctyl mercaptoacetate), and dibutyltin oxide. From the viewpoint of easy availability and catalytic performance, it is preferable to use dibutyltin dilaurate or dibutyltin diacetate as the catalyst.

[0042] From the viewpoint of further enhancing the photocurability of the resin composition, the content of the urethane oligomer is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 90 parts by mass or less, even more preferably 30 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition.

[0043] From the viewpoint of obtaining a Young's modulus suitable for the primary resin layer, the Mn of the urethane oligomer is preferably 5,000 or more and 40,000 or less, more preferably 8,000 or more and 38,000 or less, and even more preferably 10,000 or more and 37,000 or less.

[0044] The N-vinyl compound represented by the following formula (I) according to this embodiment is a photopolymerizable monomer that does not have a urethane bond. By including the N-vinyl compound represented by formula (I), the resin composition according to this embodiment has a high curing rate and can suppress defects in the primary resin layer formed and peeling between the glass fiber and the primary resin layer. Therefore, the resin composition can be suitably used as a resin composition for primary coating of optical fiber, and can improve the productivity of optical fiber.

[0045] [ka]

[0046] In formula (I), R represents an alkyl group having 1 to 5 carbon atoms. From the viewpoint of further improving the curing rate of the resin composition, R is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0047] An example of the N-vinyl compound represented by formula (I) is N-vinylmethyloxazolidinone (manufactured by BASF, trade name: VMOX).

[0048] The content of the N-vinyl compound represented by formula (I) is preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total resin composition. When the content of the N-vinyl compound represented by formula (I) is 1 part by mass or more, based on 100 parts by mass of the total resin composition, the curing rate of the resin composition tends to be further improved, and when the content is 30 parts by mass or less, the viscosity of the resin composition tends to be appropriately adjusted. The content of the N-vinyl compound represented by formula (I) may be 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, or 8 parts by mass or more, or may be 25 parts by mass or less, 22 parts by mass or less, 20 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 13 parts by mass or less, or 11 parts by mass or less.

[0049] The photopolymerizable compound according to this embodiment may further contain a (meth)acrylic acid ester in order to adjust the Young's modulus of the primary resin layer. The photopolymerizable compound according to this embodiment may further contain a (meth)acrylamide compound in order to further improve the curing speed of the resin composition.

[0050] Examples of the (meth)acrylic acid ester include monofunctional (meth)acrylic acid esters and polyfunctional (meth)acrylic acid esters. Examples of monofunctional (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Examples of suitable acrylates include methylphenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenol polyethylene glycol (meth)acrylate (for example, trade name "Aronix M-113" manufactured by Toagosei Co., Ltd.), nonylphenoxypolyethylene glycol (meth)acrylate, isobornyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and ω-carboxy-polycaprolactone (meth)acrylate.

[0051] Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,20-eicosanediol di(meth)acrylate, isopentyldiol di(meth)acrylate, 3-ethyl-1,8-octanediol di(meth)acrylate, tricyclodecanol di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, bisphenol F epoxy bifunctional (meth)acrylic acid esters such as bisphenol A EO adduct di(meth)acrylate, bisphenol F EO adduct di(meth)acrylate, bisphenol A PO adduct di(meth)acrylate, and bisphenol F PO adduct di(meth)acrylate, and trade names "Epoxy Ester 40EM," "Epoxy Ester 70PA," "Epoxy Ester 200PA," and "Epoxy Ester 80MFA" manufactured by Kyoeisha Chemical Co., Ltd.;Trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytri(meth)acrylate, trimethylolpropane polyethoxypolypropoxytri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate trifunctional or higher (meth)acrylic acid esters such as tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol polypropoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanurate;

[0052] The (meth)acrylic acid ester may be used alone or in combination of two or more. The content of the (meth)acrylic acid ester is preferably 0 to 60 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin composition.

[0053] Examples of the (meth)acrylamide compound include dimethyl(meth)acrylamide, diethyl(meth)acrylamide, (meth)acryloylmorpholine, hydroxymethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, isopropyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, dimethylaminopropylacrylamide methyl chloride, diacetone acrylamide, (meth)acryloylpiperidine, (meth)acryloylpyrrolidine, (meth)acrylamide, N-hexyl(meth)acrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-methylolpropane(meth)acrylamide.

[0054] The (meth)acrylamide compound may be used alone or in combination of two or more. The content of the (meth)acrylamide compound is preferably 0 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total amount of the resin composition.

[0055] The photopolymerization initiator according to this embodiment can be appropriately selected from known radical photopolymerization initiators. Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins), 2,2-dimethoxy-2-phenylacetophenone (trade name: Omnirad 651, manufactured by IGM Resins), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Omnirad TPO, manufactured by IGM Resins), ethyl (2,4,6-trimethylbenzoyl)-phenylphosphinate (trade name: Omnirad TPO-L, manufactured by IGM Resins), 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone (trade name: Omnirad 369, manufactured by IGM Resins), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (trade name: Omnirad 379, manufactured by IGM Resins), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Omnirad TPO, manufactured by IGM Resins). Examples of suitable amines include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins).

[0056] The photopolymerization initiator may be used alone or in combination of two or more. From the viewpoint of achieving superior rapid curing properties of the resin composition, the photopolymerization initiator preferably contains 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0057] The content of the photopolymerization initiator is preferably 0.2 parts by mass or more and 5 parts by mass or less, more preferably 0.3 parts by mass or more and 4 parts by mass or less, and even more preferably 0.4 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition.

[0058] The resin composition according to this embodiment may further contain a silane coupling agent, a photoacid generator, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, and the like.

[0059] Examples of silane coupling agents include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, 3-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)- Examples of suitable silane coupling agents include γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, bis-[3-(triethoxysilyl)propyl]tetrasulfide, bis-[3-(triethoxysilyl)propyl]disulfide, γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide, and γ-trimethoxysilylpropylbenzothiazyltetrasulfide. These silane coupling agents may be used alone or in combination of two or more.

[0060] The content of the silane coupling agent is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, even more preferably 0.3 parts by mass or more and 4 parts by mass or less, and particularly preferably 0.4 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition.

[0061] As a photoacid generator, + B -Examples of the photoacid generator include sulfonium salts such as CPI-100P and 110P (manufactured by San-Apro Co., Ltd.), Omnicat 270 and Omnicat 290 (manufactured by IGM Resins), and iodonium salts such as Omnicat 250 (manufactured by IGM Resins), WPI-113, WPI-116, WPI-124, WPI-169 and WPI-170 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0062] From the viewpoint of coatability, the viscosity of the resin composition according to this embodiment at 25°C is preferably from 0.5 to 10 Pa·s, and more preferably from 1 to 9 Pa·s. The viscosity of the resin composition at 25°C can be measured using a Brookfield type viscometer ("Digital Viscometer DV-II" manufactured by Brookfield) with a spindle No. 18 and a rotation speed of 10 rpm.

[0063] (optical fiber) The optical fiber according to this embodiment includes a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and coats the glass fiber, and a secondary resin layer that coats the primary resin layer.

[0064] 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment. The optical fiber 10 includes a glass fiber 13 including a core 11 and a cladding 12, and a coating resin layer 16 including a primary resin layer 14 provided on the outer periphery of the glass fiber 13 and a secondary resin layer 15 coating the primary resin layer 14.

[0065] The cladding 12 surrounds the core 11. The core 11 and the cladding 12 mainly contain glass such as silica glass, and for example, the core 11 can be made of germanium-doped silica glass or pure silica glass, and the cladding 12 can be made of pure silica glass or fluorine-doped silica glass.

[0066] 1, for example, the outer diameter (D2) of the glass fiber 13 is about 100 μm to 125 μm, and the diameter (D1) of the core 11 constituting the glass fiber 13 is about 7 μm to 15 μm. The thickness of the coating resin layer 16 is usually about 22 μm to 70 μm. The thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 5 μm to 50 μm.

[0067] When the outer diameter of the glass fiber 13 is about 125 μm and the thickness of the coating resin layer 16 is 60 μm to 70 μm, the thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 10 μm to 50 μm, for example, the thickness of the primary resin layer 14 may be 35 μm and the thickness of the secondary resin layer 15 may be 25 μm. The outer diameter of the optical fiber 10 may be about 245 μm to 265 μm.

[0068] When the outer diameter of the glass fiber 13 is about 125 μm and the thickness of the coating resin layer 16 is 24 μm to 48 μm, the thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 8 μm to 38 μm, for example, the thickness of the primary resin layer 14 may be 25 μm and the thickness of the secondary resin layer 15 may be 10 μm. The outer diameter of the optical fiber 10 may be about 173 μm to 221 μm.

[0069] When the outer diameter of the glass fiber 13 is about 100 μm and the thickness of the coating resin layer 16 is 22 μm or more and 37 μm or less, the thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 5 μm to 32 μm, for example, the thickness of the primary resin layer 14 may be 25 μm and the thickness of the secondary resin layer 15 may be 10 μm. The outer diameter of the optical fiber 10 may be about 144 μm to 174 μm.

[0070] The primary resin layer 14 includes a cured product of the resin composition according to the present embodiment. The primary resin layer 14 can be obtained by curing the resin composition according to the present embodiment. Such a primary resin layer 14 can suppress defects and peeling from the glass fiber, thereby suppressing an increase in transmission loss of the optical fiber at low temperatures and enabling the production of an optical fiber with excellent productivity.

[0071] From the viewpoint of improving the microbending resistance of the optical fiber, the Young's modulus of the primary resin layer 14 is preferably 0.8 MPa or less, and more preferably 0.5 MPa or less, at 23° C.±2° C. If the Young's modulus of the primary resin layer exceeds 0.8 MPa, external forces are more likely to be transmitted to the glass fiber, and the transmission loss due to microbending tends to increase significantly.

[0072] The Young's modulus of the primary resin layer 14 can be measured by the Pullout Modulus (POM) method at 23°C. Two locations on the optical fiber are fixed with two chuck devices, and the coating resin layer (primary resin layer and secondary resin layer) between the two chuck devices is removed. Next, one chuck device is fixed, and the other chuck device is slowly moved in the opposite direction from the fixed chuck device. When the length of the portion of the optical fiber sandwiched between the moving chuck devices is L, the amount of chuck movement is Z, the outer diameter of the primary resin layer is Dp, the outer diameter of the glass fiber is Df, the Poisson's ratio of the primary resin layer is n, and the load during movement of the chuck device is W, the Young's modulus of the primary resin layer can be calculated using the following formula: Young's modulus (MPa) = ((1 + n)W / πLZ) × ln(Dp / Df)

[0073] The secondary resin layer 15 can be formed, for example, by curing a resin composition containing a photopolymerizable compound including a urethane oligomer, a photopolymerization initiator, and the like. The photopolymerizable compound and photopolymerization initiator are not particularly limited and can be selected from the photopolymerizable compounds and photopolymerization initiators described above. The resin composition forming the secondary resin layer has a different composition from the resin composition for the primary coating. The resin composition for the secondary coating can be prepared using conventionally known techniques. The urethane oligomer for the secondary resin layer may be, for example, a reaction product of a polyol, a diisocyanate, and an N-hydroxyalkyl(meth)acrylamide, or a reaction product of a polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate.

[0074] From the viewpoint of improving the microbending resistance of the optical fiber, the Young's modulus of the secondary resin layer 15 is preferably 800 MPa or more, more preferably 1000 MPa or more, and even more preferably 1200 MPa or more at 23° C.±2° C. There is no particular upper limit to the Young's modulus of the secondary resin layer 15, but from the viewpoint of imparting appropriate toughness to the secondary resin layer, it may be 3000 MPa or less, 2500 MPa or less, or 2000 MPa or less at 23° C.±2° C.

[0075] The Young's modulus of the secondary resin layer 15 can be measured by the following method. First, the optical fiber is immersed in a mixed solvent of acetone and ethanol, and only the coating resin layer is extracted in a cylindrical shape. At this time, the primary resin layer and the secondary resin layer are integrated, but the Young's modulus of the primary resin layer is 1 / 1000 to 1 / 10,000 of that of the secondary resin layer, so the Young's modulus of the primary resin layer can be ignored. Next, the solvent is removed from the coating resin layer by vacuum drying, and then a tensile test is performed at 23°C (tensile speed: 1 mm / min), and the Young's modulus can be determined using the secant equation with 2.5% strain.

[0076] From the viewpoint of improving the heat resistance of the secondary resin layer 15, the Tg of the secondary resin layer 15 is preferably 70° C. or higher, and more preferably 75° C. or higher. From the viewpoint of suppressing an increase in the transmission loss of the optical fiber at low temperatures, the Tg of the secondary resin layer 15 is preferably 105° C. or lower, and more preferably 95° C. or lower.

[0077] The method for manufacturing an optical fiber according to the present embodiment includes a coating step of coating the resin composition according to the present embodiment on the outer periphery of a glass fiber including a core and a cladding, and a curing step of curing the resin composition by irradiating it with ultraviolet light after the coating step. By using the resin composition according to the present embodiment as the resin composition for the primary coating, the method for manufacturing an optical fiber according to the present embodiment can suppress defects in the formed primary resin layer and peeling between the glass fiber and the primary resin layer, thereby enabling the manufacturing of optical fiber with excellent productivity. [Example]

[0078] The present disclosure will be described in more detail below by showing the results of evaluation tests using examples and comparative examples according to the present disclosure. Note that the present disclosure is not limited to these examples.

[0079] [Synthesis of urethane oligomers] (A-1) Polypropylene glycol (PPG3000, Sanyo Chemical Industries, Ltd., product name: Sannix PP-3000) with an Mn of 3000 and 2,4-tolylene diisocyanate (TDI) were blended to an NCO / OH molar ratio (NCO / OH) of 1.5 and reacted at 60°C for 1 hour to prepare an NCO-terminated prepolymer. Dibutyltin dilaurate was added as a catalyst at 200 ppm relative to the final total charge. Next, 2-hydroxyethyl acrylate (HEA) was added so that the molar ratio of OH to NCO of the NCO-terminated prepolymer (HEA / NCO) was 1.05, and the mixture was reacted at 60°C for 1 hour to obtain a urethane oligomer (A-1) with an Mn of 11300.

[0080] (A-2) A urethane oligomer (A-2) with an Mn of 11,200 was obtained in the same manner as in the synthesis of (A-1) above, except that methanol was added so that the molar ratio of OH in methanol to NCO in the NCO-terminated prepolymer (MeOH / NCO) was 0.4, and HEA was added so that the molar ratio of OH in HEA (HEA / NCO) was 0.65.

[0081] (A-3) A urethane oligomer (A-3) with an Mn of 11,400 was obtained in the same manner as in the synthesis of (A-1) above, except that HEA was added so that the molar ratio of OH of HEA to NCO of the NCO-terminated prepolymer (HEA / NCO) was 0.8, methanol was added so that the molar ratio of OH of methanol (MeOH / NCO) was 0.2, and 3-mercaptopropyltrimethoxysilane (MPTS) was added so that the molar ratio (MPTS / NCO) of MPTS was 0.05.

[0082] (A-4) A urethane oligomer (A-4) with an Mn of 11,400 was obtained in the same manner as in the synthesis of (A-1) above, except that N-hydroxyethylacrylamide (HEAA) was added so that the molar ratio of OH of HEAA to NCO of the NCO-terminated prepolymer (HEAA / NCO) was 1.05.

[0083] (A-5) A urethane oligomer (A-5) with an Mn of 36500 was obtained in the same manner as in the synthesis of (A-1) above, except that polypropylene glycol with an Mn of 18000 (manufactured by AGC Corporation, trade name: PREMINOL S4318F) and TDI were blended so that the NCO / OH ratio was 2.0.

[0084] (Z-1) Polypropylene glycol (PPG600, manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix PP-600) with Mn 600 and TDI were blended so that the molar ratio of NCO to OH (NCO / OH) was 2, and the mixture was reacted at 60°C for 1 hour to prepare an NCO-terminated prepolymer. Dibutyltin dilaurate was added as a catalyst at 200 ppm relative to the final total charge. Next, HEA was added so that the molar ratio of OH in HEA to NCO in the NCO-terminated prepolymer was 1.05, and the mixture was reacted at 60°C for 1 hour to obtain a urethane oligomer (Z-1) with Mn 2200.

[0085] The Mn of polyols is the value listed in the product catalog. The Mn of urethane oligomers was measured using a Waters ACQUITY APC RI system under the following conditions: sample concentration: 0.2% by mass in THF solution, injection volume: 20 μL, sample temperature: 15°C, mobile phase: THF, XT column for organic solvents: particle size 2.5 μm, pore size 450 Å, column inner diameter 4.6 × column length 150 mm + particle size 2.5 μm, pore size 125 Å, column inner diameter 4.6 × column length 150 mm + particle size 1.7 μm, pore size 45 Å, column inner diameter 4.6 × column length 150 mm, column temperature: 40°C, flow rate: 0.8 mL / min.

[0086] [Resin composition for primary coating] N-vinylmethyloxazolidinone was used as the N-vinyl compound represented by formula (I), acryloylmorpholine was used as the (meth)acrylamide compound, nonylphenol EO-modified acrylate (manufactured by Toagosei Co., Ltd., product name: Aronix M-113) was used as the (meth)acrylic acid ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO) was used as the photopolymerization initiator, and 3-acryloxypropyltrimethoxysilane was used as the silane coupling agent. The components were mixed in the amounts (parts by mass) shown in Table 1 below to obtain the primary coating resin compositions for each Example and Comparative Example.

[0087] [Resin composition for secondary coating] A resin composition for secondary coating was obtained by mixing 25 parts by mass of urethane oligomer (Z-1), 36 parts by mass of tripropylene glycol diacrylate (manufactured by Osaka Organic Chemical Industry Ltd., product name: Viscoat #310-HP), 37 parts by mass of bisphenol A epoxy di(meth)acrylate (manufactured by Osaka Organic Chemical Industry Ltd., product name: Viscoat #540), 1 part by mass of Omnirad TPO, and 1 part by mass of Omnirad 184.

[0088] [Fabrication of optical fiber] A resin composition for primary coating and a resin composition for secondary coating were each applied to the outer peripheral surface of a glass fiber 13 having a diameter of 125 μm. Next, each resin composition was cured by irradiating with ultraviolet light to form a coating resin layer 16 including a primary resin layer 14 and a secondary resin layer 15, thereby producing an optical fiber 10. The thickness of the primary resin layer 14 was 35 μm, and the thickness of the secondary resin layer 15 was 25 μm. The optical fibers were produced at drawing speeds of 2500 m / min, 3000 m / min, and 3500 m / min.

[0089] [Low temperature characteristics] The optical fiber was wound in one layer around a glass bobbin with a tension of 50g, and the transmission characteristics of signal light with a wavelength of 1550nm were measured at temperatures of 23°C and -40°C, and the transmission loss was calculated at 23°C and -40°C. If the difference in transmission loss, calculated by subtracting the transmission loss at 23°C from the transmission loss at -40°C, was less than 0dB / km, it was evaluated as "A," if it was between 0dB / km and 0.01dB / km, it was evaluated as "B," and if it was more than 0.01dB / km, it was evaluated as "C."

[0090] [Table 1] [Explanation of symbols]

[0091] 10 Optical Fiber 11 cores 12 Clad 13 Glass fiber 14 Primary resin layer 15 Secondary resin layer 16 Coating resin layer

Claims

1. Contains a photopolymerizable compound and a photopolymerization initiator, The photopolymerizable compound contains a urethane oligomer and an N-vinyl compound represented by the following formula (I): A resin composition for primary coating of an optical fiber, wherein the photopolymerizable compound further contains a (meth)acrylic acid ester. 【Chemistry 1】 (wherein R represents an alkyl group having 1 to 5 carbon atoms).

2. The resin composition according to claim 1, wherein the N-vinyl compound represented by formula (I) includes N-vinylmethyloxazolidinone.

3. The content of the N-vinyl compound represented by the formula (I) is 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition. The resin composition according to claim 1 or 2.

4. 4. The resin composition according to claim 1, wherein the urethane oligomer has at least one photopolymerizable group selected from the group consisting of a (meth)acrylamide group and a (meth)acryloyloxy group at at least one end of a urethane bond.

5. A composition comprising a photopolymerizable compound and a photopolymerization initiator, The photopolymerizable compound contains a urethane oligomer and an N-vinyl compound represented by the following formula (I): The resin composition for primary coating of an optical fiber, wherein the number average molecular weight of the urethane oligomer is 5,000 or more and 40,000 or less. 【Chemistry 2】 (wherein R represents an alkyl group having 1 to 5 carbon atoms).

6. The resin composition according to claim 5, wherein the N-vinyl compound represented by formula (I) includes N-vinylmethyloxazolidinone.

7. A resin composition described in claim 5 or claim 6, wherein the content of the N-vinyl compound represented by formula (I) is 1 part by mass or more and 30 parts by mass or less, based on a total amount of 100 parts by mass of the resin composition.

8. A resin composition described in any one of claims 5 to 7, wherein the urethane oligomer has at least one photopolymerizable group selected from the group consisting of a (meth)acrylamide group and a (meth)acryloyloxy group at at least one end of the urethane bond.

9. a glass fiber comprising a core and a cladding; a primary resin layer that contacts the glass fiber and covers the glass fiber; a secondary resin layer that covers the primary resin layer, An optical fiber, wherein the primary resin layer comprises a cured product of the resin composition according to claim 1 .

10. a coating step of coating the resin composition according to any one of claims 1 to 8 on an outer periphery of a glass fiber including a core and a clad; a curing step of curing the resin composition by irradiating it with ultraviolet light after the coating step.

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