JP2005283773A - Active energy ray-curable resin composition and optical fiber single-core wire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curing resin composition to be used as for outermost layer of a single optical coated fiber having three or more coating layers, and having excellent surface smoothness, storage stability and drawing property, and to provide a single optical coated fiber having excellent drawing property by using the above composition. <P>SOLUTION: The actinic ray-curing resin composition is used to form the outermost layer (Z) of an optical coated fiber having three or more coating layers in which the outermost layer (Z) in the coating layers has 70 to 500 μm film thickness, and the composition comprises a radical polymerizable compound and a silicone compound (D1) having 10,000 to 300,000 number average molecular weight and ≤20% modification rate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable resin composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and an optical fiber single-core wire using the same.

  Optical fiber cables have been put into practical use as large-capacity information transmission media, and broadband information communication networks using optical fiber cables are currently being constructed. Recently, in particular, since it is necessary to wire optical fibers directly to homes and office buildings, a technology is required to mount a large number of optical fibers as compactly as possible, and to make it easy to take out optical fiber cables and handle terminal processing. ing. The optical fiber core is obtained by applying a single layer coating or a primary coating layer and a secondary coating layer to a waveguide glass with a photocurable resin composition or the like, and a colored core colored with a colored ink thereon. There is a form of a line. Further, there is a form in which the waveguide part is a plastic optical fiber such as a fluorine-based plastic, or a plurality of optical fiber cores called an optical fiber unit arranged in a concentric circle shape or a planar shape and integrated and bundled with a curable resin.

  In recent years, since it is necessary to wire an optical fiber core to each home, a single optical fiber strand can be easily taken out from the optical fiber cable, and it does not adversely affect other optical fibers due to hot-wire branching, etc. Must be easy to handle and connect. For this reason, an optical fiber single fiber having three or more coating layers having an outer diameter exceeding 250 microns has been proposed (see Patent Document 1).

The following performance is required for an optical fiber single core wire having such three or more coating layers and easy handling and connection work and a coating layer used therefor.
(1) Sufficient mechanical characteristics that do not break during handling: Mechanical characteristics (2) Sufficient bending rigidity that is easy to handle: Bending rigidity (3) Transmission characteristics do not deteriorate due to handling: Transmission characteristics (4) Single core wires contact each other Even if there is no surface tack so that they can be easily separated, they slide on each other: surface slipperiness (5) There is little volatilization during or after manufacture and the atmosphere is not polluted: non-contamination (6) Connection work Occasionally, the outer layer can be easily removed from the inner layer below the inner layer without being broken by a stripper or the like into a long cylindrical shape: pullability is required.

  Among the above-mentioned problems, for the purpose of improving (4) and (5), the outermost layer resin composition having good surface slipperiness includes a composition containing a modified silicone having a specific slip resistance value. It is disclosed (see Patent Document 2). This technology contains a modified silicone compound having a molecular weight of 500 to 1,000,000 and a modification rate of 0 to 40%, and a modified silicone having a molecular weight of 900 to 100,000 and a modification rate of 40 to 95%. Describes an optical fiber coating resin composition having an initial slip resistance of 800 g or less, and an optical fiber and an optical fiber unit using a cured product of the composition as an outermost layer. However, in the related art, the pullability of (6) is not taken into consideration at all, and only the use as a tape material is disclosed in the examples.

  In addition, among the above problems, for the purpose of improving (4) and (6), an outer diameter of 0. 0 mm is provided on the outer side of an optical fiber having the same coating material and outer diameter as those used for the optical fiber tape. There has been disclosed a single-core coated optical fiber that is coated with an ultraviolet curable resin concentrically without gaps so as to be 6 mm or more (see Patent Document 3). Further, for the same purpose, a liquid curable resin containing a polydimethylsiloxane having a urethane bond and an acryloyl group, a polydimethylsiloxane having an organic group nonreactive with the urethane bond, and a polydimethylsiloxane not containing a urethane bond. A composition is disclosed (see Patent Document 4).

  However, the above-described conventional technology still has insufficient pullability. In particular, recently, an optical fiber single fiber having a small outer diameter has also been demanded. The smaller the outer diameter of the optical fiber, that is, the thinner the outermost layer, the worse the pullability. In particular, this tendency is remarkable in the above-described optical fiber single fiber having an outer diameter of less than 900 microns and further less than 600 microns. Therefore, the above characteristics in a small optical fiber with a small outer diameter having three or more coating layers, In particular, there has been a strong demand for a resin composition that satisfies the pullability.

JP-A-10-010380 JP 09-328632 A JP 08-062459 JP-A-10-287717

  Accordingly, an object of the present invention is to provide an active energy ray-curable resin composition used for the outermost layer of a single optical fiber having three or more coating layers, and has excellent surface slipperiness, storage stability, and pullability. It is providing the active energy ray-curable resin composition excellent in. Another object of the present invention is to provide a single-fiber optical fiber having excellent pullability using the same.

  As a result of intensive studies in view of such circumstances, the present inventors have found that the above problem can be solved by using an active energy ray resin composition containing a silicone compound having a specific molecular weight and a specific modification rate. The present invention has been reached.

  That is, the present invention comprises three or more coating layers, and the outermost layer (Z) of an optical fiber single-core wire whose outermost layer (outermost layer Z) has a thickness of 70 to 500 μm. ) Containing a radical polymerizable compound and a silicone compound (D1) having a number average molecular weight of 10,000 to 300,000 and a modification rate of 20% or less. An active energy ray-curable resin composition for optical fibers is provided.

  The present invention also provides an optical fiber comprising three or more coating layers, the outermost layer (outermost layer Z) of the coating layers having a thickness of 70 to 270 μm and an outer diameter of 350 to 800 μm. An active energy ray-curable resin composition for forming the outermost layer (Z) of a single core wire, which has a radical polymerizable compound, a number average molecular weight of 10,000 to 300,000, and a modification rate of 20% or less The present invention provides an active energy ray-curable resin composition for optical fibers, which contains a certain silicone compound (D1).

  The present invention also provides an optical fiber single-core wire having three or more coating layers, wherein the outermost layer (outermost layer Z) of the coating layers has a thickness of 70 to 270 μm. The outer layer (Z) is formed by a cured film of an active energy ray-curable resin composition containing a radical polymerizable compound and a silicone compound (D1) having a number average molecular weight of 10,000 to 300,000 and a modification rate of 20% or less. An optical fiber single fiber is provided.

  When the resin composition of the present invention is an optical fiber single-core wire having three or more coating layers and is used for the outermost layer of an optical fiber having a relatively small outer diameter and a thick outermost layer, excellent drawing The outermost layer can be easily removed from the inner layer below it into a long cylindrical shape without breaking with a stripper or the like during the optical fiber connection operation. At the same time, excellent surface smoothness and transmission characteristics can be obtained.

The present invention is described in detail below. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to derivatives of acrylic acid or methacrylic acid.
The active energy ray-curable resin composition of the present invention is cured by irradiation with energy rays such as radiation, electron beam, and ultraviolet rays, and is usually active energy rays such as vinyl group, (meth) acryl group, and maleimide group. It is a composition containing the organic compound which has a functional group which reacts with. The active energy ray-curable resin composition is cured to form an optical fiber coating layer.

Usually, an optical fiber is obtained by applying a single-layer coating or a primary coating layer and a secondary coating layer to a waveguide glass with a photocurable resin composition or the like, and this is called an optical fiber. Furthermore, there is a form of a colored core colored with colored ink on this. The optical fiber single-core wire having three or more coating layers of the present invention is, for example,
(1) A single-core optical fiber in which an ultraviolet curable colored ink layer is provided on a single-layer coated optical fiber, and an overcoat layer is provided as an outermost layer on the upper layer.
(2) An optical fiber single fiber in which an overcoat layer as an outermost layer is directly provided on an optical fiber having a primary coating layer and a secondary coating layer;
(3) An optical fiber single-core wire in which an ultraviolet curable colored ink layer is provided on an optical fiber having a primary coating layer and a secondary coating layer, and an overcoat layer is provided as an outermost layer on the upper layer. An optical fiber single core wire in which an overcoat layer is further provided on the optical fiber of (3),
Etc.

  The single-core optical fiber having three or more coating layers of the present invention is preferably basically composed of a cured film of a resin composition in which all the coating layers are cured with an active energy ray such as an ultraviolet curing type. The layer having the thickness of 70 to 500 μm (outermost layer Z) has easy pullability (easy pullability) at the interface with the underlying layer. The thickness of the outermost layer Z having good pullability needs to be as described above, and appropriate bending rigidity cannot be obtained when the thickness is 70 μm or less. In particular, when the outer diameter is 350 to 800 μm, 70 μm or more is required. Furthermore, the Young's modulus of the outermost layer Z is 100 to 2000 MPa, preferably 300 to 1500 MPa, and more preferably 500 to 1200 MPa. Within this range, appropriate bending rigidity and good pullability can be obtained. Further, the Tg of the outermost layer Z is preferably in the range of 20 to 180 ° C., preferably 50 to 160 ° C., more preferably 80 to 150 ° C., because appropriate bending rigidity and good pullability can be obtained. If the Tg of the outermost layer Z is low, the adhesion to the lower layer becomes strong, and if the Tg is too high or too low, the toughness of the coating layer is lost and the pullability is lowered. The resin composition of the present invention may contain a pigment or dye for identification.

  The number average molecular weight of the silicone compound (D1) used in the active energy ray-curable resin composition for an optical fiber of the present invention is 10,000 to 300,000, and the modification rate is 20% or less. The number average molecular weight is preferably 30,000 to 300,000, more preferably 50,000 to 200,000. Within this range, the drawability, surface slipperiness, and transmission characteristics are good. In particular, the drawability is good. Further, the modification rate is preferably 10% or less, and more preferably 5% or less. Among these, 0% is particularly preferable. If it is this range, drawability will become favorable.

Here, the modification rate of the modified silicone indicates the ratio of the molecular weight X of the modified silicone (D1) other than the polydimethylsiloxane skeleton to the molecular weight Y of the entire modified silicone (D1) and is represented by the following formula. , ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR can be determined by quantifying the number of moles of dimethylsiloxane, terminal methylsilane and the number of moles of modifying groups.
Denaturation rate = X / Y × 100 (%)
X: Molecular weight of the portion other than the polydimethylsiloxane skeleton in the modified silicone (D1) Y: Molecular weight of the entire modified silicone (D1)

Further, the modified silicone is one in which an organic group other than a methyl group is introduced into the terminal or side chain of polydimethylsiloxane (silicone) or both, and the introduced organic group includes an amino group, a hydroxyl group, a carboxyl group, (Meth) acryloyl group, glycidyl group, mercapto group, phenyl group, alkoxy group, alkyl group, fluorine-substituted alkyl group, fluorine-substituted alkoxy group, M-OR- (wherein, M represents a (meth) acryloyl group, R Represents an alkylene group), R ₁ — (OR ₂ ) _n — (wherein R ₁ represents an alkyl group, R ₂ represents an alkylene group, and n represents an integer of 2 or more.) a group represented by, R ₁ COOR ₂ - (. wherein, R ₁ represents an alkyl group, R ₂ is representative of the alkylene group) the groups represented by, or an amino group, a hydroxyl group, a carboxyl group, (meth) acryloyl groups , Glish And alkyl groups substituted with a zyl group or a mercapto group. In general, a long-chain group represented by R _1- (OR ₂ ) _n- , a group represented by R ₁ COOR _2- , an alkyl group, an alkoxy group, a fluorine-substituted alkyl group, and a fluorine-substituted alkoxy group It is preferable because it has good compatibility with the radical polymerizable compound and its cured product, and provides excellent surface slipperiness and pullability.

  These modified silicones are prepared by, for example, reacting a polydimethylsiloxane containing a predetermined amount of silicon-hydrogen bonds with a compound having an allyl group at the terminal by a known method, or polydimethylsiloxane having a terminal hydroxyl group, a polyisocyanate and a hydroxyl group. It is produced by a method such as reacting the containing compound by a known method.

  In the active energy ray-curable resin composition for an optical fiber of the present invention, the use of the silicone compound (D2) having a modification rate of more than 20% in combination with the modified silicone (D1) alone makes it easier to draw, transfer characteristics, Storage stability is good and preferable. The number average molecular weight of the modified silicone (D2) is preferably in the range of 900 to 300,000. When the number average molecular weight is 900 or more, sufficient surface slipperiness and pullability are obtained, and when the molecular weight is 300,000 or less, the compatibility with the modified silicone (D1), the radical polymerizable compound and the cured product thereof is good. . In particular, when the number average molecular weight is in the range of 2000 to 30000, the interface between the outermost layer Z and the layer immediately below is stable, and there is no increase in optical fiber transmission loss due to microbending, and an interface having sufficient drawability can be formed. preferable. Moreover, since the modification rate of the modified silicone (D2) is 20% or less, the compatibility with the radical polymerizable compound and its cured product is poor, and when it is 95% or more, sufficient surface slipperiness and pullability cannot be obtained. 25 to 95% is preferable. Among these, a modification rate of 30 to 95% is more preferable, and a range of 45 to 90% is particularly preferable.

  In addition, when the modified silicone (D2) is used alone, sufficient pullability cannot be obtained, but compatibility with both the modified silicone (D1) and the cured product of the radical polymerizable compound is good. The modified silicone (D1), which has a relatively poor compatibility with the cured product of the radical polymerizable compound, assists in the good dispersion in the cured film, and sufficiently exhibits the pullability of the modified silicone (D1). Has a function to express.

  Further, when the modified silicone (D1) and the silicone compound (D3) having a modification rate of 20% or less and a number average molecular weight of less than 10,000 are used in combination, the pullability and storage stability are improved. The modification rate of D3 is preferably 10% or less, and more preferably 5% or less. Among these, 0% is particularly preferable.

  When the modified silicone (D1) is used alone, it is preferable to use it in the range of 0.01 to 2% by mass with respect to the entire resin composition of the present invention because the storage stability is good. Moreover, when using together modified silicone (D1) and modified silicone (D2), it is preferable to contain 0.1-20 mass% in total with respect to the whole resin composition of this invention. If it is 0.1% by mass or less, excellent surface slipperiness and pullability cannot be obtained, and if it is 20% by mass or more, Young's modulus and curability are lowered. Further, the modified silicone (D1) is preferably used at a ratio of 1 to 200% by mass with respect to the modified silicone (D2). If it is 1% by mass or less, sufficient pullability cannot be obtained, and if it exceeds 200% by mass, the compatibility is deteriorated. The range of 10-100 mass% is still more preferable.

  In the active energy ray-curable resin composition for optical fibers of the present invention, a radical polymerizable compound is used in addition to the silicones. As the radical polymerizable compound, the following radical polymerizable oligomers and radical polymerizable monomers can be used.

  The radical polymerizable oligomer is, for example, a compound having a molecular weight of 300 to 30,000 having a polymerizable unsaturated group such as a vinyl group, an acryloyl group, or a methacryloyl group at the terminal, and usually urethane acrylate or epoxy acrylate is used.

  Urethane acrylate can be manufactured by the method generally used conventionally. That is, a method of synthesizing from a polyol (a1) and a polyisocyanate (a2) and a compound (a3) having a polymerizable unsaturated group and a hydroxyl group at a terminal, or a polymerizable unsaturated group and a hydroxyl group at a polyisocyanate (a2) and a terminal. And the like, and the like.

  Examples of the polyol (a1) include polyester polyols obtained by polycondensation of polybasic acids and polyhydric alcohols, polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, and ethylene oxide. , Alkylene oxides such as propylene oxide and butylene oxide, polymers of cyclic ethers such as tetrahydrofuran and alkyl-substituted tetrahydrofuran, or polyether polyols that are copolymers of two or more of these.

  As the polyisocyanate compound (a2), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated Xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6 , 11-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6 Hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate.

  Examples of the compound (a3) having a polymerizable unsaturated group and a hydroxyl group at the terminal include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri (meth) acrylate, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-1 -(Meth) acryloxy-3- (meth) acryloxypropane, glycerin di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly ε-caprolactone mono (me ) Acrylate, 4-hydroxybutyl (meth) acrylate, .epsilon.-caprolactone mono (meth) acrylate, various types of epoxy acrylate.

  Examples of the radical polymerizable monomer that can be used in the present invention include methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen phthalate, and β- (meth) acryloyl. Oxyethyl hydrogen succinate, nonylphenoxyethyl (meth) acrylate, nonylphenoxypolyoxyethylene (meth) acrylate, nonylphenoxypolyoxypropylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, β- (meth) acrylo Ruoxypropyl hydrogen phthalate, β- (meth) acryloyloxypropyl hydrogen succinate, butoxypolyethylene glycol (meth) acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) Acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2- Hydroxyethylphthalic acid, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-1- ( (Meth) acryloxy-3- (meth) acryloxypropane, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly ε-caprolactone mono (meth) acrylate, dialkylaminoethyl (meth) acrylate, glycidyl (meth) ) Acrylate, mono [2- (meth) acryloyloxyethyl] acid phosphate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4, 4,4-hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meta Monofunctional polymerizable monomers such as acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, N-vinylpyrrolidone, 2-vinylpyridine, morpholine (meth) acrylate, N-vinylcaprolactam Etc.

  Also, for example, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol Di (meth) acrylate, di (meth) acrylate of neopentyl glycol hydroxypivalate, di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of bisphenol A ) Acrylate, 2,2'-di (hydroxypropoxyphenyl) propane di (meth) acrylate, 2,2'-di (hydroxyethoxyphenyl) propane di (meth) acrylate, bisphenol F ethylene oxide adduct di ( (Meth) acrylate, di (meth) acrylate of propylene oxide adduct of bisphenol F, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 5] Bifunctional polymerizable monomers such as undecane diacrylate and 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3 dioxane diacrylate .

  Further, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane Tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, trimellitic acid tri (meth) acrylate, triallyl trimellit There are polyfunctional polymerizable monomers such as acid and triallyl isocyanurate.

  Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra ( (Meth) acrylate, trimethylolpropane ethylene oxide or propylene oxide adduct tri (meth) acrylate, pentaerythritol ethylene oxide or propylene oxide adduct tri (meth) acrylate, pentaerythritol ethylene oxide or propylene oxide adduct tetra (meta) ) Hexa (meta) of acrylate, dipentaerythritol ethylene oxide or propylene oxide adduct Multifunctional polymerizable monomers having more than two functions, such as acrylate, tri (meth) acrylate of tetramethylolmethane ethylene oxide or propylene oxide adduct, tetramethylolmethane ethylene oxide or propylene oxide adduct tetra (meth) acrylate are tough. Is preferable. Moreover, since the monofunctional polymerizable monomer toughness containing nitrogen, such as N-vinyl pyrrolidone, 2-vinyl pyridine, morpholine (meth) acrylate, N-vinyl caprolactam, N-vinyl carbazole, is raised, it is preferable. Furthermore, the combined use of a monofunctional polymerizable monomer containing nitrogen and a polyfunctional polymerizable monomer having more than two functions is particularly preferable because the toughness becomes higher.

  If necessary, a photopolymerization initiator may be added to the active energy ray-curable resin composition for optical fibers of the present invention for the purpose of curing with ultraviolet rays or visible rays. Examples of the photopolymerization initiator include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and benzophenone derivatives, benzoyl alkyl benzoate, bis (4-dialkylaminophenyl) ketone, Benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ethers, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholine Phenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole Etc.

Among these, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 3,6 -Bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, 2,2-dimethoxy-2-phenylacetophenone, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n -Two or more kinds of light weight selected from the group of octylcarbazole Using a mixture of initiators when fast-curing property is obtained, and more preferable.
In particular, when an initiator selected from the following group is used, there are few volatilized components at the time of drawing and after drawing, and the contamination is excellent.
(Group 1)
(1) 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
(3) Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (4) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (5) 3,6-bis (2-Methyl-2-morpholinopropionyl) -9-n-octylcarbazole (6) 2-hydroxy-2-methyl-1-phenyl-propan-1-one

  In addition to the above components, polymerization inhibitors such as hydroquinone and methoquinone, hindered phenol-based, sulfur-based antioxidants, hindered amine-based yellowing inhibitors, phosphite-based decolorizing agents, pigments, and the like are added. It doesn't matter.

  The above photopolymerization initiator is added to cure the active energy ray-curable resin composition for an optical fiber of the present invention with ultraviolet rays, and includes a radical polymerizable oligomer, a radical polymerizable silicone compound, and a photo-opening polymerization initiator. It is made to contain 0.01-10 mass% normally with respect to a total of 100 mass%. Especially, 0.05-5 mass% is especially preferable at the point from which high-speed curability becomes large.

Furthermore, the active energy ray-curable resin composition for optical fibers of the present invention preferably has the following physical properties.
Viscosity: The viscosity with a B-type viscometer at 25 ° C. is preferably in the range of 0.8 to 10 Pa · S. The viscosity is less than 0.8 Pa · S or 10 Pa.s. If it exceeds S, the outer diameter fluctuates and the resin runs out during unit molding at high speed, resulting in poor high-speed workability.
Coefficient of dynamic friction: The coefficient of friction between the surfaces of the cured product is preferably in the range of 0.05 to 0.15 because of excellent surface lubricity.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by this. In addition, all the parts in an example mean a mass part.

(Synthesis Example 1)
Synthesis of radically polymerizable oligomer (A-1) 348 parts (2 mol) of TDI (2,4-tolylene diisocyanate) was charged into a flask equipped with a stirring blade, and polypropylene glycol (number average molecular weight 2000) while stirring. 2000 parts (1 mole) was charged and the temperature was raised to 70 ° C. while paying attention to heat generation. The reaction was carried out at this temperature for 7 hours, and the NCO% was measured to be 3.58%. Subsequently, 232 parts (2 mol) of HEA (2-hydroxyethyl acrylate) was added, and the reaction was further carried out at this temperature for 7 hours. After confirming that the absorption of NCO disappeared in the infrared absorption spectrum, the radical polymerizable oligomer (A-1); number average molecular weight: 2580 was obtained as the radical polymerizable oligomer (A).

(Synthesis Example 2)
Synthesis of radical polymerizable oligomer (A-2) In a flask equipped with a stirring blade, 348 parts (2 moles) of TDI (2,4-tolylene diisocyanate) was charged, and 1000 parts of polypropylene glycol (1 mole, 1 mole, OH value = 112 KOH-mg / g), and the temperature was raised to 70 ° C. while paying attention to heat generation. The reaction was carried out at this temperature for 7 hours, and the NCO% was measured and found to be 3.57%. Subsequently, 232 parts (2 mol) of HEA (2-hydroxyethyl acrylate) was added, and the reaction was further carried out at this temperature for 7 hours. After confirming that the absorption of NCO disappeared in the infrared absorption spectrum, the radical polymerizable oligomer (A-2); number average molecular weight: 1584 was obtained as the radical polymerizable oligomer (A).

(Synthesis Example 3)
Synthesis of radical polymerizable oligomer (AH-1))
A flask equipped with a stirring blade was charged with 260 parts (2 moles) of 2-hydroxypropyl acrylate (molecular weight 130), and 174 parts (1 moles) of TDI (2,4-tolylene diisocyanate) was cautious of heat generation while stirring. While dropping, the temperature was raised to 70 ° C., and the reaction was carried out at this temperature for 7 hours. After confirming that the absorption of NCO disappeared in the infrared absorption spectrum, the radical polymerizable oligomer (A) was taken out. (AH-1); Number average molecular weight: 434 was obtained.

(Synthesis Example 4)
Synthesis of radically polymerizable oligomer (AH-2) In a flask equipped with a stirring blade, 348 parts (2 mol) of TDI (2,4-tolylene diisocyanate) was charged and 192 parts (1 mol) of tripropylene glycol while stirring. The molecular weight was 192), and the temperature was raised to 70 ° C. while paying attention to heat generation. The reaction was carried out at this temperature for 7 hours, and then 260 parts (2 mol) of 2-hydroxypropyl acrylate was added, and the reaction was further carried out at this temperature for 7 hours. After confirming that the absorption of NCO has disappeared in the infrared absorption spectrum, dilute it by adding 20% by weight of isobornyl acrylate, and take out urethane acrylate (AH-2) as the radical polymerizable oligomer (A); number average molecular weight : 800 was obtained.

(Synthesis Example 5)
Synthesis of radical polymerizable oligomer (AH-3))
A flask equipped with a stirring blade, a thermometer and a reflux condenser was charged with 222 parts of isophorone diisocyanate, heated to 70 ° C. with stirring, and 116 parts of hydroxyethyl acrylate was dropped over about 1 hour to obtain Intermediate-1. Got. Next, 144 parts of acrylic acid was added to 376 parts of a bisphenol A type epoxy resin (epoxy equivalent 188 g / eq) in a flask equipped with a stirring blade, a thermometer, and a reflux condenser, and reacted at 100 ° C. for 8 hours. 338 parts of Intermediate-1 was developed and reacted at 80 ° C. for 5 hours to obtain a radical polymerizable oligomer (AH-3).

(Synthesis Example 6)
In a reaction vessel equipped with a stirrer, 6.2 parts of 2,4-tolylene diisocyanate and α- [3- (2 ′, 3′-hydroxypropyloxy) propyl] -ω-trimethylsilyloxypolydimethylsiloxane having a hydroxyl group equivalent of 2500 89.6 parts and 0.02 part of 2,6-di-tert-butyl-p-cresol were charged. And they were ice-cooled until the liquid temperature became 10 degrees C or less, stirring these. When the liquid temperature became 10 ° C. or lower, 0.05 part of dibutyltin dilaurate was added, and the liquid temperature was controlled at 20 to 30 ° C. and 40 to 50 ° C., respectively, and stirred for 1 hour and 2 hours, respectively. Then, 4.2 parts of hydroxyethyl acrylate was added thereto, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 4 hours. When the residual isocyanate was 0.1% by weight or less, the reaction was terminated and S-8 was obtained. .

(Synthesis Example 7)
In a reaction vessel equipped with a stirrer, 5.3 parts of isophorone diisocyanate, 94.7 parts of α- [3- (2′-hydroxyethoxy) propyl] -ω-trimethylsilyloxypolydimethylsiloxane having a hydroxyl equivalent weight of 2,000 and polymerization inhibition The agent, 0.02 part of 2,6-di-t-butyl-p-cresol, was charged. Then, 0.08 part of dibutyltin dilaurate was added while stirring at room temperature. After stirring for 1 hour while controlling the liquid temperature at 20 to 40 ° C., stirring was continued for 4 hours at the liquid temperature of 50 to 60 ° C., and the reaction was completed when the residual isocyanate was 0.1 wt% or less. -9 was obtained.

(Preparation of photocurable resin composition)
Resin compositions were prepared according to Tables 1 and 2 using the compounds synthesized in the above synthesis examples and the following compounds. However, the silicone compound (S) was used after thoroughly mixing.

<Radically polymerizable monomer>
M-1: isobornyl acrylate M-2: N-vinyl-2-pyrrolidone M-3: N-vinyl-caprolactam M-4: tricyclodecane dimethanol diacrylate M-5: tripropylene glycol diacrylate M- 6: Triacrylate of trimethylolpropane ethylene oxide 3 mol adduct M-7: Diacrylate of ethylene oxide 4 mol adduct of bisphenol A

<Antioxidant>
R-1: 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10- Tetraoxaspiro [5,5] undecane

<Light stabilizer>
L-1: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate

<Photopolymerization initiator>
I-1: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide I-2: 1-hydroxycyclohexyl phenyl ketone I-3: 2-hydroxy-2-methyl-1-phenylpropan-1-one I-4 : 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

<Silicone compound>
S-1: Dimethylpolysiloxane having a number average molecular weight of 80,000 (modification rate: 0%)
S-2: Polydimethylsiloxane having a number average molecular weight of 100,000 (modification rate: 0%)
S-3: polydimethylsiloxane having a number average molecular weight of 200,000 (modification rate: 0%)
S-4: Phenyl-modified polydimethylsiloxane having a number average molecular weight of 100,000 (modification rate: 8%)
S-5: Phenyl-modified polydimethylsiloxane having a number average molecular weight of 100,000 (modification rate: 15%)
S-6: Pendant-type modified polydimethylsiloxane modified with ethylene oxide / propylene oxide copolymer (50/50 molar ratio) having a number average molecular weight of 22900 (modification rate: 73.8%)
S-7: Polydimethylsiloxane modified with polyethylene glycol having an acrylic group and an aryl group at the end of number average molecular weight 1484 (modification rate: 40.2%)
S-8: Pendant-type modified polydimethylsiloxane modified with ethylene oxide / propylene oxide copolymer (50/50 molar ratio) having a number average molecular weight of 10033 (modified rate: 70.1%)
S-9: Phenyl-modified polydimethylsiloxane having a number average molecular weight of 3000 (modification rate: 0%)
S-10: Polydimethylsiloxane having a number average molecular weight of 4000 (modification rate: 0%)
S-11: Phenyl-modified polydimethylsiloxane having a number average molecular weight of 100,000 (modification rate: 25%)
S-12: Synthesis Example 6 Number average molecular weight 5200 (modification rate 15.2%)
S-13: Synthesis Example 7 Number average molecular weight 4300 (modification rate 10.2%)

<Pigment base>
P-1: phthalocyanine blue having a maximum particle size of 2 μm and containing 20% by mass, dispersed in diacrylate of bisphenol A ethylene oxide 4 mol adduct.

(Preparation of cured coating film)
The active energy ray-curable resin composition for optical fibers prepared according to Tables 1 and 2 was applied to a glass plate, and irradiated with 0.5 J / cm ² of ultraviolet light in a nitrogen atmosphere using a metal halide lamp. A cured coating was obtained.

(Evaluation of cured coating)
Each cured coating film was evaluated by the following test method.

(Measurement method of Young's modulus of cured coating)
(1) Preparation method of cured coating film: The prepared active energy ray-curable resin composition for optical fiber is applied to a glass plate, and irradiated with ultraviolet rays of 0.5 J / cm ^{2 in} a nitrogen atmosphere using a metal halide lamp. A cured coating film having a thickness of 150 μm is obtained.
(2) Test piece shape: A cured coating film was punched out using a dumbbell cutter having the shape of a No. 2 test piece of JIS K 7113. A 2 cm square metal piece with a thickness of 1.2 mm was fixed to the front and back sides of the marked line with a cyanoacrylate adhesive to obtain a test piece.
(3) Measurement model: Tensile tester manufactured by Shimadzu Corporation, Autograph AGS-100G type (4) Tensile speed: 1 mm / min
(5) Measurement condition atmosphere: 23 ° C., 50% RH

(Measurement of tensile elongation at break and breaking strength of cured coatings)
(1) Preparation method of cured coating film: The prepared active energy ray-curable resin composition for optical fiber is applied to a glass plate, and irradiated with ultraviolet rays of 0.5 J / cm ^{2 in} a nitrogen atmosphere using a metal halide lamp. A cured coating film having a thickness of 150 μm is obtained.
(2) Test piece shape and method: A cured coating film was punched out using a dumbbell cutter having the shape of No. 2 test piece of JIS K 7113, and conformed to the method of JIS K 7113.
(3) Measurement model: Tensile tester manufactured by Shimadzu Corporation, Autograph AGS-100G type (4) Tensile speed: 50 mm / min
(5) Measurement condition atmosphere: 23 ° C., 50% RH

(Measurement of Tg glass transition point of cured coating)
(1) Preparation method of cured coating film: The prepared active energy ray-curable resin composition for optical fiber is applied to a glass plate, and irradiated with ultraviolet rays of 0.5 J / cm ^{2 in} a nitrogen atmosphere using a metal halide lamp. A cured coating film having a thickness of 150 μm is obtained.
(2) Test piece shape and method: A cured coating film was punched out using a dumbbell cutter having the shape of a No. 2 test piece of JIS K 7113, and conformed to the method of JIS K 7113.
(3) Measurement model: RSA-2 manufactured by Rheometrics
(4) Frequency: 3.5Hz
(5) Measurement condition atmosphere; temperature rising rate 3 ° C./min (6) The maximum value of tan δ was defined as Tg.

(Coefficient of friction)
The resin composition shown in Table 2 was applied to a glass plate having a thickness of 1.2 mm by a spinner, and irradiated with 100 mJ / cm ² of ultraviolet rays (wavelength 365 nm) in a mixed gas of 1% oxygen and 99% nitrogen to obtain a film thickness of about A cured coating film of 100 μm was obtained. This cured coating film was cut to a width of 15 mm, wound on a mandrel having a diameter of 25 mm and a weight of 68 g, placed on a flat cured coating film (12 cm × 12 cm) produced in the same manner, and slid horizontally at a speed of 150 mm / min. The average value after the slip resistance (g) at this time was stabilized was measured with a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100G). The measurement was performed four times, and the average value of the slip resistance (g) divided by the weight of the mandrel was taken as the dynamic friction coefficient. However, the measurement was performed in an atmosphere of 23 ° C. and 50% RH.

(Manufacture and pullability of overcoat type single core wire)
Manufactured by Dainippon Ink & Chemicals, Inc., GRANDIC FC 7224 as the primary, Dainippon Ink & Chemicals, Inc., GRANDIC FC 5241 (A) or FC3261 (B) as the secondary, manufactures a single mode optical fiber with an outer diameter of 245 μm. A colored core wire having an outer diameter of 255 μm colored with UV ink GRANDIC BLUE FC8018 (A) manufactured by Nippon Ink Chemical Co., Ltd. or Cablelite 751 BLUE (B) manufactured by DSM Co., Ltd. was coated with the composition shown in Table 1 in the dimensions shown in Table 1. The resulting overcoat type single core wire was pulled out with a hotstripper, the outermost layer was pulled out, a thing pulled out in a cylindrical shape over 5 to 8 cm was marked with ◯, and a thing pulled out more than 8 cm was marked with ◎.

(Transmission characteristics of overcoat type single core wire)
The overcoat type core wire was subjected to a heat cycle test at −40 to 85 ° C., and the loss increase in the 1.55 μm band was 0.1 dB / km or more. A value of 0.05 to 0.1 dB / km was taken as Δ.

(Bending rigidity of overcoat type single core wire)
The above-mentioned overcoat type single core wire is formed into a circular bundle having an outer diameter of about 15 cm with an outer diameter of about 20 turns, and the bundle is sandwiched between two smooth acrylic plates perpendicular to the circular surface. A thing held between the acrylic plates was marked with ◯.

(Evaluation results)
The evaluation results are shown in Tables 1 and 2.

Claims (10)

For forming the outermost layer (Z) of a single optical fiber having three or more coating layers, and the outermost layer (outermost layer Z) of the coating layers has a thickness of 70 to 500 μm An active energy ray-curable resin composition comprising a radically polymerizable compound and a silicone compound (D1) having a number average molecular weight of 10,000 to 300,000 and a modification rate of 20% or less. Active energy ray-curable resin composition for use. The outermost layer (outermost layer Z) of the coating layer includes three or more coating layers, and the outermost layer (outermost layer Z) has a thickness of 70 to 270 μm and the outer diameter is 350 to 800 μm. An active energy ray-curable resin composition for forming an outer layer (Z), a radical polymerizable compound, a silicone compound (D1) having a number average molecular weight of 10,000 to 300,000 and a modification rate of 20% or less An active energy ray-curable resin composition for optical fibers, comprising: 3. The active energy ray-curable resin composition for an optical fiber according to claim 1, wherein the silicone compound (D1) has a number average molecular weight of 30,000 to 300,000. The active energy ray-curable resin composition for an optical fiber according to claim 1, wherein the silicone compound (D1) has a modification rate of 10% or less. Furthermore, the active energy ray hardening-type resin composition for optical fibers in any one of Claim 1, 2, 3 or 4 containing the silicone compound (D2) in which a modification rate exceeds 20%. An optical fiber single-core wire having three or more coating layers, wherein the outermost layer (outermost layer Z) of the coating layers has a thickness of 70 to 500 μm, and the outermost layer (Z) is a radical It is formed by a cured film of an active energy ray-curable resin composition containing a polymerizable compound and a silicone compound (D1) having a number average molecular weight of 10,000 to 300,000 and a modification rate of 20% or less. Optical fiber single core wire. The optical fiber single fiber according to claim 6, wherein an outer diameter of the optical fiber single fiber is 350 to 800 µm. The number average molecular weight of the said silicone compound (D1) is 30000-300000. The optical fiber single core wire in any one of Claim 6 or 7. The optical fiber single fiber according to any one of claims 6, 7 and 8, wherein a modification rate of the silicone compound (D1) is 10% or less. The optical fiber single fiber according to any one of claims 6, 7, 8 and 9, wherein the active energy ray-curable resin composition further contains a silicone compound (D2) having a modification rate exceeding 20%.