JPH115944A - Ultraviolet-curing coating composition for single-core coated optical fiber, and single-core coated optical fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curing coating composition which is used for a single-core coated optical fiber and gives a cured film excellent in blocking resistance and slipperiness. SOLUTION: This composition is obtained by blending an ultraviolet-curing resin composition containing a (meth)acrylate oligomer (A), a reactive diluent (B) having polymerizable double bonds, a photopolymerization initiator (C) with spherical silicone gel particles (D) having a mean particle diameter of 0.1-5 μm and a fluorinated silicone surfactant (E) respectively in amounts of 0.05-5 pts.wt. and 0.01-5 pts.wt. based on 100 pts.wt. total of components A, B and C. It can be used not only as an outermost coating material for a single- core coated optical fiber but also as a tape-forming material, a secondary coating material and a colored coating material for optical fibers. Further, it can be used as a surface protective coating material for various base materials, without limitation to the use for optical fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for a single-core coated optical fiber such as a drawn wire, indoor / indoor wiring, etc., in which a cured film is excellent in slipperiness and blocking resistance and has good curability. The present invention relates to an ultraviolet-curable outermost layer coating composition for a single-core coated optical fiber and a single-core coated optical fiber.

[0002]

2. Description of the Related Art
Single-core coated optical fibers used for dropping to general households and for indoor / premises wiring are being studied.The outer diameter of single-core coated optical fibers is considered in terms of handling, lateral pressure characteristics, and connectivity with tape cores. Is required to be 0.7 mm or more (1995 IEICE General Conference). The single-core coated optical fiber studied at this time is:
Conventionally, an optical fiber having a coating outer diameter of 250 μm is further protectively coated with an ultraviolet curable resin, and the ultraviolet curable outermost layer coating material has a curable property capable of curing a thick film and color identification. Transparency is required. In addition, by increasing the diameter, the fiber core wires are easily adhered to each other, and when wound on a bobbin in a manufacturing process, a winding disorder occurs, and inconveniences such as a decrease in unwinding property when a cable is formed occur. Therefore, the outermost layer coating material is required to have good sliding properties and blocking resistance between the coating materials.

Conventionally, as a measure for improving the slipperiness and blocking resistance, a method of applying a powder such as talc or a silicone oil to the surface of a fiber after producing the fiber is used. There is a problem that oil contaminates the manufacturing site.

[0004] Japanese Patent Application Laid-Open No. 2-170867 discloses a method of adding inorganic particles such as silica or particles of an organic resin to a curable composition. However, inorganic particles such as silica have a problem of sedimentation in the composition over time due to their high specific gravity. In addition, in the case of organic resin particles, sufficient lubricity cannot be obtained when used alone, and it is necessary to increase the amount of particles to increase the lubricity and blocking resistance. As a result, the unevenness of the coating film surface obtained becomes larger, resulting in various problems such as an increase in transmission loss, a decrease in the strength of the optical fiber core wire, and furthermore, a decrease in transparency makes it difficult to color the dyed wire. .

Therefore, it is desired to develop a coating composition for an optical fiber which does not have the above problems.

The present invention has been made in view of the above circumstances, and provides an ultraviolet-curable coating composition for a single-core coated optical fiber and a single-core coated optical fiber that provide a cured film having excellent slipperiness and blocking resistance. The purpose is to:

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and have found that (A) a (meth) acrylate oligomer, and (B) a polymerizable double bond. The ultraviolet curable resin composition containing the reactive diluent having (A), (C) the photopolymerization initiator, and the total amount of the components (A), (B) and (C) is 100 parts by weight. (D) 0.05 to 5 parts by weight of spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm and (E) a fluorosilicone surfactant (for example, the following general formulas (1) and (2)
Or a siloxane structure in the molecule as shown in (3),
By mixing 0.01 to 5 parts by weight of a fluorosilicone-based surfactant having a polyether structure and a perfluoroalkyl group or a perfluoropolyether group, the cured product obtained is mixed with the spherical silicone gel particles and the fluorosilicone. By adding a small amount of a surfactant to the extent that the transparency required for the optical fiber coating material is not impaired, it has excellent slipperiness and blocking resistance. It was found that the transparency was good and the curability was good because the amount of the surfactant added was small. In this case, the spherical silicone gel particles are surface-treated with an organosilicon compound having a triorganosilyl group represented by the following general formula (4) or a siloxane diol represented by the following general formula (5) or (6). The present inventors have found that an ultraviolet-curable coating composition for a single-core coated optical fiber can be obtained, which gives a cured product having more excellent slipperiness and blocking resistance, and the present invention has been accomplished.

[0008]

Embedded image (Wherein, Rf ¹ is a perfluoroalkyl group having 4 to 10 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ¹ is a polyethylene glycol chain, a polypropylene glycol chain or a mixture thereof) R ¹ is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, k and m are each 0 or 1, and n is 1 to 3 It is an integer of 3.)

[0009]

Embedded image (Where Rf ² is a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ² is a polyethylene glycol chain, a polypropylene glycol chain or R ² is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, p and r are each 0 or 1, q is 1 or 2,
x is 2 or 3. )

[0010]

Embedded image (Where R ³ is a methyl group or a phenyl group, R ⁴ is a methyl group, a trimethylsiloxy group or a trifluoropropyl group, and a is 0, 1, 2, or 3.)

Accordingly, the present invention provides an ultraviolet-curable resin composition comprising (A) a (meth) acrylate oligomer, (B) a reactive diluent having a polymerizable double bond, and (C) a photopolymerization initiator. (D) 0.05 to 5 parts by weight of spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm, based on 100 parts by weight of the total of the components (A), (B) and (C); E) an ultraviolet-curable coating composition for a single-core coated optical fiber comprising 0.01 to 5 parts by weight of a fluorosilicone-based surfactant, and (D) spherical silicone gel particles comprising the general formula (4) UV curable coating compositions for single-core coated optical fibers surface-treated with an organosilicon compound having a triorganosilyl group represented by the following or a siloxane diol represented by the general formula (5) or (6), and compositions thereof With things Providing a single-core coated optical fiber was reversed.

Hereinafter, the present invention will be described in more detail. A: (Meth) acrylate oligomer As the (meth) acrylate oligomer which is the first component of the ultraviolet-curable coating composition for a single-core coated optical fiber of the present invention, a conventionally known ultraviolet ray containing a (meth) acrylate resin as a main component is used. What is usually used for a curable resin composition can be used, for example, an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, an ether (meth) acrylate oligomer, an ester (meth) acrylate oligomer, Polycarbonate (meth) acrylate oligomers and the like can be mentioned. The (meth) acrylate oligomer preferably has a number average molecular weight of usually 200 to 20,000.

[0013] The (meth) acrylate oligomer is
Reaction of compounds such as polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolak type epoxy resin, adduct of polyhydric alcohol and ε-caprolactone with (meth) acrylic acid Alternatively, it can be synthesized by urethane-forming a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.

The epoxy (meth) acrylate oligomer may be any reaction product of a compound having a glycidyl group and (meth) acrylic acid. Among them, a benzene ring, a naphthalene ring, a spiro ring, A reaction product of a compound having a cyclic structure such as cyclopentadiene or tricyclodecane and having a glycidyl group and (meth) acrylic acid is preferred because the cured product has a high Young's modulus.

In particular, among these, bisphenol A,
Bisphenols such as bisphenol S and bisphenol F and glycidyl ethers of phenols containing an aromatic ring such as phenolic resin are preferably used because they have a high Young's modulus and a reaction product of (meth) acrylic acid.

The urethane (meth) acrylate oligomer can be obtained by urethanizing a polyol or isocyanate compound shown below and a (meth) acrylate compound having a hydroxyl group.

Further, an ether (meth) acrylate oligomer, an ester (meth) acrylate oligomer, and a polycarbonate (meth) acrylate oligomer are obtained by reacting a polyol corresponding to each of the following examples with (meth) acrylic acid. be able to.

(Polyether polyol) Examples of the polyether polyol include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, a copolymer of propylene oxide and ethylene oxide, a copolymer of tetrahydrofuran and propylene oxide, and tetrahydrofuran. And propylene oxide; an ethylene oxide adduct of bisphenol A; a propylene oxide adduct of bisphenol A, and the like.

These commercial products include, for example, (1)
As polyethylene glycol, "PEG 600", "PEG 1000", "PEG
2000 ", and (2) Takeda Pharmaceutical Co., Ltd.'s" Takerac P-22 "as polyoxypropylene glycol,
"Bamboo rack P-21", "Bamboo rack P-23",
(3) As polytetramethylene ether glycol,
“PTG650” and “PTG85” manufactured by Hodogaya Chemical Co., Ltd.
0 "," PTG 1000 "," PTG 2000 ",
“PTG 4000”, (4) “ED-28” manufactured by Mitsui Toatsu Chemicals, and “Exenol 5” manufactured by Asahi Glass Co., Ltd. as copolymers of propylene oxide and ethylene oxide
10), (5) As a copolymer of tetrahydrofuran and propylene oxide, "PPTG" manufactured by Hodogaya Chemical Co., Ltd.
1000 "," PPTG 2000 "," PPTG 4
000 "and" Unisafe DCB-11 "manufactured by NOF Corporation
00, "Unisafe DCB-1800", (6) "Unisafe DC-1100" manufactured by NOF Corporation as a copolymer of tetrahydrofuran and ethylene oxide,
"Unisafe DC-1800", (7) "Uniol DA-400", "Uniol DA-400" manufactured by NOF Corporation as an ethylene oxide adduct of bisphenol A
700, (8) As a propylene oxide adduct of bisphenol A, "UNIOR DB" manufactured by NOF Corporation
-400 ".

(Polyester polyol) Examples of the polyester polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Reaction product of a diol compound such as neopentyl glycol and ε-caprolactone or β-methyl-δ-valerolactone; such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, and tetrahydrophthalic acid; Reaction product of a dibasic acid; the above diol compound, the above dibasic acid and ε-caprolactone or β
And 3-component reaction products with -methyl-δ-valerolactone.

(Polycarbonate polyol) Examples of the polycarbonate polyol include 1,6-hexanediol, 3-methyl-1,5-pentanediol,
Neopentyl glycol, 1,4-butanediol,
1,5-octanediol, 1,4-bis- (hydroxymethyl) cyclohexane, 2-methylpropanediol, dipropylene glycol, dibutylene glycol,
A diol compound such as bisphenol A, ethylene oxide 2 to 6 mol addition reaction product or a diol compound such as polyester diol which is an ε-caprolactone or β-methyl-δ-valerolactone addition reaction product with diol compound and dimethyl carbonate; A polycarbonate polyol obtained by a reaction with a short-chain dialkyl carbonate such as a dialkyl carbonate having about 1 to 4 carbon atoms such as diethyl carbonate is exemplified.

Further, ethylene oxide, propylene oxide, ε-
Polyester diol, which is a caprolactone or β-methyl-δ-valerolactone addition reaction product, can also be used.

As a commercially available polycarbonate polyol, "Desmophen 2020" manufactured by Sumitomo Bayer Ltd. is available.
E "," DN-980 "," D
N-981 "," DN-982 "," DN-983 "and the like.

(Polyisocyanate) Examples of the above-mentioned polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and the like. 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-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane Triisocyanate,
Trimethylhexamethylene diisocyanate or the like is used. Among these, a polyisocyanate having a cyclic structure is particularly preferable because a cured product having a high Young's modulus can be obtained.

B: Reactive Diluent Having a Polymerizable Double Bond In the present invention, a reactive diluent having a polymerizable double bond is blended for adjusting the viscosity of the composition. Examples of such a reactive diluent include compounds having a structure in which (meth) acrylic acid is bonded to a compound containing an amino group or a hydroxyl group by an esterification reaction and an amidation reaction. And a polyfunctional polymerizable diluent.

(Monofunctional polymerizable diluent) methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, phenoxyethyl (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, butoxy polyethylene 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-ethylhexyl (meth) acrylate, dicyclopentadiene (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate 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, polyε-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 (meth) acrylate, tricyclodecanyloxy Ethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, morpholine (meth) acrylate,
N, N'-dimethylacrylamide, N-vinylpyrrolidone, N-vinylpyridine, N-vinylcaprolactone and the like.

(Bifunctional polymerizable diluent) 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di (meth) acrylate, ethylene glycol di (meth) acrylate, tetra 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 bisphenol A ethylene oxide adduct ) Acrylate, propylene oxide adduct of bisphenol A di (meth) acrylate, 2,2'-di (hydroxypropoxyphenyl)
Di (meth) acrylate of propane, di (meth) acrylate of 2,2′-di (hydroxyethoxyphenyl) propane, di (meth) of tricyclodecane dimethylol
Acrylates, dicyclopentadiene di (meth) acrylate, pentanedi (meth) acrylate, tricyclodecane dimethatordiacrylate, and (meth) acrylic acid adducts of 2,2′-di (glycidyloxyphenyl) propane.

(Polyfunctional polymerizable diluent) trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) A) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tris (acryloxy) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (hydroxypropyl) isocyanate Nurate tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate and the like.

These diluents are generally used in an amount of 10 to 20 per 100 parts by weight of the (meth) acrylate oligomer (A).
It is preferable to use 0 parts by weight.

C: Photopolymerization Initiator As the photopolymerization initiator, known ones can be used. For example, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2 −
Benzophenone derivatives such as phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, alkyl benzoylbenzoate, Screw (4-
Dialkylaminophenyl) ketone, benzyl derivatives such as benzyl and benzyl methyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, xanthone, Thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Trimethylpentylphosphine oxide, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1
-(Morpholinophenyl) -butanone-1 and the like. These may be used alone or in combination of two or more.

Among these, 1-hydroxycyclohexylphenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1 or a mixture of two or more thereof is curable. Is particularly preferred because the

The amount of the photopolymerization initiator is 0.1 to 1 per 100 parts by weight of the (meth) acrylate oligomer (A).
0 parts by weight is preferred.

In the present invention, in addition to the above essential components, a tertiary amine such as triethylamine and triethanolamine, and a tertiary amine such as triphenylphosphine may be used, if necessary, in order to accelerate the photopolymerization reaction by the above photopolymerization initiator. An alkylphosphine-based photopolymerization accelerator, a thioether-based photopolymerization accelerator such as p-thiodiglycol, or the like may be added. The addition amount of these compounds is usually preferably in the range of 0.01 to 10 parts by weight per 100 parts by weight of the (meth) acrylate oligomer (A).

In the present invention, an ultraviolet-curable resin composition comprising (A) the (meth) acrylate oligomer, (B) a reactive diluent having a polymerizable double bond, and (C) a photopolymerization initiator. The product is mixed with spherical silicone gel particles having a specific particle size as the component (D) and a specific fluorosilicone-based surfactant as the component (E). in this case,
When the spherical silicone gel particles of the component (D) are subjected to a surface treatment with an organosilicon compound having a triorganosilyl group represented by the general formula (4) or a siloxane diol represented by the general formula (5) or (6). Slipperiness and blocking resistance are further improved. Hereinafter, this point will be described in more detail.

D: Spherical Silicone Gel Particles The spherical silicone gel particles used in the present invention are those represented by the following formula (7): RSiO _3/2 (7) (where R is a monovalent organic group). It is a so-called polyorganosilsesquioxane spherical particle having an organosiloxane unit as a main component and having a three-dimensional network structure formed by siloxane bonds. In the above formula, as an organic group (for example, the above R) bonded to a silicon atom, For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, alkyl group such as decyl group, cycloalkyl group such as cyclohexyl group, Alkenyl such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, etc. Group, a phenyl group, a tolyl group, a xylyl group,
Aryl groups such as naphthyl group, benzyl group, aralkyl groups such as phenylethyl group, and further a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, and bromine or cyano groups. An unsubstituted or substituted monovalent hydrocarbon having usually 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms not having an aliphatic unsaturated bond, such as a chloromethyl group, a chloropropyl group, a bromoethyl group, and a trifluoropropyl group. Groups are preferred. Of these, a lower alkyl group such as a methyl group is preferred from the viewpoints of availability of raw materials, ease of industrial production, and stability of silicone gel particles, but a vinyl group and a phenyl group are partly used. Group, 3,
It may contain a 3,3-trifluoropropyl group or the like. Unless the effects of the present invention are impaired, spherical modified silicone gel particles containing a substituent having another functional group such as an amino group or a (meth) acryl group as an organic group bonded to a silicon atom may be used. Can also.

The spherical silicone gel particles are polyorganosilsesquioxane particles having a monoorganosiloxane unit as a basic structural unit as described above.
This includes triorganosiloxy units (R ₃ SiO _1/2 units), diorganosiloxane units (R ₂ SiO _2/2 units), SiO _4/2 units, and the like as part of the constituent units. (Where R is as defined above). In addition,
The content of the monoorganosiloxane unit in the spherical silicone gel particles is preferably at least 50 mol%, particularly preferably at least 70 mol%.

Such spherical silicone gel particles can be prepared by a known method, for example, the following formula (8): RSiY ₃ (8) (wherein R has the same meaning as described above. Y is a halogen atom such as chlorine or bromine). Or an alkoxysilane having a hydrolyzable group or atom represented by the formula (1), wherein the compound is hydrolyzed in the presence of an acid or alkali catalyst, that is, a so-called sol-gel method. Can be. At this time, a hydrolyzable group represented by the formula: R ₃ SiY, R ₂ SiY ₂ , and SiY ₄ (where R and Y are as described above) together with an organosilane represented by the formula (8) in some cases. Alternatively, one or more of the organosilanes having atoms may be co-hydrolyzed.

As the spherical silicone gel particles in the present invention, the above-mentioned spherical silicone gel particles may be obtained by using an organosilicon compound having a triorganosilyl group represented by the following general formula (4) or the following general formula (5) or (6). It is preferable to use a surface-treated one using the indicated siloxane diol.

[0039]

Embedded image (Where R ³ is a methyl group or a phenyl group, R ⁴ is a methyl group, a trimethylsiloxy group or a trifluoropropyl group, and a is 0, 1, 2, or 3.)

In this case, by the surface treatment, the silanol group present on the surface of the spherical silicone gel particles becomes a triorganosilyl group represented by the above formula (4) or a siloxane residue represented by the following general formulas (5a) and (6a). It is presumed that the silanol group is blocked by the group and the silanol group is inactivated, thereby improving the slipperiness and blocking resistance of the obtained cured product.

[0041]

Embedded image (In the formula, R ⁴ and a are as described above.)

As the organosilicon compound having a triorganosilyl group represented by the above formula (4), for example, a compound represented by the formula (4)
a) an alkoxysilane, a silylamine of the formula (4b),
The silazane of the formula (4c) and the like can be mentioned, and among these treating agents, it is preferable to use silylamine or silazane having high treating ability.

[0043]

Embedded image (Wherein, R ³ is the same as described above. Each R ³ may be the same or different. R ⁵ has 1 to 4 carbon atoms.)
A monovalent hydrocarbon group such as an alkyl group or an alkenyl group;
R ⁶ and R ⁷ each represent a monovalent hydrocarbon group having 1 to 4 carbon atoms such as an alkyl group and an alkenyl group. )

Specific examples of the organosilicon compound containing a triorganosilyl group include the following compounds.

[0045]

Embedded image

The siloxane diols of the above formulas (5) and (6) can be produced by a known method.
In the case of the compound of formula (5), for example, 1,1,1,3,5
7,7,7-octamethyltetrasiloxane and 3,5-
Bis (trimethylsiloxy) -1,1,1,7,7,7
-Can be obtained by a method such as hydrolysis of hexamethyltetrasiloxane with a Pd / C catalyst.

In particular, the siloxane diol of the formula (6) can be obtained by the following known method.

[0048]

Embedded image

The surface treatment of the spherical silicone gel particles with the above-mentioned compound includes an organosilicon compound having a triorganosilyl group of the above formula (4), a siloxane diol of the above formula (5) or (6) and an untreated spherical silicone gel particle. After mixing and contacting the silicone gel particles in the reaction vessel, heat treatment can be easily performed. When the treatment agents are mixed and contacted, a method of mixing the treatment agents as they are or a method of mixing water and spherical silicone gel particles in advance and then mixing and contacting the treatment agents can be used.

The amount of the surface treating agent used is determined based on the specific surface area of the spherical silicone gel particles and the molecular occupation area of the treating agent, and is usually 0.05 to 10% by weight of the spherical silicone gel particles, particularly 0.1 to 5% by weight. % By weight is preferred.

The spherical silicone gel particles have an average particle size of 0.01 to 5 μm, preferably 0.1 to 5 μm, irrespective of the surface treatment, from the viewpoint of the slipperiness of the obtained cured product surface and the sedimentation of the particles. It needs to be 3 μm. If the average particle size is less than 0.01 μm, the desired blocking resistance and slipperiness cannot be obtained. If the average particle size exceeds 5 μm, the surface condition of the cured film deteriorates, and the particles tend to settle. Is generated.

The amount of the spherical silicone gel particles to be blended is usually (A) to (C), regardless of the presence or absence of surface treatment, in that the resulting cured film has better transparency and slipperiness.
0.05 to 5 based on 100 parts by weight of the total amount of the component (C)
Parts by weight, preferably 0.1 to 3 parts by weight. If the amount is less than 0.05 part by weight, a satisfactory effect cannot be obtained and 5
If the amount is more than 10 parts by weight, there arises a problem that transparency is lowered and spherical silicone gel particles are liable to coagulate and settle.

E: Fluorosilicone-Based Surfactant As the fluorosilicone-based surfactant of the component (E),
Any surfactant can be used as long as it has a siloxane structure, a polyether structure and a perfluoroalkyl group or a perfluoropolyether group in the molecule. Specifically, the following general formulas (1) and (2) ) Or (3)
Are used.

[0054]

Embedded image (Wherein, Rf ¹ is a perfluoroalkyl group having 4 to 10 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ¹ is a polyethylene glycol chain, a polypropylene glycol chain or a mixture thereof) R ¹ is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, k and m are each 0 or 1, and n is 1 to 3 It is an integer of 3.)

[0055]

Embedded image (Where Rf ² is a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ² is a polyethylene glycol chain, a polypropylene glycol chain or R ² is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, p and r are each 0 or 1, q is 1 or 2,
x is 2 or 3. )

Here, the degree of polymerization of the polyether groups of Q ¹ and Q ² may be usually determined in consideration of the balance with the hydrophobic fluorine-containing organic group Rf. When used, the degree of polymerization is preferably 3 to 2
0, more preferably 3 to 12.

When propylene glycol having a lower hydrophilicity than ethylene glycol is used as a homopolymer chain, a polymer chain having a relatively high degree of polymerization is preferable, and one having a polymerization degree of 100 to 200 is more preferable.

In the case of a copolymer chain of propylene glycol and ethylene glycol, the content of propylene glycol in the entire polyether group is usually from 0 to 0.
It is in the range of 50 mol%, preferably 2 to 10 mol%, and the degree of polymerization as a copolymer chain is preferably 5 to 200.

The fluorosilicone surfactants of the above formulas (1) and (2) can be prepared by the method described in JP-A-3-47190, and specific examples include the following compounds. it can.

[0060]

Embedded image

[0061]

Embedded image

The fluorosilicone surfactant represented by the above formula (3) can be produced by condensing a compound represented by the following general formula (9).

[0063]

Embedded image (Wherein, Z represents a hydrogen atom or a hydroxyl group, and Rf ² , Q ² ,
R ² , p, q, and r are as described above. )

In the above formula (9), if Z is a hydrogen atom, it is hydrolyzed and condensed in an aqueous alkali hydroxide solution, and if Z is a hydroxyl group, it is dehydrated and condensed in the presence of a catalyst. Compound (3) can be obtained. The compound of the above formula (9) has the following general formula (1)
0) and a polyether compound represented by the following general formula (11) can be obtained by performing a hydrosilylation reaction in the presence of a platinum-based catalyst.

[0065]

Embedded image (In the formula, Rf ² , Q ² , R ⁴ , p, q, and r are as described above.)

The compound represented by the above formula (10) can be produced, for example, by the method described in JP-A-3-197484.

Specific examples of such a fluorosilicone surfactant of the above formula (3) include the following compounds.

[0068]

Embedded image

[0069]

Embedded image

The above fluorosilicone surfactant is
One of these can be used alone, or two or more can be used as a mixture. The compounding amount is usually (A) to (A) in that transparency, smoothness and slipperiness of the obtained cured film are better. It is 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total of component (C). The amount is 0.01
If the amount is less than 5 parts by weight, a satisfactory compounding effect cannot be obtained. If the amount exceeds 5 parts by weight, transparency and smoothness deteriorate.

The ultraviolet-curable coating composition for a single-core coated optical fiber of the present invention contains, in addition to the above components, for example, an antioxidant,
Stabilizers such as ultraviolet absorbers, coloring pigments, fillers other than the component (D) surface-treated with the component (D) and the processing agent, surfactants other than the component (E), solvents and the like are used in the present invention. It can be added as needed as long as the purpose is not impaired.

The composition of the present invention can be prepared by blending the above-mentioned necessary components and kneading with a three-roll mill or the like. From 1,000 to 10,
The range is preferably 000 cp (25 ° C.).

The above composition is a conventional ultraviolet-curable composition
Cured by irradiating ultraviolet light in the same manner as in
The cured film obtained in this way is
30-15 desirable to protect the optical fiber from external forces
0kgf / mm^Two Can achieve a high Young's modulus
Wear.

The single coated optical fiber of the present invention is obtained by forming a cured film of the above coating composition over the optical fiber. In this case, the optical fiber has a diameter of 1
Those having a thickness of 00 to 1,000 μm, particularly 200 to 800 μm are preferably used. The thickness of the cured coating covering the optical fiber is 5 to 500 μm, particularly 10 to 30 μm.
The thickness is preferably 0 μm, and the obtained single-core coated optical fiber is suitably used for a draw-down wire, indoor / in-building wiring, and the like.

[0075]

The ultraviolet curable coating composition for a single-core coated optical fiber of the present invention provides a cured coating having excellent blocking resistance and slipperiness, and is used as an outermost coating material for a single-core coated optical fiber. Not only that, it can be applied as a tape material, a secondary coating material, and a coloring coating material for optical fibers. Further, the present invention can be used not only for optical fibers but also as a surface protective coating material for various substrates.

[0076]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight. (1) Synthesis of Spherical Silicone Gel Particles (Spherical Silicone Gel Particles-I, II, III) 3,660 g of water having a pH of 6.8 and 90 g of aqueous ammonia (concentration: 28%) were added to a 5-liter glass container and stirred. . 750 g of methyltrimethoxysilane was added dropwise to the obtained liquid mixture over 3 hours while maintaining the liquid temperature at 5 to 10 ° C under low-speed stirring in which the stirring blade was rotated at a rotation speed of 200 rpm. Furthermore, after stirring for 4 hours while maintaining the liquid temperature at 5 to 10 ° C,
The liquid temperature was heated to 40 to 50 ° C., and the mixture was stirred at that temperature for 1 hour. As a result, a silicone gel slurry was obtained. Next, the silicone gel slurry thus obtained was filtered under pressure to form a cake having a water content of about 30%.
It dried in the dryer of ° C. The obtained dried product was crushed by a jet mill. Observation of the obtained microparticles with an electron microscope revealed that the microparticles were spherical particles having a particle size of 1.6 to 2.0 μm, which had a large amount of active silanol groups on the surface. The product thus obtained is referred to as spherical silicone gel particles-I.

Next, the spherical silicone gel particles-I
Was mixed with 1.0 g of ion-exchanged water using a mixer, and heated at 60 ° C. for 24 hours. The treated mixture is cooled to room temperature and 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diol 4.0.
g was added and mixed, and allowed to stand at room temperature for 24 hours. In addition, 12
Heat treatment was carried out at 0 ° C. for 24 hours to obtain surface-treated spherical silicone gel particles-II.

Further, the same treatment as that of the spherical silicone gel particles-II was carried out except that 4.0 g of hexamethyldisilazane was used as a surface treating agent to obtain surface-treated spherical silicone gel particles-III.

(2) Synthesis of urethane acrylate oligomer [Synthesis Example 1] 2,4-tolylene diisocyanate 871
g, 540 g of tetramethylene ether glycol (number-average molecular weight: 3,000), 250 g of polyoxypropylene glycol (number-average molecular weight: 1,000), and 109 g of trioxypropylene glycol in a reaction vessel, and heated to 70 to 80 ° C. under a nitrogen atmosphere. For 3 hours. Next, after cooling the reaction mixture to 40 ° C., the inside of the reaction vessel was replaced with dry air, and 0.82 g of 2,6-di-tert-butylhydroxytoluene (BHT), 0.27 g of dibutyltin dilaurate, 947 g of ethyl acrylate was added and reacted at a temperature of 60 to 70 ° C. for 3 hours to obtain a polyurethane oligomer having a number average molecular weight of 700 (hereinafter simply referred to as oligomer A).

[Synthesis Example 2] In the same manner as in Synthesis Example 1, 2, 4
-696 g of tolylene diisocyanate, tetramethylene ether glycol (number average molecular weight 2,000) 1,3
BHT was added to the reaction product obtained from 00g and 140 g of polyoxypropylene glycol (number average molecular weight 400).
0.72 g, dibutyltin dilaurate 0.24 g, 2-
697 g of hydroxyethyl acrylate was added and reacted to obtain an oligomer B having a number average molecular weight of 1,000.

(3) Preparation of UV Curable Resin Composition For 70 parts of each oligomer obtained above, 10 parts of N-vinylpyrrolidone, 20 parts of isobornyl acrylate,
3 parts of 1-hydroxycyclohexyl phenyl ketone was mixed as a photopolymerization initiator to prepare a base composition. The viscosity at 25 ° C. of each base composition was 4,500 cp for the base composition A comprising the oligomer A, and 5,000 cp for the base composition B comprising the oligomer B.

Examples 1 to 7, Comparative Examples 1 to 4 Tables 1 and 2
The treated or untreated spherical silicone gel particles and the fluorosilicone-based surfactant were blended with the base composition so as to have the composition shown in Table 2, and the resulting mixture was kneaded twice using a three-roll mill. A cured film was prepared from the ultraviolet-curable coating composition thus obtained as described below, and the physical properties were evaluated. For comparison, a cured film was similarly prepared using spherical silica instead of spherical silicone gel particles, and the physical properties were evaluated. Table 1 shows the results.
Also described in 2.

The spherical silicas in Tables 1 and 2 are spherical silicas (Admafine SO-C5, manufactured by Admatech, Inc.).
The average particle diameter is 2 μm and the particle size distribution is 0.1 to 5 μm), and the surface is treated with octamethyltetrasiloxane-3,5-diol in the same manner as the spherical silicone gel particles-II.

[0084]Evaluation methods (1) Preparation of sample A UV curable coating composition having a thickness of about 200 μm was placed on a glass plate.
Apply to film thickness, 200mJ / cm^Two (Wavelength 350nm)
Was irradiated to obtain a cured film. (2) Blocking resistance The cured film cut into 5 cm x 5 cm is made of two glass sheets.
Place it on a plate, apply a load of 100 g and at 40 ° C for 24 hours
After standing, the degree of adhesion was evaluated according to the following criteria. ：: easily peeled off: closely adhered (3) slipperiness (dynamic friction coefficient) The cured film was kept at 25 ° C. and 50% relative humidity for 24 hours.
After adjustment, load 200g, table speed 150m
Cured under the conditions of m / min (according to ASTM D1894)
The dynamic friction coefficient between the films was measured. (4) Measurement of Young's modulus (elastic modulus) The cured film is kept at 25 ° C. and 50% relative humidity for 24 hours.
After adjustment, 25 mm between marking lines, pulling speed 1 mm / m
The sample was pulled 2.5% under the conditions of "in" and the elastic modulus was measured. (5) Sedimentation The ultraviolet-curable coating composition before curing is left at 25 ° C. for 3 months.
After that, the sedimentation state of the particles was visually observed. ：: No separation (sedimentation) ×: Separation (sedimentation) present (6) Transparency A cured film having a thickness of 200 μm was prepared, and the film was thinned.
The other side of the film can be seen through when viewed through the eyes
The evaluation was based on whether or not it was possible. ○: Transparent ×: Transparent

[0085]

[Table 1]

[0086]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 75/16 C08L 75/16 (72) Inventor Mitsuhiro Nishimura 2-17-85 Jusanhoncho, Yodogawa-ku, Osaka-shi, Osaka Takeda Pharmaceutical Inside the Chemicals Company of Kogyo Co., Ltd. (72) Inventor Setsu Uemura 2-17-85 Jusanhoncho, Yodogawa-ku, Osaka, Osaka Prefecture Inside of the Chemicals Company Takeda Pharmaceutical Co., Ltd. (72) Akira Yamamoto Usui, Gunma Prefecture 1-10, Hitomi, Matsuida-cho, Guni, Japan Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Masatoshi Asano 1-10, Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture, Japan Silicone Electronic Materials Technology Laboratory (72) Inventor Hiromasa Yamaguchi 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Shin-Etsu Chemical Co., Ltd. In Materials Technology Laboratory (72) inventor Shohei Kosakai Gunma Prefecture Usui District Matsuida Oaza people viewed the first address 10 Shin-Etsu Chemical Co., Ltd. silicone electronic materials technology within the Institute

Claims (4)

[Claims] 1. An ultraviolet-curable resin composition comprising (A) a (meth) acrylate oligomer, (B) a reactive diluent having a polymerizable double bond, and (C) a photopolymerization initiator. (D) 0.05 to 5 parts by weight of spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm, and (E) fluorine based on 100 parts by weight of the total amount of the components (B) and (C). An ultraviolet-curable coating composition for a single-core coated optical fiber, comprising 0.01 to 5 parts by weight of a silicone surfactant. 2. The ultraviolet curing for single-core coated optical fiber according to claim 1, wherein the component (E) is a fluorosilicone-based surfactant represented by the following general formula (1), (2) or (3). Mold coating composition. Embedded image (Wherein, Rf ¹ is a perfluoroalkyl group having 4 to 10 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ¹ is a polyethylene glycol chain, a polypropylene glycol chain or a mixture thereof) R ¹ is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, k and m are each 0 or 1, and n is 1 to 3 It is an integer of 3.) (Where Rf ² is a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, Q ² is a polyethylene glycol chain, a polypropylene glycol chain or R ² is a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 3 carbon atoms, p and r are each 0 or 1, q is 1 or 2,
x is 2 or 3. ) 3. The spherical silicone gel particles according to claim 1, wherein the organosilicon compound having a triorganosilyl group represented by the following general formula (4) or a siloxane diol represented by the following general formula (5) or (6): The ultraviolet-curable coating composition for a single-core coated optical fiber according to claim 1, which has been surface-treated. Embedded image (Where R ³ is a methyl group or a phenyl group, R ⁴ is a methyl group, a trimethylsiloxy group or a trifluoropropyl group, and a is 0, 1, 2, or 3.) 4. A single-core coated optical fiber coated with a cured product of the ultraviolet-curable coating composition according to claim 1, 2 or 3.