JPH1077421A - UV-curable optical fiber tape material composition and tape-type core wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curable optical fiber tape material composition in which a cured film has excellent blocking resistance and good sliding properties between the films. (A) (meth) acrylate oligomer, (B) a reactive diluent having a polymerizable double bond,
(C) The total amount of the components (A), (B) and (C) is 1 in the ultraviolet curable resin composition containing a photopolymerization initiator.
(D) spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm and surface-treated with an organosilicon compound having a triorganosilyl group or siloxane diol, based on 00 parts by weight of 0.05 to 5 parts by weight (E) 0.01 to 5 parts by weight of a fluorosilicone surfactant is blended.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable optical fiber tape material composition and a tape-type core wire which provide a cured film having excellent blocking resistance and good slipperiness between the films.

[0002]

2. Description of the Related Art
A representative example of the most mass-produced optical fiber core is a tape-type core. In this method, several coated fibers are formed by applying a soft urethane-based acrylate primary coating having a small Young's modulus temperature dependency around a quartz fiber, and then applying a hard urethane-based acrylate secondary coating having a high Young's modulus around the silica fiber. And the entire outer periphery thereof is cured with a urethane-based acrylate-based ultraviolet-curable tape-forming material, and is a tape-shaped (plate-shaped) one (ribbon structure).

[0003] However, these tape-type core wires are produced in a manufacturing process so as to be wound on a bobbin, and are superposed. At this time, since the tape core wire is plate-shaped, the superposed area is large. That is, so-called blocking, in which the tape cores are stuck together, is likely to occur. in this case,
If the blocking property is high, there are the following problems. That is, the optical fiber cable constituted by these tape cores has a laminated structure in which the tape cores are overlapped with each other. In such a structure, when the cable is bent or a temperature change occurs, stress is applied to the core wires in the longitudinal direction, but if the core wires are not stuck together and free from movement, stress concentrates locally. This causes a problem that transmission characteristics are adversely affected. For this reason, the tape material is required to have good blocking resistance and slipperiness.

For this reason, in the past, a method of applying talc or silicone oil to the surface of a tape core wire after manufacturing it in order to improve blocking resistance has been carried out. There is a problem that it adheres to the production site and contaminates the manufacturing site, which is hardly practical.

[0005] 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. Increasing the amount increases the unevenness of the coating film surface, resulting in various problems, such as an increase in transmission loss, a decrease in the strength of the tape core wire, and a decrease in transparency, which makes it difficult to color the dyed wire.

Therefore, development of a tape material composition for an optical fiber which does not have the above problems is desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a UV-curable optical fiber tape material composition and a tape-type core wire which provide a cured film having excellent blocking resistance and slipperiness. And

[0008]

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 (C) the photopolymerization initiator and the total amount of the components (A), (B) and (C) was 100 parts by weight, D) Silanol groups present on the surface after being surface-treated using an organosilicon compound having a triorganosilyl group represented by the following general formula (1) or a siloxane diol represented by the following general formula (2) or (3) Is blended with spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm and a fluorosilicone-based surfactant represented by the following general formula (4), (5) or (6). By using UV light It has been found that a UV-curable optical fiber tape material composition that gives a cured film having excellent transparency and excellent slipperiness and anti-blocking properties can be obtained by being easily cured, thereby leading to the present invention. Was.

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. And (D) an organosilicon compound having a triorganosilyl group represented by the following general formula (1) or 100 parts by weight based on the total amount of the components (A), (B) and (C), or 0.05 to 5 parts by weight of spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm and surface-treated with the siloxane diol represented by the general formula (2) or (3). ), A UV-curable optical fiber tape material composition comprising 0.01 to 5 parts by weight of a fluorosilicone-based surfactant represented by (5) or (6), and this composition To irradiate ultraviolet rays Ri obtained to provide a tape type core wire coated with a cured product.

[0010]

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

[0011]

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 ³ 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.)

[0012]

Embedded image(However, in the formula, Rf^TwoIs perfluoro with 4 to 14 carbon atoms
Peralkyl group having 5 to 14 carbon atoms
Reether group, Q^Two Is polyethylene glycol chain, poly
Divalent of propylene glycol chains or both
A polyether group, R^FourIs hydrogen atom, allyl group, carbon atom
Alkyl group having 1 to 4 carbon atoms or acyl having 2 to 3 carbon atoms
P and r are each 0 or 1, q is 1 or 2,
x is 2 or 3. )

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 ray-curable optical fiber tape material composition of the present invention, a conventionally known ultraviolet ray-curable type mainly containing a (meth) acrylate resin as a main component. Those commonly used in resin compositions can be used. For example, epoxy-based (meth) acrylate oligomer, urethane-based (meth) acrylate oligomer, ether-based (meth) acrylate oligomer, ester-based (meth) acrylate oligomer, and polycarbonate-based (Meth) acrylate oligomers and the like. The (meth) acrylate oligomer preferably has a number average molecular weight of usually 200 to 20,000.

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.

Examples of the epoxy (meth) acrylate oligomer include 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 with (meth) acrylic acid is preferable because the cured product has a high Young's modulus.

Further, among these, bisphenol A,
Reaction products of glycidyl ethers of bisphenols such as bisphenol S and bisphenol F and phenols containing an aromatic ring such as a phenol resin and (meth) acrylic acid are preferred because of their high Young's modulus.

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

Further, ether (meth) acrylate oligomers, ester (meth) acrylate oligomers, and polycarbonate (meth) acrylate oligomers 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 commercially available 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,
Examples thereof include polycarbonate polyols composed of a diol compound such as bisphenol A, or a reaction product of a diol compound and a short-chain dialkyl carbonate such as an ethylene oxide 2 to 6 mol addition reaction product, dimethyl carbonate, or diethyl carbonate.

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 "and" 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, hexane Methylene 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, isopolnyl (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 is a curable one or a mixture of two or more. 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 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. A spherical silicone gel particle having a specific particle diameter, which is surface-treated with a specific compound as the component (D), and a specific fluorosilicone surfactant as the component (E) are added to the product. Hereinafter, this point will be described in more detail.

D: Surface-treated spherical silicone gel particles
The spherical silicone gel particles used in the present invention are mainly composed of a monoorganosiloxane unit 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 a three-dimensional network structure by bonding, and in the above formula, the organic group (for example, the above R) bonded to a silicon atom includes:
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, vinyl group, allyl group, propenyl group, isopropenyl group,
Alkenyl groups such as butenyl group, isobutenyl group, and hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups such as benzyl group and phenylethyl group; and some hydrogen atoms in these groups Or, all of which are substituted with a halogen atom such as fluorine, chlorine, bromine or the like, a cyano group or the like, and usually have 1 to 10 carbon atoms such as a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, and particularly an aliphatic group. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms having no unsaturated bond is preferred. Among these, the availability of raw materials,
A lower alkyl group such as a methyl group is preferable from the viewpoint of easiness of industrial production and stability of the silicone gel particles, but a vinyl group, a phenyl group, a 3,3,3-
It may contain a trifluoropropyl group or the like.
As long as the effects of the present invention are not 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 are used. You can also.

The spherical silicone gel particles are polyorganosilsesquioxane particles containing 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).

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 represents a halogen such as chlorine or bromine) An organosilane compound having a hydrolyzable group or atom represented by an atom or an alkoxy group having 1 to 4 carbon atoms) is synthesized by a so-called sol-gel method in which the compound is hydrolyzed in the presence of an acid or alkali catalyst. be able to. 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.

The component (D) in the present invention comprises an organosilicon compound having a triorganosilyl group represented by the following general formula (1), wherein the spherical silicone gel particles described above are represented by the following general formula (1):
It has been surface-treated using a siloxane diol represented by the following general formula (2) or (3).

[0040]

Embedded image (Wherein, R ¹ is a methyl group or a phenyl group, R ² is a methyl group, a trimethylsiloxy group, a vinyl 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 (1) or a siloxane residue represented by the following general formulas (2a) and (3a). It is presumed that the silanol group is blocked by the group and the silanol group is inactivated, so that the obtained cured product is greatly improved in slipperiness and blocking resistance.

[0042]

Embedded image (R ² and a are as described above.)

On the other hand, the spherical silicone gel particles obtained by the above synthesis method are usually added to the composition of the present invention in a small amount that does not impair the transparency, Slipperiness and blocking resistance are not improved. The reason for this is considered to be that a considerable amount of silanol groups is present on the surface of the spherical silicone gel particles, which adversely affects the slipperiness and blocking resistance of the cured product surface.

As the organosilicon compound having a triorganosilyl group represented by the above formula (1), for example, a compound represented by the formula (1)
a) an alkoxysilane, a silylamine of the formula (1b),
Silazane of the formula (1c) and the like can be mentioned, and among these treating agents, it is preferable to use silylamine or silazane having high treating ability.

[0045]

Embedded image (R ¹ is the same as above. Each R ¹ may be the same or different. R ⁵ is a monovalent hydrocarbon group such as an alkyl group or alkenyl group having 1 to 4 carbon atoms, ^6, R ⁷ is a monovalent hydrocarbon group such as an alkyl group, an alkenyl group having 1 to 4 carbon atoms.)

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

[0047]

Embedded image

The siloxane diols of the above formulas (2) and (3) can be produced by a known method.
In the case of the compound of formula (2), 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 (3) can be obtained by the following known method.

[0050]

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 (1), a siloxane diol of the above formula (2) or (3) and an untreated siloxane diol. After mixing and contacting the spherical silicone gel particles in the reaction vessel, heat treatment can be easily performed. When the treating agents are mixed and contacted, a method of mixing the treating agents as they are, or a method of mixing water and spherical silicone gel particles in advance and then mixing and contacting the treating 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 surface-treated spherical silicone gel particles have an average particle diameter of 0.1 to 5 μm, preferably 0.2 to 3 μm, in view of the slipperiness of the surface of the obtained cured product and the thickness of the tape material. It is necessary to be. If the average particle diameter is less than 0.1 μm, the desired blocking resistance and slipperiness cannot be obtained. If the average particle diameter exceeds 5 μm, disadvantages such as deterioration of the surface state of the cured film and easy precipitation of the particles will occur. Is generated.

The compounding amount of the surface-treated spherical silicone gel particles of the component (D) is usually the total amount of the components (A) to (C) in that the resulting cured film has better transparency and slipperiness. It is 0.05 to 5 parts by weight, preferably 0.1 to 0.4 parts by weight, per 100 parts by weight. If the amount is less than 0.05 part by weight, a satisfactory effect cannot be obtained. If the amount exceeds 5 parts by weight, the color of the colorant cannot be distinguished due to a decrease in transparency, and the spherical silicone gel particles are liable to aggregate and settle. Problem arises.

E: Fluorosilicone Surfactant As the fluorine silicone surfactant of the component (E),
What is shown by the following general formula (4), (5) or (6) is used.

[0056]

Embedded image

[0057]

Embedded image

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 preferred, and a polymer chain having a degree of polymerization of 100 to 200 is more preferred.

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%.

The fluorosilicone surfactants of the above formulas (4) and (5) can be produced by the method described in JP-A-3-47190, and specific examples include the following compounds. it can.

[0062]

Embedded image

[0063]

Embedded image

The fluorosilicone surfactant represented by the above formula (6) can be produced by condensing a compound represented by the following general formula (9).

[0065]

Embedded image (Z represents a hydrogen atom or a hydroxyl group, and Rf ² , Q ² , R ⁴ ,
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. If Z is a hydroxyl group, it is dehydrated and condensed in the presence of a catalyst. The compound of (6) 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.

[0067]

Embedded image (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 (6) include the following compounds.

[0070]

Embedded image

[0071]

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
When the amount is less than 5 parts by weight, a satisfactory compounding effect cannot be obtained. When the amount exceeds 5 parts by weight, no further improvement in smoothness and slipperiness is observed, but the transparency of the cured film is poor or the The surfactant may undergo phase separation.

In the tape material composition of the present invention, in addition to the above-mentioned components, for example, stabilizers such as antioxidants and ultraviolet absorbers, coloring pigments, fillers other than the above-mentioned component (D), and fillers other than the above-mentioned component (E) Surfactants, solvents and the like can be added as needed within a range not to impair the purpose of the present invention.

The composition of the present invention can be prepared by mixing and stirring the above-mentioned necessary components, and kneading them with a three-roll mill. Normally 1,000 ~ due to compatibility with manufacturing conditions
A range of 10,000 cp (25 ° C.) is desirable.

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
Protects optical fiber from external forces as sheath of loop-type core wire
30 to 150 kgf / mm^Two High degree of ya
Rate can be achieved. In addition, the tape type core wire
Other configurations are the same as those of a known tape type core wire.

[0076]

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

[0077]

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) In a 5 liter glass container, 3,660 g of water having a pH of 6.8 and 90 g of aqueous ammonia (concentration: 28%) were added. The addition was 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 in the case of the spherical silicone gel particles-II was carried out except that 4.0 g of hexamethyldisilazane was used as a surface treatment material to obtain surface-treated spherical silicone gel particles-III.

(2) Synthesis of urethane acrylate oligomer Polytetramethylene ether glycol having a number average molecular weight of 2,000 (trade name: PTG-200, manufactured by Hodogaya Chemical Co., Ltd.)
0) 201 g, 2,4-tolylene diisocyanate 5
2.5 g was charged into a reaction vessel, and this mixture was charged to 60 to 70 g.
The reaction was carried out at a temperature of 6 ° C. for 6 hours. Next, polytetramethylene ether glycol having a number average molecular weight of 650 (trade name: PTG-650, manufactured by Hodogaya Chemical Co., Ltd.) was added to the reaction mixture.
3 g and 92.9 g of 2,4-tolylene diisocyanate were added, and the mixture was further reacted at a temperature of 60 to 70 ° C. for 6 hours.
The reaction mixture thus obtained was cooled to about 40 ° C., and 0.15 g of tert-butylhydroxytoluene was added thereto.
Add 0.08 g of dibutyltin laurate and 118.4 g of 2-hydroxyethyl acrylate,
The reaction was performed at 70 ° C. for 3 hours to obtain a urethane acrylate oligomer. The product thus obtained is referred to as urethane acrylate oligomer A.

Polyoxypropylene glycol having a number average molecular weight of 2,000 (P21, manufactured by Takeda Pharmaceutical Co., Ltd.)
167 g, polytetramethylene ether glycol having a number average molecular weight of 650 (trade name: PTG-6, manufactured by Hodogaya Chemical Co., Ltd.)
50) 163 g, 2,4-tolylene diisocyanate 2
09.0 g was charged into a reaction vessel, and
The reaction was performed at a temperature of 0 ° C. for 6 hours. Next, the reaction mixture was cooled to about 40 ° C., and 0.16 g of tert-butylhydroxytoluene and 0.1 ml of dibutyltin laurate were added thereto.
09 g and 2-hydroxyethyl acrylate 202.
8 g was added and reacted at a temperature of 60 to 70 ° C. for 3 hours.
A urethane acrylate oligomer was obtained. The product thus obtained is referred to as urethane acrylate oligomer B.

(3) Preparation of UV Curable Resin Composition Urethane acrylate oligomer 55 obtained above
Parts, 15 parts of tricyclodecane dimethanol diacrylate (manufactured by Mitsubishi Kasei Kogyo Co., Ltd., SA-1002), 10 parts of bisphenol A ethylene oxide-modified diacrylate (manufactured by Toagosei Co., Ltd., M-210), N-vinylpyrrolidone 1
0 parts, isobornyl acrylate 10 parts, 1-hydroxycyclohexyl phenyl ketone 3 as a photopolymerization initiator
The parts were mixed to prepare a base composition. The viscosity of the base composition A using the urethane acrylate oligomer A is 2
It was 8,000 cp at 5 ° C. Further, the viscosity of the base composition B using the urethane acrylate oligomer B is 2
It was 6,000 cp at 5 ° C.

Examples 1 to 8 and Comparative Examples 1 to 6
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 with a three-roll mill. A cured film was prepared from the tape-forming material composition thus obtained as described below, and the physical properties were evaluated. For comparison, a cured film was similarly prepared using spherical silica IV instead of the spherical silicone gel particles, and the physical properties were evaluated. The results are shown in Tables 1 and 2.

The spherical silicas IV in Tables 1 and 2 are spherical silica (Admafine SO-C5, manufactured by Admatech Co., Ltd., average particle diameter 2 μm, particle size distribution 0.1-5 μm) and spherical silicone gel particles-II. Similarly, the surface was treated with octamethyltetrasiloxane-3,5-diol.

Evaluation method: (1) Preparation of sample A tape-forming material composition of 200 to 300 μm was placed on a glass plate.
Apply to film thickness, 500mJ / cm^Two (Wavelength 350nm)
Was irradiated to obtain a cured film. (2) Blocking resistance The cured film cut into 5 x 5 cm was applied to two glass plates.
Scissors, apply 100g load and leave at 60 ° C for 24 hours
Thereafter, the degree of adhesion was evaluated according to the following criteria. ：: easily peeled off. ×: Adhered. (3) Sliding property (dynamic friction coefficient) Cured film at 25 ° C and 50% relative humidity for 24 hours
After adjustment, load 200g, table speed 150m
m / min (ASTM D1894)
The coefficient of kinetic friction between the lumps was measured. (4) Measurement of Young's modulus Condition the cured film at 25 ° C and 50% relative humidity for 4 hours.
After adjustment, the distance between the marked lines is 25 mm, and the pulling speed is 1 mm / mi.
Under the conditions of n, a 2.5% tensile modulus was measured. (5) Settling property The tape-forming material composition before curing was left at 40 ° C. for 1 month.
Thereafter, the sedimentation state of the particles was visually observed. ：: No separation (no sedimentation) ×: Separation (sedimentation) (6) Transparency A cured film having a thickness of 50 μm was prepared and the film was visually observed.
The other side of the film can be seen through when viewed through
Or not as a criterion. ：: See through. ×: Invisible.

[0087]

[Table 1]

[0088]

[Table 2]

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08F 290/00 MRW C08F 290/00 MRW (72) Inventor Shohei Kosakai Matsuda-machi, Daimahito, Usui-gun, Gunma Prefecture No. 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Masatoshi Asano 1-10 Hitomi Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Hiromasa Yamaguchi 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[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. ), 100 parts by weight of components (B) and (C), and (D) an organosilicon compound having a triorganosilyl group represented by the following general formula (1) or the following general formula (2) ) Or 0.05 to 5 parts by weight of spherical silicone gel particles having an average particle diameter of 0.1 to 5 μm and surface-treated with the siloxane diol represented by (3).(Where R¹Is a methyl or phenyl group, R^TwoIs meth
Group, trimethylsiloxy group, vinyl group or trifluoro
A is 0, 1, 2, or 3. (E) 0.01 to 5 parts by weight of a fluorosilicone-based surfactant represented by the following general formula (4), (5) or (6)(However, in the formula, Rf¹Is perfluoro with 4 to 10 carbon atoms
Peralkyl group having 5 to 14 carbon atoms
Reether group, Q¹Is polyethylene glycol chain, poly
Divalent of propylene glycol chains or both
A polyether group, R^ThreeIs hydrogen atom, allyl group, carbon atom
Alkyl group having 1 to 4 carbon atoms or acyl having 2 to 3 carbon atoms
K and m are each 0 or 1, and n is an integer of 1 to 3.
Is a number. )(However, in the formula, Rf^TwoIs perfluoro with 4 to 14 carbon atoms
Peralkyl group having 5 to 14 carbon atoms
Reether group, Q^Two Is polyethylene glycol chain, poly
Divalent of propylene glycol chains or both
A polyether group, R^FourIs hydrogen atom, allyl group, carbon atom
Alkyl group having 1 to 4 carbon atoms or acyl having 2 to 3 carbon atoms
P and r are each 0 or 1, q is 1 or 2,
x is 2 or 3. )
UV curable optical fiber tape material composition. 2. A tape type core wire coated with a cured product of the tape material composition according to claim 1.