JP2001166189A - Slip imparting agent for coated optical fiber ribbon and coated optical fiber ribbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slip imparting agent which imparts excellent slipperiness and blocking resistance to a coated optical fiber ribbon by a small amt. of coating application, is free of trouble such as splashing and sticking in coating application and is excellent in usability. SOLUTION: The slip imparting agent consists of silicone rubber spherical particles of 0.01 to 50 μm in average grain size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coating a small amount of optical fiber tape on the surface thereof without impairing transmission characteristics.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slip imparting agent for an optical fiber ribbon, which can greatly reduce friction between tape ribbons, and an optical fiber ribbon coated with the same.

[0002]

2. Description of the Related Art At present, a large number of tape-type optical fibers having advantages such as high density of optical fibers of a cable and multi-core connection can be produced at a time.
This means that a number of coated fibers made by applying a soft and small temperature-dependent primary coating of Young's modulus around a quartz fiber, and then applying a secondary coating of a hard high Young's modulus around the silica fiber are arranged in a line. Tape-shaped (plate-shaped) whose outer periphery is covered with an ultraviolet-curable tape material, cured, and bundled
(Ribbon structure). These are produced and wound up on a bobbin in the manufacturing process. At this time, the tape core wire has a large area to be superimposed due to the plate shape, so that the tape core wires are stuck together, so-called blocking is likely to occur, and the winding process cannot be aligned and wound, and the tape core wire has a small bent shape. , And transmission loss increases. Also, there is a problem in the process of storing and manufacturing the cable. Furthermore, the following problem occurs when the blocking property is high. 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. With this 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 do not move freely together, the stress will be concentrated locally and the transmission characteristics Adversely affect Therefore, the tape core wire is required to have good blocking resistance and slipperiness.

[0003]

As an improvement, Japanese Patent Application Laid-Open Nos. Sho 60-134211 and Sho 62-98314 have been proposed.
As disclosed in Japanese Unexamined Patent Publication, during or after the manufacturing process of the tape core wire, a method of applying an oil such as powder or silicone such as talc to the surface has been performed.
Powder has a problem that it scatters and adheres to various parts of the manufacturing equipment, contaminating the manufacturing site, and oil has a sticky feeling, furthermore, it is difficult to apply uniformly, and there is a problem that stable slipperiness cannot be obtained. is there.

The present invention has been made in order to improve the above circumstances, and has no problems such as scattering and stickiness, and can provide an excellent slipperiness and blocking resistance with a small amount of coating. It is an object to provide a slip imparting agent for use and an optical fiber ribbon.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that silicone rubber spherical fine particles having an average particle diameter of 0.01 to 50 μm, especially The silicone rubber spherical fine particles are dispersed in water, and the liquid state is applied to the surface of the tape core wire. Then, the water is volatilized and the silicone rubber spherical fine particles remain to provide good slipperiness to the tape core wire. It was confirmed that silicone rubber spherical fine particles were not scattered because of being liquid at the time of application, and that the problem of contamination could be solved. Furthermore, when spherical particles of silicone rubber are used as the powder, excellent sliding properties are achieved even with a small amount, and since the spherical particles are a soft rubber elastic body, they do not damage the surface of the tape core wire, and transmission loss due to stress. Can also be reduced, and since the silicone rubber spherical fine particles have the same density as water when made into an aqueous dispersion,
The inventor has found that it is a stable slip imparting agent that is unlikely to settle or float, is easy to redisperse, and has completed the present invention.

Therefore, according to the present invention, the average particle size is from 0.01 to
Provided are a slip imparting agent for an optical fiber tape made of 50 μm silicone rubber spherical fine particles and an optical fiber tape coated on the surface with the silicone rubber spherical fine particles.

Hereinafter, the present invention will be described in more detail.
The slip imparting agent for an optical fiber ribbon of the present invention is made of silicone rubber spherical fine particles having an average particle diameter of 0.01 to 50 μm, and is preferably dispersed in water. In this case, in order to produce an aqueous dispersion of silicone rubber spherical fine particles in the present invention, the curable liquid silicone rubber composition has an average particle size of 0.01 to 50.
A method of emulsifying and dispersing in water using a surfactant so as to have a thickness of μm and curing is preferable. The curing reaction of the curable silicone rubber composition may be any of an addition reaction, a curing by a condensation reaction, an ultraviolet curing, and a radiation curing, but the addition reaction is particularly preferable in terms of reactivity and a reaction step. This addition reaction-curable silicone rubber composition comprises:
It is possible to obtain a composition in which (a) an alkenyl group-containing organopolysiloxane and (b) an organohydrogenpolysiloxane are subjected to an addition reaction in the presence of a (c) platinum-based catalyst.

[0008] The component (a) of the addition reaction composition is an organopolysiloxane which is a main component for providing spherical fine particles of silicone rubber, and (b) an alkenyl group which undergoes an addition reaction and curing with the organohydrogenpolysiloxane. And it is necessary to have at least two alkenyl groups bonded to a silicon atom in one molecule. The alkenyl group may be present in any part of the molecule,
From the viewpoint of reactivity and physical properties of the resulting silicone rubber spherical fine particles, it is preferable that the fine particles are present at the terminal of the molecular chain. Examples of the alkenyl group include a vinyl group and an allyl group, and a vinyl group is particularly preferable. Organic groups (R ¹ groups) bonded to silicon atoms other than alkenyl groups include 1
Selected from species or two or more monovalent organic groups having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl group such as hexyl group and octyl group, aryl group such as phenyl group and tolyl group, aralkyl group such as β-phenylethyl group and β-phenylpropyl group, chloromethyl group, and 3,3,3-trifluoropropyl group ,
Examples include unsubstituted or substituted monovalent hydrocarbon groups such as halogenated alkyl groups such as 3,3,4,4,5,5,6,6,6-nonafluorohexyl groups. 90% of this organic group
The above is preferably a methyl group. The structure of the organopolysiloxane may be linear, branched, or cyclic, and may be a mixture thereof. Examples of the organopolysiloxane of the component (a) include those represented by the following general formula.

[0009]

Embedded image (Wherein R ¹ is as defined above, and a and b are 0, 1,
2 or 3, and a + b = 3, c is a positive number, d is 0 or a positive number, and 2a + d ≧ 2. )

[0010]

Embedded image (Wherein, R ¹ is the same as above, e is a positive integer of 2 or more, f is 0 or a positive integer, and (e + f) = 4 to
8 )

[0011]

Embedded image (Wherein R ¹ is the same as above, g is 1, 2 or 3,
h is 0, 1 or 2 and (g + h) = 3;
i, j and k are positive numbers. )

The organopolysiloxane (a) has a viscosity at 25 ° C. of 1 to 10,000 mPa · s.
s, particularly preferably 10 to 5,000 mPa · s.

The organohydrogenpolysiloxane as the component (b) is a crosslinking agent for the component (a),
Hydrogen atom (SiH) bonded to silicon atom in component (b)
Is cured by the addition reaction of the alkenyl group of the component (a) with the catalytic action of the component (c). Thus, component (b) is required to have at least two hydrogen atoms bonded to silicon atoms within each molecule, organic groups bonded to silicon atoms other than the hydrogen atom, similar to R ¹ of the Of 1
And preferably 90 mol% thereof.
The above is the methyl group. The structure of the organohydrogenpolysiloxane may be linear, branched, or cyclic, and may be a mixture thereof. In order to obtain good rubber properties after curing, the amount of the component (b) is such that the hydrogen atom bonded to the silicon atom of the component (b) per one alkenyl group in the component (a) is: 0.5
５5.0, preferably 0.8-2.0. Examples of the organohydrogenpolysiloxane of the component (b) include those represented by the following general formula.

[0014]

Embedded image (Wherein, R ¹ is the same as above, L is 0 or 1, m is 2 or 3, and L + m = 3, n is 0 or a positive number, p
Is 0 or a positive number, and 2L + p ≧ 2. )

[0015]

Embedded image (In the formula, R ¹ is the same as above, q is a positive integer of 2 or more, r is 0 or a positive integer, and (q + r) = 4 to
8 )

[0016]

Embedded image (Wherein, R ¹ is the same as above, s is 1, 2 or 3,
t is 0, 1 or 2, and (s + t) = 3, and u, v
And w are positive positive numbers. )

The viscosity of the organohydrogenpolysiloxane of the component (b) is 0.1 to 25 ° C at 25 ° C.
5,000 mPa · s, especially 1 to 5,000 mPa · s
It is preferred that

The component (c) is a catalyst for causing an addition reaction between an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom. Examples of the catalyst include carbon supported on platinum or silica, chloroplatinic acid, a platinum-olefin complex, Examples thereof include a platinum-alcohol complex, a platinum-phosphorus complex, and a platinum coordination compound. The amount of component (c) used is (a) component and (b)
If the amount of platinum atoms is less than 0.5 ppm with respect to the total amount of the components, poor curing may result. If the amount exceeds 100 ppm, no significant improvement in curability can be expected, and it is not economical. １００100 ppm.

The production of the spherical fine particles of silicone rubber of the present invention is carried out by mixing a predetermined amount of the alkenyl group-containing organopolysiloxane (a) and the organohydrogenpolysiloxane (b). Then, water and a surfactant are added to the obtained composition, and the mixture is emulsified using a homomixer or the like. As the surfactant used,
As a nonionic surfactant polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester,
Glycerin fatty acid esters, etc., are selected from those having an HLB in the range of 1.5 to 20, preferably in the range of 7 to 19. Examples of the ionic surfactant include alkyl sulfates, alkyl benzene sulfonates, dialkyl sulfosuccinates, alkyl phosphates,
Anionic surfactants such as polyoxyethylene alkyl ether sulfate and polyoxyethylene alkyl phenyl ether sulfate, and cationic surfactants such as alkyltrimethylammonium chloride, alkylamine hydrochloride, alkylamine acetate and alkylbenzenemethylammonium chloride And zwitterionic surfactants such as N-acylamidopropyl-N, N-dimethylammoniobetaine and N-acylamidopropyl-N, N'-dimethyl-N'-β-hydroxypropylammoniobetaine. No. Among these, a nonionic surfactant which does not adversely affect the addition reaction is preferable.

If the amount of these surfactants is less than 0.01 part by weight based on 100 parts by weight of the emulsion, fine particles cannot be formed, and the dispersion may become unstable. is there. If the amount exceeds 20 parts by weight, the ability as a slip imparting agent may be reduced. Therefore, it is effective to set the content in the range of 0.01 to 20 parts by weight, but preferably 0.05 to 10 parts by weight.

Further, (a) in this emulsion
When the content of the alkenyl group-containing organopolysiloxane as the component and the content of the organohydrogenpolysiloxane as the component (b) are less than 1 part by weight based on 100 parts by weight of the emulsion, production efficiency is disadvantageous. If it is more than 80 parts by weight, it may not be possible to form an emulsion of independent cured particles,
It preferably ranges from 1 to 80 parts by weight, more preferably from 10 to 60 parts by weight.

The thus prepared emulsion is then cured by adding the platinum catalyst of the component (c) to cure the organopolysiloxane to form a dispersion of a cured silicone rubber. A known reaction control agent may be added to the platinum-based catalyst. If the platinum-based catalyst and the reaction control agent are difficult to disperse in water, a water-dispersing agent may be added using a surfactant. May be added after it becomes possible. By the above method, an aqueous dispersion of silicone rubber spherical fine particles can be obtained.

It is necessary that the silicone rubber spherical fine particles thus obtained have an average particle diameter in the range of 0.01 to 50 μm. This average particle size is 0.01 μm
When the average particle diameter is less than 50 μm, the effect of improving the slipperiness cannot be imparted when used as the slip imparting agent of the present invention. It is necessary to be in the range of 0.01 to 50 μm, and preferably in the range of 0.1 to 20 μm.

The hardness of the silicone rubber spherical fine particles is determined by measuring the hardness of the silicone rubber curable composition in the form of a sheet into a sheet having a hardness of 10 to 90 as measured by an A-type spring hardness tester according to JIS-K6801. It is better to indicate a value within the range. Preferably it is in the range of 20-80. If the hardness is less than 10, no remarkable slipperiness can be given to the tape core wire. If the hardness is more than 90, the transmission characteristics of the tape core wire may be adversely affected, and it is difficult to obtain industrially. . In addition, the silicone rubber spherical fine particles may have a thin surface coated with a relatively hard material such as a cured silicone resin for the purpose of preventing aggregation and blocking.

In order to use these aqueous dispersions of silicone rubber spherical fine particles as the slip imparting agent for the tape core wire of the present invention, the content of silicone rubber spherical fine particles in the aqueous dispersion should be less than 0.1% by weight. If it is present, remarkable slipperiness cannot be imparted to the tape core, and if it exceeds 50% by weight, further improvement in slipperiness cannot be expected, and it is not economical, and furthermore, the transmission characteristics of the tape core are adversely affected. May have an effect. Therefore, it is preferably 0.01 to 50% by weight, and more preferably 0.1 to 10% by weight. The tape core wire slip imparting agent may be obtained by diluting the aqueous dispersion of the silicone rubber spherical fine particles obtained by the above method to a desired concentration with water.

The optical fiber ribbon of the present invention is obtained by applying the above-mentioned slip imparting agent to the surface thereof, and the method of application and the amount of application are appropriately selected. The optical fiber ribbon itself is not limited and may be a known one.

[0027]

The slip-imparting agent of the present invention imparts excellent slip and blocking resistance to the optical fiber ribbon with a small amount of application, and has no inconvenience such as scattering or stickiness at the time of application. It is excellent.

[0028]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Production Example 1 Methylvinylpolysiloxane 50 represented by the following formula (A) having a viscosity of 600 mPa · s
0 g and 20 g of methylhydrogenpolysiloxane having a viscosity of 30 mPa · s represented by the following formula (B) were charged into a 1-liter glass beaker, and stirred and mixed at 2,000 rpm using a homomixer. Number of moles added 9) Octyl ether 5 g, water 150
g and continued stirring at 6,000 rpm,
A phase inversion occurred from the W / O type to the O / W type, and thickening was observed. Then, while stirring at 2,000 rpm, water 32
When 9 g was added, a uniform cloudy O / W emulsion was obtained. This emulsion was transferred to a glass flask equipped with a stirrer equipped with anchor-type stirring blades, and 1 g of a toluene solution of chloroplatinic acid-olefin complex (platinum content: 0.05% by weight) and polyoxyethylene (Pt content: 0.05% by weight) were stirred at room temperature. Number of moles added 9) A mixture of 1 g of octyl ether was added, and 1
When the reaction was carried out at room temperature for 2 hours, a uniform cloudy dispersion (hereinafter referred to as aqueous dispersion-1) was obtained. The average particle size of the particles in this dispersion was measured using a Coulter counter (manufactured by Coulter Electronics Co., Ltd.).
The content of the silicone rubber particles was 52% by weight. When a small amount of the aqueous dispersion-1 was dried at room temperature, an elastic white powder was obtained, and it was confirmed by an optical microscope that the powder was spherical.

[0030]

Embedded image

Separately, a mixed solution of 500 g of methylvinylpolysiloxane represented by the above formula (A) and 20 g of methylhydrogenpolysiloxane represented by the above formula (B) is mixed with a toluene solution of the chloroplatinic acid-olefin complex ( 1 g of platinum content (0.05% by weight) was immediately added, and immediately poured into an aluminum dish having an inner diameter of 60 mm and a depth of 10 mm, and allowed to stand at room temperature for 12 hours to obtain a silicone rubber sheet. The hardness of this rubber sheet was measured by an A-type spring hardness tester according to JIS-K6301, and was 29.

[Production Example 2] The same treatment as in Production Example 1 was carried out except that 1 g of polyoxyethylene (additional number of 9) octyl ether used in the preparation of the O / W emulsion in Production Example 1 was changed to 1 g. A white turbid dispersion (hereinafter referred to as aqueous dispersion-2) was obtained. Similarly, when the average particle size of the particles in this dispersion was measured, it was 15 μm, and the content of the silicone rubber particles was 52% by weight. When a small amount of aqueous dispersion-2 was dried at room temperature,
An elastic white powder was obtained, which was confirmed to be spherical by observation with an optical microscope.

Production Example 3 Methylvinylpolysiloxane 280 having a viscosity of 10 mPa · s represented by the following formula (C)
g and 90 g of methylhydrogenpolysiloxane having a viscosity of 200 mPa · s represented by the following formula (D) were charged into a 1-liter glass beaker, stirred and mixed at 2,000 rpm using a homomixer, and then mixed with polyoxyethylene ( Number of moles added 9) 3 g of octyl ether, 70 g of water
Was added and stirring was continued at 6,000 rpm.
A phase inversion from the / O type to the O / W type occurred, and thickening was observed.
Then, while stirring at 2,000 rpm, 295 g of water
Was added to obtain a uniform cloudy O / W emulsion. This emulsion was transferred to a glass flask equipped with a stirrer equipped with anchor-type stirring blades, and 1 g of a toluene solution of chloroplatinic acid-olefin complex (platinum content: 0.05% by weight) and polyoxyethylene (Pt content: 0.05% by weight) were stirred at room temperature. A mixture of 1 g of octyl ether was added and reacted at room temperature for 12 hours.
Aqueous dispersion-3) was obtained. The average particle size of the particles in this dispersion was measured using a Coulter Counter (manufactured by Coulter Electronics Co., Ltd.) and was 4 μm. The content of silicone rubber particles was 50% by weight.
Met. When a small amount of the aqueous dispersion-3 was dried at room temperature, an elastic white powder was obtained, and it was confirmed by observation with an optical microscope that the powder was spherical.

[0034]

Embedded image

Separately, a mixed solution of 280 g of methylvinylpolysiloxane represented by the above formula (C) and 90 g of methylhydrogenpolysiloxane represented by the above formula (D) is mixed with a toluene solution of the chloroplatinic acid-olefin complex ( Production Example 1 with the addition of 1 g of platinum content 0.05% by weight)
In the same manner as in the above, a silicone rubber sheet was obtained. The hardness of this rubber sheet was measured by an A-type spring hardness tester according to JIS-K6301, and was found to be 75.

[Production Example 4] (Preparation of UV-curable resin composition as tape material and preparation of cured film) 2,
A mixture of 515.7 g of 4-toluene diisocyanate, 422.9 g of polytetramethylene ether glycol having an average molecular weight of 2,000, 219.9 g of polyoxypropylene glycol having an average molecular weight of 400, and 16.2 g of trioxypropylene glycol was placed under a nitrogen atmosphere. 70-80
The reaction was performed at a temperature of ° C. for 3 hours. Then, after cooling the reaction mixture to 40 ° C., the inside of the reaction vessel was replaced with dry air, and 492.0 g of 2-hydroxyethyl acrylate was added.
0.5 g of a polymerization inhibitor 2,6-di-t-butylhydroxytoluene was added, the temperature was gradually raised, and the mixture was reacted at 60 to 70 ° C. for 2 hours. Next, 0.54 g of the reaction catalyst 1,8-diazabicyclo [5.4.0] undecene-7 was charged,
After further reacting for 4 hours, it was confirmed that there was no absorption due to the isocyanate group (NCO) in the infrared absorption spectrum.
Polyurethane acrylate oligomer (PUA-1) 1,
667.7 g were obtained.

70 parts by weight of the obtained urethane acrylate oligomer (PUA-1), 20 parts by weight of isobornyl acrylate, 10 parts by weight of N-vinylpyrrolidone, and 3 parts by weight of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Geigy) It was blended to prepare an ultraviolet-curable tape-formed resin composition. The viscosity of the resin composition at 25 ° C. was 4,800 cp.

The resulting ultraviolet-curable tape-forming resin composition is applied on a glass plate to a thickness of 70 to 100 μm,
Irradiation with ultraviolet light of 1,000 mJ / cm ² (wavelength 350 nm) was performed to obtain a cured film.

[Examples 1 to 5, Comparative Example 1] (Preparation of slipperiness imparting agent) Water was added to the aqueous dispersions 1-3 of the silicone rubber obtained above so as to have the concentrations shown in Table 1 below. The mixture was uniformly mixed with a propeller type stirring apparatus to prepare a slipperiness imparting agent. (Evaluation of the surface slip property of the tape-formed material cured film) The slip property imparting agent obtained above was applied onto the cured film obtained above.

This film was subjected to a temperature of 25 ° C. and a relative humidity of 5
After air drying at 0% for 24 hours, a load of 200 g and a test speed of 150 mm / min (ASTM D1894)
The dynamic friction coefficient between the films was measured under the following conditions. Table 1 shows the results.

[0041]

[Table 1]

Examples 6 and 7 and Comparative Example 2 (Evaluation of surface slipperiness of tape core) Using the above-mentioned ultraviolet-curable tape-forming resin composition, four single-core optical fibers are shown in FIG. As described above, tapes were formed in parallel, and at the same time, the slipperiness imparting agents of the above Examples 1 and 2 were applied in this tape forming step to prepare optical fiber ribbons. At the time of preparation, no scattering of fine particles was observed. Also, no increase in transmission loss was observed as compared with the tape core wire (bobbin wound state) to which the slipperiness imparting agent was not applied. In FIG. 1,
1 is a glass fiber, 2 is a color core, and 3 is a tape material. The obtained tape core wire was dried at 40 ° C. for 24 hours, and the slip property was evaluated by the following method.

As shown in FIG. 2, using a jig 4 having a groove having the same width as the tape core wire on the circumference, the tape core wire 5 was wound around the groove and fixed. Another tape core 6 is superimposed on the tape core 5, one is fixed 7, and the other one is 1
A jig 4 was pulled up integrally by attaching a weight 8 of 00 g and pulling up a frame 9 attached to the jig 4 at a test speed of 150 mm / min using a tensile tester, and the load was measured. The friction force was evaluated.

The evaluation of the frictional force is a relative value based on the case where the frictional force between the tape cores of Comparative Example 2 in which the slipperiness imparting agent was not applied was 1.0. Table 2 shows the results.

[0045]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a core ribbon of an example and a comparative example.

FIG. 2A is a schematic view of a tape core wire frictional force measuring device, and FIG. 2B is a partially enlarged view thereof.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass fiber 2 Color core wire 3 Tape material 4 Jig 5 Tape core wire 6 Tape core wire 7 Fixation 8 Weight 9 Frame

Continued on the front page (72) Inventor Yoshinori Iguchi 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term (reference) 2E001 BB15 DD16 KK16 4D075 CA08 CA09 CA47 DA01 DB13 DC24 EA06 EB10 EC07 EC24 EC53 EC60

Claims (3)

[Claims] 1. A slip imparting agent for optical fiber ribbons comprising spherical fine particles of silicone rubber having an average particle size of 0.01 to 50 μm. 2. A slip imparting agent according to claim 1, wherein said silicone rubber spherical fine particles are dispersed in water. 3. An optical fiber ribbon coated with the slip imparting agent according to claim 1 or 2 on its surface.