JPS5988344A - Coating agent for fiber for optical communication - Google Patents

Abstract

PURPOSE:To facilitate the stripping of a coated layer from an optical fiber by using a coating agent contg. organosilane or organopolysiloxane having aliphatic unsatd. groups in the molecule and an org. compound having mercapto groups in the molecule such as polyol. CONSTITUTION:A coating agent for a fiber for optical communication is composed of an org. compound (A) having two or more aliphatic unsatd. groups bonding to Si in one molecule represented by formula I , an org. compound (B) having two or more mercapto groups in the molecule or an org. compound having two or more mercapto groups bonding to Si in one molecule represented by formula II, and a photosensitive agent (C). In the formulae I , II, R<1> is an aliphatic unsatd. group, each of R<2> and R<4> is an optionally substituted univalent hydrocarbon group other than an aliphatic unsatd. group, R<3> is a hydrocarbon group contg. a mercapto group, each of a and c is 0.0004-4, each of b and d is 0-2.5, a+b=1.1-4, and c+d=1.1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating material for optical communication fibers, and particularly to a silicone composition for coating quartz fibers for optical communication.

Various types of optical communication fibers are known, including quartz-based fibers, multi-component glass-based fibers, and plastic threads.
In reality, quartz fibers have been put into practical use due to their light weight, low loss, non-absorption properties, heat resistance, weather resistance, and transmission capacity. However, this quartz thread is extremely thin and easily deteriorates over time.For swords 1 and 1, the surface is first coated with a suitable material, and then the final coating is applied. This coating material has low temperature dependence, can be used over a wide temperature range, is effective in maintaining strength and relieving stress, and is also less likely to cause transmission loss due to microbending and less likely to generate noise due to scattering. Therefore, it is considered preferable to use silicone resin.

However, the method currently in practical use is a thermosetting silicone resin containing an organic peroxide.
Alternatively, it is mainly used to react an organopolysiloxane containing a vinyl group in the molecule with an organohydrodiene polysiloxane containing an f-SiH group in the molecule in the presence of a platinum catalyst. Once the silicone resin is applied, it must be cured in a high-temperature oven; therefore, this has the disadvantage that the temperature of the oven is difficult to control (the disadvantage is that it is difficult to control the temperature of the oven), and its curing speed is limited. The varnish beads also have their limitations because the coating is cured at high temperatures, so the silicone coating adheres firmly to the quartz fibers, making it difficult to make electrical connections between the fibers. This coating had the disadvantage of being difficult to remove.

The present invention relates to a coating material for optical communication fibers that solves such disadvantages, and is composed of 2 A) a) whose average molecular formula is RaRb51o4-a, , b
(Here, vcRl is an aliphatic unsaturated group, R2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group,
a=0.0004-4.0. b=o~2.5, a+b
= 1.1 to 4.0) or b) an organosilicon compound having at least two aliphatic unsaturated groups bonded to silicon in one molecule, or b) at least two aliphatic unsaturated groups in the molecule. organic compound with groups.

B) a) an organic compound having at least two mercapto groups in its n atoms, or b) an average molecular formula containing a group-containing hydrocarbon group - R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated groups; Group Q c=0.0004-4.0. d=O
~2,5, c 1 d = 1.1 ~ 4.0) An organosilicon compound having at least two mercapto groups bonded to silicon in one molecule and C) a sensitizer and Katana 1 et al. and the molar ratio of this aliphatic unsaturation to the mercapto group is 0.
．． As a result of various studies on combinations of organosilicon compounds and organic compounds of 1 to 1O and silicone resin coatings for quartz fiber materials as material-e, it was found that if a radiation-curable coating material is used as the coating material, We focused on the fact that the curing speed is faster than that of thermal curing or the above-mentioned Tsuna reaction, and that it can be done at low temperatures, and we carried out experiments on this. A reaction between an organosilane or organopolysiloxane containing an aliphatic unsaturated group in its molecule and an organic compound such as a polyol having a mercapto group in its molecule, or an organic compound having an aliphatic unsaturated group in its molecule. It is possible to form a cured film through a reaction with an organosilane or an organoborisiloxane having a mercapto group in its molecule, and that it is also possible to form a cured film through a reaction between the metal and organosilane or organoborisiloxane, which has a mercapto group in its molecule. It was discovered that this process could be carried out quickly by applying the varnish to the quartz fiber. Although the film is completely coated, it was confirmed that this hardened film has a suitable adhesion and that this film can be easily removed when connecting quartz fibers. Ta.

The organosilane or organopolysiloxane as component a) in component A constituting the coating material of the present invention has an average formula % formula % as described above. Examples include propyl group, r-methacryloxy 1avir group, etc., and examples of this R2 group include alkyl groups such as menal group-ethyl group and propyl group.

An aryl group such as a phenyl group-tolyl group, a dugloalkyl group such as a cydalohexyl group or a cidabutyl group, and a hydrogen group bonded to a carbon atom of these hydrocarbon groups are partially substituted with a halogen atom, a cyano group, a mercapto group, etc.
Examples include groups.

These may be homologous or heterogeneous combinations thereof.

That is, this organosilane or organosimixane has at least two silicon atoms directly connected to VC in its molecule.
It is good to have aliphatic unsaturated groups, which means that the molecular structure is spade-like or tin-like.

It may be either ring-shaped or net-shaped, and may be used alone or in combination of two or more types. Examples of the organosilane or organopolysiloxane include (OH, Si (OH=OH), CHSi
(CH=CH direct)j.

(OH,), S i (CH・,L), 0000 (
OH3) =OH:1,C,H,.

"H8(OH2)ssi -(CH=CH,).%0H
=OH-CH-CH=CH,.

1 KO (OH-=CH) Si, now (here e, f, g, -h, i, j, all positive integers), this is also an example. 1, methylsiloxy unit (CH, SiO2 unit), methylvinyl σkizu unit (OH
3, (C!H□=OH)SiO unit] 1O mole, dimethylsiloxy unit ((OJ mole 81O unit)) 220 mol% 71 Organacuole 1J diaxanthate and SiO unit 47 mole 1 Organopolysiloxane, 10H=OH-0-○-0,,H,S i (OCRρ.

Hydrolysis product -OR,0 11 CH,==C-0-0-c,? H, /8i (OCH3
), may be a hydrolysis product of. In addition, these organopolysiloxanes can be mixed with corresponding organosilanes to produce synergistic zero water decomposition. Alternatively, it can be easily produced by carrying out an equilibrium reaction between a disiloxane containing the terminal group and a cyclic polysiloxane in the presence of an alkali IJM medium.

Next, the organic compound as component b) in component A) may have at least two aliphatic unsaturated groups in its molecule; These are various monomers, arepolymers, or mixtures thereof, which can further contain ester groups, ether groups, ketone groups, halides, amide groups,
It may contain a hydroxyl group, etc., and its molecular structure may be linear or monobranched, and this may include 0 (OH,, 00 CH=OH Yu). 40H,,C((
3H2QC) I20H=cHρ.

Oh...

CH,: =CHCH, O÷0HCtH, o-7CH,
, cH=OH,.

0Hi==OH-000+cH2,OH,:,0)-O
COOH=oH.

CH.

OH Yu = O-Coo-OH,, CH oath, 000-NHO
OO-OH,,OH,0-Co-0=OH,.

CH Yu, CHI, cHi -0000H
=OHi etc. are exemplified.

On the other hand, a) in component B) constituting the coating material of the present invention
The organic compound having a mercapto group as a component may have at least two mercapto groups in its molecule, and includes ethylene glycol bis(thioglycolate), ethylene glycol bis(β-mercapto 70 pyone), -13-trimethylolpropane tris (
thioglycolate) - trimethylolpropane tris(
β-mercapto 70 bionate], pentaerythritol tetrakis (thioglycolate).

Examples include pentaerythritol tetrakis (β-mercaptopropionate).The organosilicon compound as component b) has at least two mercapto groups bonded to silicon atoms in its molecule. An organosilane or organopolysiloxane, which has the average molecular formula R8RdS104-od as described above.
This R3 group includes a mercaptomethyl group, a mercaptoethyl group, a mercaptobutyl group, a mercaptobutyl group, and a cyclic divalent hydrocarbon group containing a mercapto group represented by Examples of the R4 group include an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a phenyl group, a tolyl group, and a cycloalkyl group such as a cyclohexyl group and a cyclobutyl group.

Examples include groups in which the water atom bonded to the carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, a cyano group, etc., but these groups may be a combination of the same or different types. good. This mercaptoalkyl group is represented by the formula 8H(OH・)-con (where n is an integer of 1-10), which means that organosilane or organopolysiloxane having a mercaptopropyl group is It is easier to synthesize than organosilanes or organopolysiloxanes having mercaptoalkyl groups, and the odor in the uncured state is relatively tolerable.
It is preferable to include a mercaptopropyl group in which is 3. This organosilane or organopolysiloxane containing a mercapto group is used in combination with the above-mentioned organic compound containing an aliphatic unsaturated group in the molecule, and the attachment of the SH group to the aliphatic unsaturated group DI]vc Thus, a hardened film is formed. However, in order to cause an entrance reaction of a mercapto group to this aliphatic unsaturated group, it is necessary to have 011 to 10 mercapto groups for one aliphatic unsaturated group. The silane or σ-chitin preferably contains at least two mercapto groups in its molecule. The molecular structure of this organosilane or organopolysiloxane may be linear, branched, cyclic, or II4, and may be a single component or a mixture of two or more thereof. It may be. An example of the organosilane or organopolysiloxane containing this mercapto group is 0)(,si((OH,)aSHE,).

(0'E(JyuSi((OH,) 8H)8 Yu3
Examples include those represented by 0, H, SH 1 0H, C, HSH (where 1Cp-q-r, s, and t are all positive integers), and this also includes, for example, CHSiO
3/2 unit 60 mol%.

H8(OH) 5iOa/+ unit 20 moles.

Process 1 (OH, = 3.It may be an organopolysilochitin consisting of 20 moles of Si0 units, each of which is a force generated by cohydrolysis of a corresponding organosilane mixture)
Alternatively, it can be easily obtained by a method in which a disiloxane containing the terminal group and a cyclic siloxane are subjected to an equilibration reaction in the presence of an acid catalyst. However, this organopolysiloxane may be any one from a monomolecular one to a solid one with a high degree of polymerization, and in the case of this solid organopolysiloxane, it can be dissolved in another liquid organopolysiloxane, or It may be used in a form dissolved in a solvent such as benzene-toluene.

Next, the photosensitizer as component C) constituting the coating material □ of the present invention is a catalyst that promotes the addition reaction of the aliphatic unsaturated group to the mercapto group in the organic compound containing the aliphatic unsaturated group described above. The organic peroxide may be a known one, such as various organic peroxides and photosensitizers. Examples of the organic peroxide include benzoyl peroxide and t-butyl peroxide. Examples of photosensitizers include benzoate, digymyl lenochloride oxide, t-butyl peroxide, and photosensitizers such as acetophenone, pensophenone-bensoin ethyl ether-penzoin iso7
Examples include aromatic ketones such as pyl ether and benzoin butyl ether, and azo compounds such as azobisisobutyronitrile.Note that the addition of the photosensitizer as component 0) is component A). The type of aliphatic unsaturated group-containing compound (%) may be adjusted as appropriate depending on the preferred curing speed of silane or siloxane as components A) and B), but for the purpose of obtaining good curability, It is preferably within a range of 20% or less based on the organosilane or organopolysiloxane.

The coating material of the present invention includes the above-mentioned A)-B) and C)A),
B) As for the components, one of them must be an organic silicon compound and the other must be an organic compound that does not contain silicon atoms. However, various energizing agents may also be added to this, for example, pyrocatechol, hydroquinone, or their monoethers, or alkyl-substituted pyrocatechol, hydroquinone, etc., to prevent deterioration of the present coating material due to oxidation. , their ethers, etc., in an amount of 0.001-10%, preferably 0.001-10%, preferably 0.
．． It may be added about 0.002 to 1%. Furthermore, in order to improve the impact resistance, flexibility, etc. of the cured product, a non-functional organoborisaxane may be added to the coating material of the present invention. Pigments, dyes, etc. may be added to the extent that they do not significantly interfere with the curing reaction, and this also depends on the solubility of the aliphatic unsaturated group-containing compound as component A) and the mercapto group-containing compound as component B). For the purpose of improving the benzene-toluene, xylene, acetone, etc. solvents may be used in combination. The coating material of the present invention can be changed from a gel-like state to a fixed state by appropriately selecting the above-mentioned organosilane or organopolysiloxane as the main ingredient, but this is for the purpose of treatment. It may be set arbitrarily according to the characteristics of the optical communication fiber.

The surface treatment of a quartz fiber for optical distribution using the coating material of the present invention is as follows: After applying this coating material to the surface of the fiber,
This coating may be cured by irradiating it with radiation, but this coating may be done using, for example, a coating die. The thickness may be adjusted. Regarding this radiation irradiation, it is sufficient to irradiate the coated surface with ultraviolet rays, deep ultraviolet rays-electron beams, ≧ Ultraviolet rays are preferable, and sources of this ultraviolet ray include high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps,
Examples include hydrogen discharge tubes. Note that the atmosphere for this radiation irradiation is arbitrary, and may be, for example, air or inert gas.

Next, examples of the present invention will be given. All parts in the examples indicate parts by weight, and the viscosity of the organopolysilochitin used is the value measured at 25°C.〇Example Dimethylpolysiloxane with a 1° viscosity of 1'0OOcS and both ends of the molecular chain blocked with dimethylvinylsiloxy groups +
Mix 116 parts of 00 mvc-pentaerythritol tetrakis (thioglycole), 10 parts of benzoin isobutyl ether, and 0.25 parts of butylated hydroxytoluene, and apply the mixture to the surface of a quartz fiber for optical communication with a diameter of about 150 μm using a die. After applying two coats of about 50 μm, apply I to this while moving at a speed of 30 m/bamboo
When the distance blade of an O-saw was irradiated with ultraviolet rays using an 80 W/z mercury lamp, the layer on the surface of this quartz fiber became a hardened material with no surface tags.This hardened film was peeled off by squeezing with fingers. , it was easily peeled off and no coating layer remained on the fiber.

Example 2 10.6 parts of pendaerythritol tetrakis (thioglycolate) was added to 100 parts of methylphenylpolysiloxane (phenyl base amount: 20 moles), which had a viscosity of 4000 cS and had both molecular chain ends capped with dimethylvinylsiloxy groups.
- 10 parts of benzoin isobutyl ether and 0.25 parts of butylated hydroxytoluene were mixed, applied to a quartz fiber under the same conditions as in the previous example, cured with ultraviolet irradiation, and examined for adhesion to the quartz fiber. The cured film could be easily peeled off by squeezing with fingers.

Example 3゜7! Nil77 Cloxy unit (c, H, 5iOa/
z) 50 mol%, vinyl i/Cloxy units (OH,
,=CHS i OV2 J20 moles, dimethylsiloxy unit C (OHj 5in) 30 moles) 100 parts of eupolysiloxane, 15.0 parts of trimethylolpropane tris(thioglycole), butylhydroxytoluene A solution of 0.05 oL 4-/toxybenzophenone with the addition of 1 part and 15 parts of toluene was applied to quartz fiber Vr- under the same conditions as in Example 1, and cured by ultraviolet irradiation. After examining its physical properties, it was found that it could be easily detached from the quartz fiber by squeezing with fingers.

Example 4 5.9 parts of a mercapto group-containing organopolysiloxane represented by 100 parts of polyoxypropylene with a viscosity of about 500 cS, both ends of which were capped with allyl chains, 0.05 part of butylated hydroxytoluene, and 4- Mix 1 part of methoxybenzophenone.

This was applied to quartz fiber under the same conditions as in Example 1,
When irradiated with ultraviolet rays, this layer became a cured film with no surface tack, but it had such adhesion that it could be easily peeled off from the quartz fiber knife 1 by squeezing with fingers.

Patent applicant: Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A) a3 semi-uniform bamboo shoot formula is RR8i0 a b 4-a-b (here, vcd is an aliphatic unsaturated group, and z is an unsubstituted or substituted monovalent group containing no aliphatic unsaturated group) Hydrocarbon group 41
a = 0.0004-4. O, b=0~2.5゜a
+ b = 1.1 to 4.0) or b) a silicon compound having at least 23% of aliphatic unsaturated groups bonded to each other in one molecule; B) an organic compound having at least two aliphatic unsaturated groups; a) an organic compound having at least two mercapto groups in its molecule; or b) an average molecular formula of RcR(I
SiO4-c-d (where R is a mercapto group-containing hydrocarbon group, R4 is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, c = 0.0004 to 4.0-d
= 0 to 2.5°c + d = 1.1 to 4.0]; A coating material for optical communication fibers comprising a combination of an organosilicon compound and an organic compound in which the molar ratio of the aliphatic unsaturated group to the mercapto group is from 0.1 to 10.