JPS61191545A - Clad material for optical fiber - Google Patents

Abstract

PURPOSE:To obtain the titled clad material capable of inhibiting generation of H2 in the clad stage and causing no increase of transmission loss by constituting the material of a specified organopolysiloxane, organohydrogenpolysiloxane, and Pt based addition reaction catalyst. CONSTITUTION:Organopolysiloxane (A) having at least two groups expressed by the formula (II) in one molecule of a compd. expressed by the formula (I) (where b and c are positive integers) is mixed with organohydrogenpolysiloxane (B) having at least two bonds expressed by the formula (IV) in a molecule of a compd. expressed by the formula (III) (where j, k, and l are positive integers) wherein the molar ratio of the group (II) to the group (IV) is >=1 and the amt. of the bond (IV) in 100g (A+B) is <=0.05mol (C) 0.1-20ppm (per total amt. of A+B) addition reaction catalyst comprising a Pt base metal compd. such as Pt, Rh, Pd, etc., is mixed uniformly therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of application for M industry) The present invention relates to a coating material for optical fibers, and particularly to a coating material for coating quartz fibers for optical communications.

(Prior art) Various fibers for optical communication are known, such as quartz thread, multi-component glass, and plastic. Quartz-based materials have been put into practical use as weather-resistant materials due to their transmission capacity and other factors. However, since this quartz-based material is extremely thin and easily deteriorates over time, its surface is coated with an appropriate material.

In addition, this coating material has low temperature dependence, can be used over a wide temperature range, maintains one strength, and is effective in stress relief.
Moreover, it also invites transmission loss due to microbending.
It is preferable to use silicone resin because it is less likely to cause noise due to scattering.

However, silicone resins currently in practical use mainly contain vinyl groups bonded to silicon atoms in the molecule [YoS i
(CH=CH) group]! Contains organopolysiloxane and hydrogen atoms bonded to silicon atoms in the molecule (=SiH bond)
! This is a method in which an addition reaction is carried out with the organohydrodiene polycloxane containing (I), and from the viewpoint of the properties or curability of the cured silicone resin, the Mi-SiH bonds remain after the addition reaction in the hydrodiene polysiloxane, and these react with moisture in the air to form hydrogen gas, which has the disadvantage of increasing the transmission loss of the glass fiber. .

(Structure of the Invention) The present invention relates to an optical fiber coating material that solves the above-mentioned disadvantages, and has the following features: 1) 1i81(O)l is added to the vinyl group bonded to a silicon atom in one molecule.

=CH) group], 2) a hydrogen atom bonded to a silicon atom in one molecule (=
has at least two SiH bonds).

The molar ratio of the ;81(CH=CH,) group to the 381H bond in the first component is Te81(CH=CH,)/=Sin≧1, and the amount of this =SiH bond is the same as that of the first component. Total of second component 11100. Less than 130.05 moles per F! The amount that can be obtained is organohedrogienborishiro-san.

3) A platinum-based addition reaction catalyst.

To explain this, the present inventors conducted various studies on the development of an optical fiber coating material that can suppress the generation of hydrogen gas when coated on an optical fiber.
The molar ratio of the vinyl group [=81 (CH=CH2) group] in the vinyl group-containing organosiloxane to be subjected to the addition reaction and the hydrogen atom [mi81H bond] in the organohydrodiene siloxane = Si (CH=CH2) =si in the addition reaction product with /=SiH as 1 or more than 1
It was discovered that it is sufficient to reduce the remaining a bonds as much as possible, and to make the organohydrodiene siloxane such that the amount of =siH bonds is less than 0.05 mol or less per total ff1100 gK of these siloxanes. The present invention was completed.

Organopolysiloxane tX as the first component constituting the coating material Y of the present invention contains at least 2 vinyl groups (:;5i(OH=CIH2) groups) in each molecule.
It is well known in the industry and is usually considered to be a linear organopolysiloxane having a vinyl group at the end of the molecular chain, but the vinyl group is not limited to the end of the molecular chain. It may be contained in one molecule side chain, or it may be contained in both the end of one molecule chain and the side chain of one molecule. In addition, organic groups other than the vinyl group bonded to the silicon atom in this organosiloxane include a methyl group,
Hydrogen bonded to alkyl groups such as ethyl, propyl, and butyl groups, cycloalkyl groups such as phenyl and tolyl groups, cycloalkyl groups such as cyclohexyl and cyclobutyl groups, or carbon atoms of these groups. It is considered to be the same or different unsubstituted or substituted monovalent hydrocarbons selected from groups in which some or all of the atoms are substituted with hydrogen atoms, atom-cyano groups, etc.
If it contains a S i (0H=CH2) groups, its molecular structure is linear, monobranched, or cyclic.

It may be either in the form of a net, or it may be used alone or in a mixture of two or more.

This organopolysiloxane has the following formula: -81-ORmOH,.

wealth Oh.

Oh.

■ -31-OR-OH,.

Cao Oh.

OH -8i-ORmOH 01(.

e, f, g, h, i+X positive integer) are exemplified;
R38100, units) 70 mol%, methyl vinyl #siloxy units (OH, (O)1-OR,) 810 units]
10 mol%, dimethylsiloxy units ((OH1).

810 consisting of 120 mol% of units, furthermore, 37 mol% of trimethylsiloxy units ((0H8), s s o, units), dimethylvinylsiloxy units [(OH
1) It may also be an organosiloxane cocarbonate composite consisting of 2(OH=OI(,)SiOol, 116 mol% units and 47 mol% Si, O units.

These organopolysiloxanes can be easily produced by mixing corresponding organosilanes and cohydrolyzing them, or by subjecting a disiloxane containing the terminal group to an equilibrium reaction with a cyclic polysiloxane in the presence of an alkali catalyst. - These can be anything from low viscosity, with a viscosity of 0.708 at 25°C, to solid, high degree of polymerization; It may be used in a form dissolved in polysiloxane or in a solvent such as benzene or toluene.

Next, the organohydrodiene polysiloxane as the second component may also be one well known in the art;
It is necessary to contain at least two iI (bonds). This Mi-SiH bond may be included at the end of the engineering molecule chain or may be included in the side chain, but this is because it reacts with the vinyl group in the first component to give a cured product. Since this is a necessary functional group, if there are only two vinyl groups in the first component, there must be at least three in the second component. When there is no K, the number of vinyl groups in the first component must be small (3 in total. = 81 in this !22 composition) 1
The organic group other than the bond may be the same or different type of unsubstituted or substituted monovalent hydrocarbon group as the organic group other than the vinyl group in the first component. The molecular structure of this organohedrogen polysiloxane may be linear, monobranched, cyclic, or network-like, and may be used alone or in a mixture of two or more types. Examples include those represented by the formula (j, where t is O or a positive integer, respectively), and in particular; SiH bond is OH.

Since it is preferable that the compound exists in the molecule in the form of H-8i-0-OR, the compound represented by the following formula is preferable.

OH30H30m’l, 07lI.

B-81-0-81-0-81-0-8i -Hl
1 1 1 0 H@ OOHs OHs O)! -81-OH8 B-81-0-81-0-81-H l 1 1 0H300H.

Iris OH, -81-0H3! ];1[h-st-o-s io-s 1-o-s 1ea
II I+ OH3000BS 0)1. -81-OH,0H3-81-CI(.

HH The amount of this second component to be blended with the first component is the =s1 (aa=on2) base amount in the first component and the a8 in the second component.
It may be determined based on the amount of 1H bond.

This is to minimize the =Sin groups remaining after the reaction is completed, =81(C!H=OH,)/! H81
) l ≧ 1 (molar ratio), but from the viewpoint of preventing an increase in optical fiber transmission loss due to the presence of hydrogen gas caused by SiH bonds, In this second component, B
51I (the amount of bond is the total of the first component and the second component 11t)
It has been experimentally confirmed that the amount should be set to 130.057 g/10011 or less.

Further, examples of the addition reaction catalyst as the third component include platinum, rhodium, palladium, nickel, and compounds thereof, and platinum compounds that are commonly used commercially may be used. Examples of platinum compounds include chloroplatinic acid, alcohol-modified chloroplatinic acid, and complex salts of chloroplatinic acid and olefins. It is often used in dissolved form, and the amount used is the same as the above-mentioned wJ1 component and the second component.
The amount may be in the range of 0.1 to 20 ppm based on the total weight of the components.

The optical fiber coating material of the present invention can be obtained by uniformly mixing predetermined amounts of the first to third components described above, and if necessary, hydrogen gas remaining in the addition reaction product may be adsorbed. Platinum, rhodium, palladium and their compounds 1, such as platinum powder, have substantially no addition reaction catalytic ability.

Platinum asbestos, platinum barium cyanide, platinum black.

Platinum dichloride, potassium chloroplatinate, rhodium powder, rhodium acetylacetone, rhodium chloride, rhodium oxide, palladium powder, palladium acetate, Padge 9 Moor asbestos,
Palladium black, palladium chloride, or powdered silica or alumina.

Those supported on a carrier such as calcium carbonate, or even fine powders such as alloys of these metals may be added, and powders of these metals and alloys are added in the form of fine powders of, for example, 5 μm or less. This is desirable. This coating material contains phosphorus-nitrogen-sulfur! to control the addition reaction between the wJl component and the second component. A reaction control agent such as a compound contained therein or an acetylene compound may be added, and further, an inorganic filler such as fumed silicate, zinc carbonate, or titanium oxide, or a pigment may be added.

Next, Examples of the present invention will be given. Examples 1 to 4 and Comparative Example 1 are those in which this composition was used as a primary,
Examples 5 to 7 and Comparative Example 2 are examples in which this was used as a buffer.The parts in each example are parts by weight, and the viscosity is a value measured at 25°C.

Examples 1-3 The molecular chain ends were capped with dimethylvinylsiloxy groups.

It contains 25 mol% of phenyl groups and 0.04 mol% of vinyl groups. 1.6 mol/10 ESiH bonds were added to 100 parts of methylphenylpolysiloxane with a viscosity of 2.0OOoS.
0. Add 2.4 parts of methylhydrodiene polysiloxane containing lid, 0.5 part of an octyl alcohol modified solution of chloroplatinic acid (containing platinum 112%), and 0.5 part of a silicone modified product of acetylene alcohol, and mix uniformly. Composition ■ was prepared.

In place of the octyl alcohol modified solution of chloroplatinic acid in the above, 0.05 part of the same solution and 0.0 part of platinum oxide powder were used.
Composition II was prepared by adding 11 parts of 6), and in addition, in place of the methylhydrodiene polysiloxane in the above, -1siH of the formula (a(aH)sto )$30jT (a6H,s1o,s)s
Composition (2) was prepared by adding 6.0 parts of methylphenylhydrodiene polysiloxane containing 0.63 mol/100.9 bonds.

Example 4 It is shown by the formula. Phenyl group'& 25 mol%-vinyl group tylphenyl polysiloxane t00i, E81H bond 'k
1.6 mol/100. ! Add 3.7 parts of methylhydrodienepolysiloxane containing i+, 0.05 parts of 1#L of octyl alcohol modified solution of chloroplatinic acid (platinum content 2%) and 0.015 parts of palladium powder, and mix uniformly. Composition ■ was prepared.

Example 5 The molecular chain ends were capped with dimethylvinylsiloxy groups.

To 100 parts of dimethylpolysiloxane containing 0.007 mol 7100 g of vinyl groups; SiH bond? 1.2 parts of methylhydrodiene polysiloxane containing 0.53 mol/100.9, 1.5 parts of 1.3-divinyltetradimethyldisiloxane-platinum complex (platinum content gk 2%) and siloxane modified product of acetylene alcohol 1 .5 parts were added and mixed uniformly to make Composition V.

Examples 6 to 7 Viscosity 3.0 containing 0.007 mol/Ion of monovinyl group whose molecular chain terminal is capped with dimethylvinylsiloxy group
To 100 parts of dimethylpolysiloxane 00c8, (○H
, ), 8 iooJ units.

(OR=CH) (CH) 40 parts of a copolymer with 810 units and 810 strips in a molar ratio of to: 0.15: 1.00.

8.0 parts of methylhydrodiene polysiloxane containing 0.53 mol/100 g of ff1siH bonds, l.

3-divinyl-tetramethyldisiloxane-platinum salt (
platinum content 2%) 0.05 part, rhodium powder 0.015 part and siloxane modified product of acetylene alcohol 0.0
Add 5 parts of methyl hydrodiene polysiloxane and mix vigorously to prepare composition (1).
) 2810°, a copolymer with a molar ratio of 4:l of units and SiO
．． Composition (2) was prepared using the same composition as above except that 5 parts were used.

Comparative example 1 The molecular chain ends were capped with dimethylvinylsiloxy groups.

Phenyl group'& 25 mol%, vinyl group 0.04 mol/
100 parts of methylphenylpolysiloxane with a viscosity of 2,000 aS containing 10 (l).

3.8 parts of methylhydrodiene polysiloxane containing 1.6 mol/10 (l) of ESiH bonds, 0.05 parts of an octyl alcohol modified solution of chloroplatinic acid (platinum content 2%) and 0.0 parts of a silicone modified solution of acetylene alcohol. 0
5 parts were added to make composition ■.

Comparative example 2 The molecular chain ends were capped with dimethylvinylsiloxy groups.

60 parts of dimethylpolysiloxane containing 0.007 mol/100.9 vinyl groups.

(OR1)sSin. , unit, (aH,=ca)(ca
,).

810°, units and S10. Unit of 1.0 = 0.15
: 1.00 molar ratio copolymer (vinyl group content 0.1 mol/100,140 parts; Sin bond 0.53 mol/1
0 (l containing methylhydrodiene polysiloxane 1
2.5i15.1, 0.1 part of 3-divinyltetramethyldisiquaxane-platinum complex salt (platinum content 2%) and 0.1 part of a silicone-modified acetylene alcohol were added and mixed uniformly to form a composition. Had made.

(Measurement of transmission loss as optical fiber coating material) Compositions ① to ①, ⑥Y Ge20-P2O as described above.

The surface of a quartz fiber doped with 125 μm in diameter was coated with a primer layer to a thickness of 50 μm and Un, and then a buffer layer of compositions V to 1 and 2 obtained above was coated on the outside to a thickness of 87.5 μm. Then, nylon was applied to this to a thickness of 250 μm,
The optical fiber Y2O obtained in this way was heat-treated at 0°C for 4 hours, and the transmission loss increased! Upon investigation, the results shown in Table 1 were obtained.

Table 1

Claims (1)

[Claims] 1.1) Vinyl bonded to a silicon atom in one molecule [≡
An organopolysiloxane containing at least two Si (CH=CH_2) groups. 2) Hydrogen atoms bonded to silicon atoms in one molecule (≡Si
H bonds). The molar ratio of ≡Si(CH=CH_2) groups and ≡SiH bonds in the first component is ≡Si(CH=CH_2)/≡SiH≧
1, and the amount of ≡SiH bonds is such that the amount of ≡SiH bonds is 0.05 mol or less per 100 g of the total amount of the first component and the second component. 3) Platinum-based addition reaction catalyst. An optical fiber coating material comprising: