JPS5945944A - Manufacture of light-transmission glass fiber - Google Patents

Abstract

PURPOSE:To manufacture a glass fiber having excellent water resistance and breaking strength, by coating the surface of a light-transmission glass fiber with an electron radiation-curing coating composition giving a cured product having a specific glass transition temperature, and curing the composition with specific electron radiation. CONSTITUTION:The surface of a light-transmission fiber is coated with an electron radiation-curing coating composition having a cured film having a glass transition temperature of <=-20 deg.C or >=70 deg.C. The composition is obtained by compounding an unsaturated monomer and/or unsaturated oligomer with a monomer for modifying the glass transition temperature and if necessary, with an additive. The unsaturated polymer is a resin obtained by reacting the base resin such as acrylic resin with a vinyl monomer such as acrolein. The unsaturated oligomer is, e.g. diallyl phthalate, and the modifying monomer is, e.g. methyl acrylate. The coated composition is cured by irradiating 50-5,000KeV electron radiation at a dose of about 0.2-15Mrad.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method VC for manufacturing a glass 7-eyeper for optical transmission, and more particularly to a method for coating a 7-eyeper for optical transmission with a coating phase.

In general, glass fiber materials for optical transmission, which are manufactured by optical power 2-speed material companies such as Ikoei, have a small amount of light transmission 4-bi arrows and a large ρf ratio, and they can be Characteristic Case 1j ζ - In recent years, glass fiber feeders, 7'l et al.'s Special Features 1. It is conveniently used for various purposes.

In general, the diameter of a 7° radius fiber for optical transmission is generally 200 microns or more in order to maintain river control properties.

It is known that the strength of such glass 7γ ipar deteriorates over time due to the shadow of moisture. 1. Also, during the manufacturing process of force cis fibers (cl), it is easy to cause scratches on the surface of the fiber, and these scratches can cause the mechanical strength to be low and moisture content in the atmosphere. It absorbs (7) and the scratches are rough on the water! 1"'C long and 11" long. 7 Mechanical properties
It is difficult to use C-glass fiber T Sozu J-4-Fuji original transmission wire body (7), and it is well-known that C name Yuzu method is used for optical transmission power 'Las 7 eye bar kC Where] 1-(There.

Addition to the method of sheeting optical transmission glass fiber
- Law (Unexamined Japanese Patent Publication 1'/454-15) +942su, Unexamined Publication Shou 5
5-140741 Kenato), ultraviolet m-curing, and other methods of curing the derivative materials of persimmons are being investigated, and among them, from the viewpoint of productivity of optical transmission glass 7-iper, there are many advantages as primary fft-7 paulownia material. ? It is concluded that the ultraviolet curable coating polishing +1 is advantageous. Examples of this method include JP-A-54-4249ti and JP-A-1D55-42246. Glass fibers for optical transmission are spun using sieve frequency heating furnaces, resistance heating furnaces, and oxyhydrogen flames.

This is done using a heat source such as carbon dioxide gas.

As shown in Japanese Patent Application Laid-Open No. 54-42496, coating of fiberglass fibers is done immediately after spinning the fiberglass fibers.
The ultraviolet curable resin I composition is applied to the 1f11-shaped article, and 9 steps are performed to bake it and dry it until it reaches the winding machine. Complete fC baking 1. To dry the fibers, Vc is the distance from the spinning furnace to the joining frame, and a drying oven with a length of 9% is installed. In order to increase productivity, it is necessary to have large-scale equipment for non-VC, and in order to control the accuracy of the optical transmission 7γ fiber, the line speed must be higher than a certain value during spinning. Therefore, it is necessary to manufacture at high speed. One method for this is ultraviolet irradiation in Japanese Patent Application Laid-Open No. 54-424904d. From this, a method of hardening the compound is proposed.

However, the curing of light-curable rice straw using ultraviolet rays is limited to H1Om/minute culm, and if productivity is to be increased further, the equipment will be larger, and the cost of running and maintenance will increase. rise inside.

The present inventors have discussed the above 1. What are the drawbacks of the conventional method? The inventor has now completed a wave dipping method for a fiber optic fiber for optical transmission, which eliminates the need for ultraviolet curing and significantly improves the μA resistance compared to the ultraviolet curing method.

The present invention provides an electronic curing composition in which the glass transition IIl'11 degree of the cured material must be -20'C or higher or 70°C or higher on the surface of a glass 7-eyeper for optical transmission. The present invention relates to a method for producing a seven-eye bar for optical transmission, characterized in that the electron beam is cured by applying an electron beam of 50 KeV to 500 KeV.

In the present invention, electronic PM curable fIJl whose glass transition temperature of the coating after curing is -20-C or less or 70"C or more is used as a +& material for optical transmission glass 7-eyeper.
fM composition is used.

W's sieving composition is obtained by blending a saturated polymer and/or unsaturated oligomer with a glass transition adjustment monomer and optional additives.

The unsaturated polymer used in the present invention refers to a ftIt resin that can be crosslinked and bonded by electron beam irradiation, has a saturated bond skeleton, and has a functional base as shown in Table 1. A resin that can be polymerized and cured by the energy of an electron beam, which is obtained by reacting a vinyl spindle body (exemplified in Table 2) with a resin having a vine group that is capable of addition or bonding with the functional group by a conventionally known reaction method. Examples of the base resin include acrylic resin, polyester resin, epoxy resin, amino resin (for example, melamine resin),
Examples include polyamide resins, polycrethane resins, vinyl resins, silicone resins, diene fibers, and the like. Examples of the functional groups in the vinyl yarn monomer that are to be reacted with the functional groups of each wing contained in these base resins are shown in Table 1.

Further, specific examples of vinyl monorods having such functional groups are listed in Table-2.

In addition, as an unsaturated oligomer, for example, the molecule 111
,000 or less and having 2 to 4 polymerizable vinyl groups, specific examples of which include diallyl phthalate,
Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bis-(ethylene glycol 7-talate) di(meth)acrylate, bis-(ethylene glycol 7-talate) di(meth)acrylate, polyethylene glycol di(meth)acrylate, meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, l:1 (molar ratio) of tolylene diincyanate and (meth)acrylic acid hydroxyalkyl ester
1-J addition reaction products of adducts and trimethylolethane or trimethylolpropane, pentaerythritol tetra(meth)acrylate), M4 water, talic acid, adipic acid, succinic acid, hexahydrophthalic anhydride, etc. These include polysalt M, mono- or di-esterified mono- or diesters of methacrylic hydroxyethyl, acrylic hydroxyglobil, methacrylic hydroxyethyl, and methacrylic hydroxyglobil.

Dlr 7>i unsaturated polymer and A-ligomer i,
j, i 1 goods 1.11 (111f/per (1.5yt)
Ishi 511I! ! Ic/)a, lnoA, and preferably have a finnically unsaturated bond.

Clothing ~ 1 Table-1 (Pecks) Table-1 (Nine @) Table-2 Table-2 (Tsuzuki) Examples of unsaturated polymers that are compatible with the above-mentioned unsaturated polymers or oligomers include acrylic acid and its Nisdels, methacrylic acid and its esters, aromatic vinyl monocaps, vinyl uF acid, vinyl needles, etc. are used. Typical examples include - Methyl acrylate, autoethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, octyl acrylate, decyl acrylate, ucrylic acrylate, carpitol acrylate, methyl methacrylate, methacrylate Ethyl acid, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, octyl methacrylate, tesyl methacrylate, lauryl methacrylate, carbitol methacrylate, hydroxyethyl acrylate, acrylic hydroxyglobil, bitroxyethyl methacrylate, methacrylic acid Hydroxyglobil; etherified product of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and hydroxyethyl acrylate, hydroxyglobil acrylate, hydroxyethyl methacrylate, hydroxyglobil methacrylate; acrylic acid, methacrylic acid; Styrene, vinyltoluene; etc. are used.

According to the present invention, the #4 child's hyperbaricizing assemblage lIk is 6
Glass transition #ra around F9'r by combining unsaturated polymers and/or unsaturated oligomers with unsaturated polymers like ours
By combining # pages so as to make IW itself, it is necessary to create 4 pages by VC. Polymers that provide a glass transition width of -2 ()°C or less can be selected from polybutadiene, acrylic yarn, phrethane, and modified polyester yarn. The provided polymer is generally selected from acrylic yarns, polyester groups, epoxy yarns, silicone yarns, and the like.

Further, by blending a bifunctional, 3'-functional or tetrafunctional unsaturated oligomer, the effect of increasing the crosslinking density and increasing the force-lase transition resistance can be obtained.

In addition to the above-mentioned essential components, the electron beam curable coating composition of the present invention may optionally contain pigments commonly used in paints.
Additives such as dyes and fillers can be added.

By blending unsaturated polymers and/or unsaturated oligomers with unsaturated polymers and additives as desired, the glass transition temperature after curing is 70"C or more or -20"C.
℃ or less can be easily cured. The thus obtained coating composition is coated on a light transmission glass fiber and cured to produce a light transmission fiber using, for example, a manufacturing apparatus as shown in Figures 1 to 3. In the figures of Koil, et al., IS7 and 14 are high frequency heating spinning furnaces, 2.8.15 are spun glass fibers, 3, 9 and 16 are coating devices for electron beam curable coating compositions, and 4.10 and 17 is the electron beam irradiation device ID, 11
18 is a post-heating device, 18 is an ultraviolet irradiation MM, 5.12 and 1
9 is a guide roll and 6゜13 and 20 are winding machines? show.

When applying an electron beam coating composition to the surface of spun glass fibers, the coating film thickness of the coating composition whose glass transition temperature is 120°C or less after curing is usually 10 to 120°C.
200 microns, while 5 to 50 microns is usually advantageous if the glass transition temperature is above 70°C. In the former case, if the membrane thickness is less than 10 microns, the water resistance of the eardrum will deteriorate rapidly, and if it exceeds 200 microns, the electron beam penetration power will deteriorate. In the latter case, if the film thickness is less than 5 microns, the water resistance will be poor, and if it is more than 500 microns, the flexibility of the film will be poor.

It is necessary that the specific volume of the coating of the optical transmission fiber does not substantially change in the #A degree range in which it is normally used, and if the specific volume changes, the optical transmission 7 eyeper will cause microbending and the optical However, according to the present invention, when applying an electron beam curable coating composition in which the glass transition temperature of the cured coating is below 120" CPi or above 70° C., it is difficult to apply light. In the transmission 7 eyeper, there is virtually no change in the specific volume of the pickled material in the MA range of normal use, so the above-mentioned defects do not occur at all.

As an accelerator for the electron beam source used for electron beam irradiation after the electron beam curable coating composition has been completely coated, N Makotsu Croft'M* Kotsuku Croft Walton type, No(N de Googu 7 type), resonant transformer type , transformer type, insulated core transformer type,
There are dynamidron type, linear filament type, high frequency type, etc. The electron beam energy for curing and drying the electron beam curable coating composition coating film of the present invention is 50 KeV.
~500 KeV.

Preferably, a range of 10 (I KeV to 300 KeV) is suitable.
ad ~15 Mrad is suitable, I Mrad ~5
hlrad is preferred. If the irradiation rate is less than 0.2 Mrad, the coating will not be completely cured and sufficient coating performance will not be obtained. Mako irradiation welfare force 515
Mrad-il1a, which also affects glass core ink and reduces mechanical strength 2-11
．． There is.

When irradiating an electron beam onto a fairly wide object, the electron beam should be uniformly [
1], and this method usually includes the skinning method and the linear filament method (US Pat. No. 4246
297) is a typical female method. Either method has already been put into practical use for curing pickled items, with medium or approximately 1 m long lengths. Since the bare side of the glass fiber for optical transmission is very thin (less than 20 microns), a length of several centimeters to several tens of centimeters in the direction of the electron beam irradiation is sufficient.

If it is a linear filament type, moving the VC electron beam curing coating composition PL coated fiber in a direction parallel to the filament and irradiating the electron beam will more effectively obtain a high line speed and improve fertility. .

Since electron beam curing occurs instantaneously, there are cases where stress is easily applied to the coating film, and such cases are shown in Figure 2. Due to the wood-making method, the stress is softened after the first crack. Electronics with 1 glass case and multiple lids! irradiation may cause night discoloration. In such cases, heat energy is generated using the manufacturing method shown in Figures @2 and Figures 3.

Coloring is generally resolved when increasing energy is applied.

According to the method of the present invention, the curing and drying speed using an electron beam is 150 n1/min to 90 n1/min in a length of approximately 1 m of the electron beam irradiation section.
(A speed of 1 m/min was obtained, productivity' was significantly improved,
Furthermore, the obtained product has extremely good water resistance, volume stability, etc., and an optical transmission glass fiber with excellent characteristics can be obtained.

Hereinafter, the present invention will be explained with reference to practical examples. ! will be explained in detail.

Note that "F section" means m-tooth section.

Example l Acrylated polybutadiene (polymerized Jf 1 (100)
Coating M consisting of 100% of ethylhexyl acrylate, 2% of ethylhexyl acrylate, and 1 part of All O with silicone thread added to the matrix was heated to 2130 m/9 at about 211°C (10'C).
Glass fiber (diameter 120μ) softened at a speed of
) was coated with VC so that the thickness of the pickled product was 50μ. Thereafter, the object to be coated was irradiated with an electron beam using a scanning electron beam accelerator at a speed of 1200 m/min in a direction parallel to the scanning direction under the conditions of an electron beam energy of 300 KV and an electron beam type/i of 30 mA. 60 during scanning
At crn, 1'' of the electron beam was about 3 am.

The glass transition temperature of the obtained pickled product was -48°C.

The film thickness of the Takou 7 Eyeper coated with fallen gauze was 50μ, and its average breaking strength was 400Kg/1m. This coated optical fiber was exposed to water under normal conditions for 30 days, after which the breaking strength was 380 Kf/2.

Example 2 60 n-butyl acrylate, ethyl acrylate
35 parts of glycidyl acrylate and 5 parts of glycidyl acrylate were added to J
10 parts of acrylic acid was added to Kira to obtain an unsaturated acrylic resin with a molecular weight of 80 (1 (l). 20 parts of 4-nonylphenoxypolyethoxy acrylate manufactured by Co., Ltd. (product name) and 2 parts of trimethylolpropane triacrylate were added to obtain an electron beam curable coated All tube.

B type glass 7 eyes heated to 2000 IC and drawn, (-(diameter 010 μ) coated with the above coating A+J
The coating was applied so that the k
V, electron beam current 40mA, scanning width 90crn
The coating was applied in a direction parallel to the ski X' nonning direction (electron beam irradiation was performed in an inert gas atmosphere at a speed of 10 m/min).

After this, 21) the paint-coated glass 7γ ipar was exposed for 2 seconds in an atmosphere at 0°C. The glass transition temperature of this ethama cured product was -25°C.

V-sampled glass fiber has good water resistance, boiling resistance, and water repellency.

Example 3 Polyether cretan, acrylate m fat (molecule jik
2000 Wood unsaturated acrylate M, 2 pieces/molecule)
100 parts of carpitol acrylate 1 OHB was added, and all of the electron beam curable material to be coated was obtained.

The above coating agent was applied to a glass 7-eyeper (90 μm in diameter) to a thickness of 2 μm (4i L, linear filament type electron beam). Using an accelerator, the coating material was flowed in the direction of the filament and the skewer, and the entire electron beam was irradiated in an inert gas atmosphere.During the irradiation of the electron beam in the direction of the linear filament, the electron beam energy was 60z and the electron beam energy was i:!2 (IOKV,
Electronic AM style 25mA7ch ft. The irradiation speed of the electron beam for C(1) was 250 m/min.

This was followed by after-heating at 280° C. for 1 frJ). The glass transition temperature of this cured coating is -30'C
Also, the strength and water resistance of glass fiber are good.

Example 4 Fuu, Phase-/ :/ 'It's a lil IJlf
(2EHA, i BA, ffEMA are all 111, L IIEA is introduced into the L/Tano reaction, unsaturated, !t Th introduced 1.% (1)) (Molecular 1
30 (10, molecule jl&]0 (2111 bonds per 10, tl, 5 pieces) 100 parts, To-L/ Thiokol 1
．． P-3 (polysulfide polymer manufactured by Toshi Thiokol Co., Ltd., I) 9 product names) 20 srs, iB body with Telonics fluoro glass upper body? 20 (Heat to 10-C, complete spinning of glass fibers, and immediately apply the above paint to a thickness of 50μ. 17 Linear filament!
Tube electron beam accelerator VC', J: The electron beam was irradiated in the VC direction parallel to the refilament at an electron beam irradiation speed of 400 m/molecule.

Thereafter, it was irradiated with a 20 KW ultraviolet lamp for 05 seconds.

The force transition temperature of this cured coating was 129'C.

The coated glass fiber had good breaking strength and water resistance.

Example 5 Epoxy acrylate resin (molecule jt fioo)
1110 parts, 20 parts of hexanediol diacrylate,
An electron beam curable paint was obtained containing 5 parts of trimerylolbroban triacrylate and 1 part of a silicone additive.

Immediately after spinning the glass fiber (diameter 100μ), which is the entire component of filtrate glass, the above-mentioned coating was coated so as to have a diameter of 0μ, and the coating was applied using a linear filament type electron beam accelerator.
Electron beam irradiation was carried out at 500 mA).

The glass transition temperature of the obtained coating was 82° C., and the breaking strength and water resistance of the obtained glass fiber were good.

Example b Frethane acrylate resin (700 parts) 100 parts, pentaerythritol triacrylate (20 parts), neobentyl glycol diacrylate) 20 parts, F6
An electron beam curable paint consisting of 1 part of additive was obtained.

4944' k 21) Spun glass fibers made entirely of silica glass by heating to 00'C, and immediately after that, apply the above paint to a thickness of 5()μ'' to form a scanning type turtle line. Irradiation speed 250m by accelerator
The electron beam was irradiated twice at /min.

Thereafter, one sheet of glass fiber was temporarily piled in a 311+1°C fume×7 enclosure. The glass transition width JW of this pickled product was 105°C.

The obtained glass fiber had good water resistance and breaking strength.

[Brief explanation of drawings]

Figures 1, 2 and 3 are 7 r1. This is a schematic diagram of the optical transmission glass fiber manufacturing apparatus used in the present invention.

Claims (1)

[Claims] (1) On the surface of the original transmission glass fiber, the force glass transition width of mosquito-like pickles is 120℃ or higher or 70℃ or higher.
Applying an electron beam curable composition of C or higher to 50 KeV
A method for producing a transmission fiber in which the F-ray curable coating composition is cured by irradiating with 111 consonant beams.