JP2784339B2 - Optical fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical fiber obtained by applying a resin composition having ultraviolet curability to glass fiber and curing the glass fiber.

[0002]

2. Description of the Related Art Glass fibers used in optical fibers are brittle and easily damaged, and are coated with an ultraviolet (UV) curable resin for protection and reinforcement. From the viewpoint of long-term reliability, it is necessary for the UV-curable resin to have a small change in the Young's modulus over time. For this purpose, the content of the uncured material in the UV-curable resin film is low. Required. That is, since the transmission characteristics of an optical fiber are strongly affected by the physical properties of the coating of the UV-curable resin, specifically, the Young's modulus, etc., a high content of the uncured resin in the UV-cured resin indicates that the uncured resin has a high content. Causes a change in physical properties over time as compared with the case where the content of is low. Direct causes of this change in physical properties include post-polymerization of the uncured resin, bleeding of the uncured resin from the UV-cured resin, and the like.

[0003]

The UV-curable resin compositions for coating optical fibers conventionally used have a relatively high curing speed, but are not suitable for improving the productivity of optical fibers. When the drawing speed from the material is increased, there is a problem that in the subsequent coating step with the UV curable resin, the amount of UV irradiation decreases, and the content of the uncured resin in the UV curable resin increases.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventionally used UV-curable resin composition for coating an optical fiber, and provides a resin composition for coating an optical fiber having an excellent UV curing rate with a glass. An object of the present invention is to provide an optical fiber which is applied to a fiber and cured.

That is, the present invention provides (A) a polyether polyol-based urethane oligomer having an ethylenically unsaturated group, (B) a reactive diluent, (C) a general formula (I)

Embedded image (Wherein R ¹ , R ² and R ³ may be the same or different and are monovalent organic groups). A resin composition containing the compound represented by the formula is applied to glass fiber and cured. It does not provide optical fibers.

The component (A) used in the present invention is a polyether having preferably 2 to 5, more preferably 2 to 3, ethylenically unsaturated groups such as (meth) acrylic acid in one molecule. Polyol-based urethane oligomers can be mentioned. The polyether polyol urethane oligomer having an ethylenically unsaturated group is a diol having a polyoxyalkylene structure composed of at least one oxyalkylene group having 2 to 10 carbon atoms (hereinafter, simply referred to as “polyoxyalkylene structure”); It is obtained by reacting a (meth) acrylic compound having a hydroxyl group with diisocyanate.

Examples of the diol having a polyoxyalkylene structure include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol, and two or more ion-polymerizable cyclic compounds. And a polyether diol obtained by ring-opening copolymerization of Here, as the ion-polymerizable cyclic compound, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, Tetraoxane, cyclohexene oxide,
Styrene oxide, epichlorohydrin, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, glycidyl benzoate, etc. Cyclic ethers. Further, the above ion-polymerizable cyclic compound, a cyclic imine such as ethyleneimine, p-
Polyether diols obtained by ring-opening copolymerization with cyclic lactones such as propiolactone and glycolic lactide or cyclic siloxanes such as dimethylcyclopolysiloxane can also be used. Specific combinations of the two or more ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and the like. it can. Further, a ring-opening copolymer of two or more ion-polymerizable cyclic compounds may be bonded at random. Further, diols having a polyoxyalkylene structure include, for example, PTMG1000 (Mitsubishi Kasei Kogyo Co., Ltd.), PTMG2000 (same as above), PPG1000
(Asahi Orin Co., Ltd.), PPG2000 (same as above), EXC
ENOL2020 (same as above), EXCENOL1020
(Same as above), PEG1000 (Nippon Oil & Fats Co., Ltd.), Unisafe DC1100 (same as above), Unisafe DC1800
(Same as above), PPTG2000 (Hodogaya Chemical), PPTG
1000 (same), PTG400 (same), PTGL200
It can also be obtained as a commercial product such as 0 (the same).

In the present invention, these diols having a polyoxyalkylene structure may be used in combination with diols and / or diamines having no polyoxyalkylene structure. Here, examples of the diol having no polyoxyalkylene structure include polyester diol, polycaprolactone diol, and polycarbonate diol. Examples of the polyester diol include polyhydric alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol, and phthalic acid, isophthalic acid, terephthalic acid, and maleic acid. Polyester diols obtained by reacting with a polybasic acid such as acid, fumaric acid, adipic acid, sebacic acid and the like. As polycaprolactone diol, ε-caprolactone and, for example, ethylene glycol, tetramethylene glycol, 1,6
-Hexanediol, neopentyl glycol, 1,4
-Polycaprolactone diol obtained by reacting a divalent diol such as butanediol. As the polycarbonate diol, DN-980 (Nippon Polyurethane Co., Ltd.), DN-981 (same as above), DN-982
(The same), DN-983 (the same), PC-8000 (US P
PG). Examples of the diamine include diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, and 4,4'-diaminodiphenylmethane, diamines containing a hetero atom, and polyetherdiamines.

Examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate,
Pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 1,4
-Butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-
Hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, and (meth) acrylate represented by the following structural formula Can be.

Embedded image

Embedded image (Wherein R ⁴ is a hydrogen atom or a methyl group, and n is 1
Among them, 2-hydroxyethyl (meth) acrylate can be mentioned as a preferable example.

Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, and p-phenylene diisocyanate. 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Examples thereof include bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, and lysine diisocyanate.

The number average molecular weight of the polyether polyol-based urethane oligomer having an ethylenically unsaturated group used in the present invention is preferably from 1,000 to 7000, and particularly preferably from 1,500 to 5,000. When the number average molecular weight of the polyether polyol-based urethane oligomer is less than 1,000, the elongation at break of the cured product of the obtained composition is reduced, and the toughness is easily reduced. Is likely to cause transmission loss, and the number average molecular weight is 70
If it exceeds 00, the viscosity of the composition becomes high and it becomes difficult to handle.

In the present invention, in addition to the polyether polyol-based urethane oligomer having an ethylenically unsaturated group as the component (A), a polyester polyol-based urethane oligomer having an ethylenically unsaturated group, a polycaprolactone polyol-based urethane oligomer, or the like may be used. In this case, the proportion of the polyoxyalkylene structure in the component (A) is also 50-
It is preferably 98% by weight, particularly preferably in the range of 60-93% by weight, most preferably in the range of 70-90% by weight. If the proportion of the polyoxyalkylene structure in the component (A) is less than 50% by weight, the low-temperature side Young's modulus of the cured product increases, and when used as a coating material for an optical fiber, it tends to cause transmission loss of the optical fiber. .
In the present invention, the proportion of the ethylenically unsaturated group in the component (A) is usually 0.5 to 10% by weight, preferably 1 to 8% by weight.

The compounding ratio of the component (A) in the resin composition applied in the present invention is usually 14 to 70% by weight,
Preferably it is 16-60% by weight. When the proportion of the component (A) is less than 14% by weight, the elongation at break of the cured product of the obtained composition decreases, and when it exceeds 70% by weight, the viscosity of the composition increases and the handleability tends to deteriorate. . The component (B) used in the present invention is a compound which is liquid at ordinary temperature and has at least one ethylenically unsaturated group in a molecule acting as a reactive diluent for the component (A).

Embedded image (The average value of n is 1-3), a compound represented by the formula:

Embedded image (The average value of p is 1-12), isobornyl acrylate, vinylpyrrolidone, and the like, and two or more of these may be used as desired.

In addition to the above reactive diluents, the following monofunctional compounds and polyfunctional compounds may be further added as reactive diluents. For example, when a cured product having a relatively low elastic modulus is desired, a monofunctional compound may be mainly used, but the elastic modulus of the cured product may be adjusted by using a polyfunctional compound in an appropriate ratio. it can.

Next, such reactive diluents will be exemplified. Monofunctional compounds: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methyltriethylene glycol (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, lauryl (meth) acrylate, N-vinyl Rorakutamu, vinyl phenol,
Acrylamide, vinyl acetate, vinyl ether, and styrene Multifunctional compound: trimethylolpropane tri (meth)
Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate,
Tricyclodecane dimethanol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, tris-2-hydroxyethyl isocyanurate tri (Meth) acrylate, and tris-2-hydroxyethyl isocyanurate di (meth) acrylate The mixing ratio of these reactive diluents in the resin composition applied in the present invention is usually 10 to 70% by weight,
It is preferably 15-60% by weight.

In the present invention, the component (C) is a compound represented by the above general formula (I). The component (C) is a compound that functions as a photopolymerization initiator when the components (A) and (B) are UV-cured. In the above general formula (I), R ¹ , R ² and R ³ represent methyl, ethyl, propyl, butyl, amyl, hexyl,
Heptyl, octyl, ethylhexyl, isononyl, dimethylheptyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, norbornadienyl, madamamantyl Group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, phenyl group, methylphenyl group, ethylphenyl group, trimethylphenyl group, tertiary butylphenyl group, ethoxyphenyl group, isopropylphenyl group, methoxyphenyl group, dimethoxyphenyl Enyl group, isopropoxyphenyl group, thiomethoxyphenyl group, naphthyl group, thiophenyl group, pyridyl group, dimethylphenyl group, dimethoxyphenyl group, chlorophenyl group, dichlorophenyl group, dibu Mophenyl, chloromethoxyphenyl, chloromethylthiophenyl, trimethylphenyl, trimethoxyphenyl, tetramethylphenyl, dimethylbutylphenyl, naphthyl, dimethylnaphthyl, dimethoxynaphthyl, dimethoxy Chlornaphthyl group, dimethoxynaphthyl group, trimethylpyridyl group, dimethoxyfuran group, trimethylthiophene group,-
A group represented by OY (where Y is a methyl group, an ethyl group,
Isopropyl, n-propyl, n-butyl, amyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, chlorophenyl,
Dichlorophenyl, methylphenyl, ethylphenyl, isopropylphenyl, tertiary butylphenyl, diethylphenyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, thiophenyl, pyridyl, etc.) And the like.

Among the compounds represented by the above general formula (I),

Embedded image The compound represented by is mentioned as a preferable compound.
The compound represented by the general formula (I) is a compound that functions as a photopolymerization initiator when the components (A) and (B) are UV-cured. By using the compound represented by the general formula (I) as a photopolymerization initiator, the resin composition for coating an optical fiber can be more quickly cured. Therefore, it is possible to improve the productivity of the optical fiber without affecting the physical properties of the UV curable resin.

In the present invention, a photopolymerizing agent such as benzyl ketal, benzoin ether, benzoin ester or benzophenone may be used in combination as the component (C).

The amount of the component (C) is preferably about 0.1 to 10% by weight of the composition. If the amount is too small, the effect of the present invention cannot be sufficiently exhibited,
If the amount is too large, no further improvement in the curing speed can be expected, and practically, it is preferably within the above range. In addition, the resin composition applied in the present invention includes epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, SBS (styrene /
Butadiene / styrene block copolymer) and its hydrogenated products SEBS, SIS (styrene / isoprene / styrene block copolymer), petroleum resin, xylene resin, ketone resin, fluorine-based oligomer, silicone-based oligomer,
A polymer or oligomer such as a polysulfide-based oligomer can be blended.

Further, various additives other than those described above, for example, antioxidants, coloring agents, ultraviolet absorbers, leveling agents, storage stabilizers, leaching agents, lubricants, solvents, fillers, antioxidants, wetting improvers, coatings A surface improving agent and the like can be added as needed.

The viscosity of the resin composition applied in the present invention thus prepared is usually from 1,000 to 20,000.
cp / 25 ° C, preferably 2000-10000 cp / 25
° C.

[0022]

The present invention will be further described below with reference to examples. In the following, “parts” means “parts by weight”. Example 1 1 mol of polytetramethylene glycol having a number average molecular weight of 2000, 1 mol of polypropylene glycol having a number average molecular weight of 3000, 3 mol of tolylene diisocyanate and 2 mol
To 60 parts of a polyether-based urethane acrylate oligomer (hereinafter referred to as oligomer A) obtained by reacting at a rate of 2 mol of hydroxyethyl acrylate,

Embedded image Reactive diluent represented by the formula (trade name T by Nippon Kayaku Co., Ltd.)
C-110S) 10 parts and formula

Embedded image 30 parts of a reactive diluent (ARONIX M-114 manufactured by Toa Gosei Chemical Co., Ltd.) represented by the following formula, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin manufactured by BASF)
LR8728) was added to obtain a composition A.

Example 2 Example 1 was repeated except that the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was changed to 0.5 part.
In the same manner as in the above, a composition was obtained. The obtained composition was used as composition B
And

Example 3 2 mol of polytetramethylene glycol having a number average molecular weight of 2000, 3 mol of isophorone diisocyanate and 2 mol of
And 60 parts of a polyether polyol-based urethane acrylate oligomer obtained by reacting at a ratio of 2 mol of hydroxyethyl acrylate (hereinafter referred to as oligomer B), 10 parts of a reactive diluent TC-110S and 10 parts of ARON
IX M-114, 30 parts, and 2,4,6-
Composition C was prepared by mixing 0.1 part of trimethylbenzoyldiphenylphosphine oxide.

Example 4 Copolymerized polyether polyol of tetrahydrofuran having a number average molecular weight of 2,000 and 2- and 3-methyltetrahydrofuran (PTGL20 (trade name, manufactured by Hodogaya Chemical Co., Ltd.))
00) Reactive with 60 parts of a polyether polyol urethane acrylate oligomer (hereinafter referred to as oligomer C) obtained by reacting 2 mol, 3 mol of 2,4-tolylene diisocyanate and 2 mol of 2-hydroxyethyl acrylate. A diluent TC-110S, 10 parts and ARONIX M-114, 30 parts were added, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1.5 parts was blended to obtain a composition D.

Example 5 2 mol of polypropylene glycol having a number average molecular weight of 3000, 3 mol of 2,4-tolylene diisocyanate and 2 mol
-60 parts of a polyether polyol-based urethane acrylate oligomer (hereinafter referred to as oligomer D) obtained by reacting at a ratio of 2 mol of hydroxyethyl acrylate, a reactive diluent TC-110S, 10 parts and ARON
IX M-114, 30 parts, and 2,4,6-
Composition E was prepared by mixing 10 parts of trimethylbenzoyldiphenylphosphine oxide.

Example 6 To 30 parts of oligomer B shown in the previous example, 30 parts of oligomer D, 10 parts of reactive diluent TC-110S and 30 parts of ARONIX M-114 were added, and 2,4,6 -Composition F was prepared by mixing 5 parts of trimethylbenzoyldiphenylphosphine oxide and 0.1 part of benzophenone.

Example 7 Polycaprolactone diol 2 having a number average molecular weight of 2000
Mole, 2,4-tolylene diisocyanate at a ratio of 3 moles and 2-hydroxyethyl acrylate at a ratio of 2 moles, and 30 parts of a polycaprolactone polyol-based urethane acrylate oligomer (hereinafter referred to as oligomer E) and 30 parts of an oligomer C , Reactive diluent TC
-110S 10 parts and ARONIX M-114
30 parts, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.5 part and benzyldimethyl ketal (trade name I, manufactured by Ciba Geigy)
(RGACURE651) 0.5 part to obtain a composition G.

Example 8 2 mol of a polycarbonate diol having a number average molecular weight of 2,000 (trade name: DN982, manufactured by Nippon Polyurethane KK)
30 parts of oligomer B is added to 30 parts of a polycarbonate polyol-based urethane acrylate oligomer (hereinafter referred to as oligomer F) obtained by reacting 3 mol of isophorone diisocyanate and 2 mol of 2-hydroxyethyl acrylate, and reactive diluent TC- 110S 1
0 parts and 30 parts of ARONIX M-114,
To this, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was blended to obtain Composition H.

Example 9 Polyether polyol-based urethane acrylate oligomer obtained by reacting 1 mol of polytetramethylene glycol having a number average molecular weight of 2,000, 2 mol of 2,4-tolylene diisocyanate and 2 mol of 2-hydroxyethyl acrylate (This is called oligomer G) 6
The reactive diluent tricyclodecane dimethanol diacrylate (trade name: SA1002, manufactured by Mitsubishi Yuka Co., Ltd.) is used in 0 part.
20 parts, isobornyl acrylate, 10 parts and N-
10 parts of vinylpyrrolidone were added, and 2,4,6-
Composition I was prepared by mixing 0.5 parts each of trimethylbenzoyldiphenylphosphine oxide and bendimethylketal.

Example 10 2 mol of polytetramethylene glycol having a number average molecular weight of 2000, 2 mol of isophorone diisocyanate and 2 mol of
-60 parts of a polyether polyol-based urethane acrylate oligomer (hereinafter referred to as oligomer H) obtained by reacting at a ratio of 2 mol of hydroxyethyl acrylate, 20 parts of a reactive diluent SA1002, 10 parts of isobornyl acrylate and N- 10 parts of vinylpyrrolidone was added, and 1.0 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was added thereto.
And

Example 11 2 mol of copolymerized polyether polyol of tetrahydrofuran and propylene oxide (PPTG2000, manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight of 2,000, 3 mol of isophorone diisocyanate and 2 mol of 2-hydroxyethyl acrylate To 60 parts of a polyether polyol-based urethane acrylate oligomer (hereinafter referred to as oligomer I) obtained by reacting at a ratio of 100 parts, 20 parts of reactive diluent SA100, 10 parts of isobornyl acrylate and 10 parts of N-vinylpyrrolidone were added. Then, 1.0 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was added to the mixture to obtain composition K.

Example 12 40 parts of oligomer G were added to 20 parts of a urethane acrylate oligomer obtained by reacting 2 moles of 2-hydroxyethyl acrylate with 1 mole of 2,4-tolylene diisocyanate (hereinafter referred to as oligomer J). , Reactive diluent SA1002, 20 parts, isobornyl acrylate 10 parts and N-vinylpyrrolidone 10 parts, to which 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5.0 parts and benzophenone 0.
One part was blended to obtain composition L.

Example 13 20 parts of a urethane acrylate oligomer obtained by reacting 1 mol of isophorone dissocyanate with 2 mol of 2-hydroxyethyl acrylate (hereinafter referred to as oligomer K), 40 parts of oligomer H, Diluent S
A1002, 20 parts, 10 parts of isobornyl acrylate and 10 parts of N-vinylpyrrolidone were added.
Composition M was prepared by mixing 0.1 part of 4,6-trimethylbenzoyldiphenylphosphine oxide.

Example 14 1 mol of bisphenol A ethylene oxide added diol having a number average molecular weight of 400 (DA400 manufactured by NOF Corporation)
10 parts of a urethane acrylate oligomer (hereinafter referred to as oligomer L) obtained by reacting 2 moles of 2,4-tolylene disocyanate with 2 moles of 2-hydroxyethyl acrylate and 40 parts of oligomer G and 10 parts of oligomer J Parts, 100 parts of reactive diluent SA1002, 10 parts of isobornyl acrylate and 10 parts of N-vinylpyrrolidone, and 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was added thereto. The product was designated as N.

Comparative Example 1 Instead of 1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone (trade name IRG manufactured by Ciba Geigy) was used.
ACURE 184) A composition was obtained in the same manner as in Example 1 except for using 1 part. The obtained composition was used as composition P.

Comparative Example 2 A composition was obtained in the same manner as in Example 1 except that 0.5 part of 1-hydroxycyclohexylphenyl ketone was used instead of 1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide. . The obtained composition was used as composition Q.

Comparative Example 3 Reactive diluent TC-110S, 1
0 parts and 30 parts of ARONIX M-114,
This was mixed with 1.0 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to obtain composition R.

Comparative Example 4 Reactive diluent SA-1002, 60
0 parts, isobornyl acrylate, 10 parts, and N-vinylpyrrolidone, 10 parts were added, and 0.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was added thereto to obtain composition S.

Comparative Example 5 0.5 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethyl ketal 0.1 part
A composition was obtained in the same manner as in Example 9, except that 3.0 parts of 1-hydroxycyclohexylphenyl ketone was used instead of 5 parts. The obtained composition was used as composition T.

Test Example Using an optical fiber drawing apparatus, two layers of the compositions prepared in each example were applied to an optical fiber according to the combinations shown in Table 2.
Further, the coated optical fiber was obtained by irradiating ultraviolet rays. The average optical fiber diameter of the core material of the coated optical fiber was about 125 μm, and the diameter of the coated optical fiber was 200 μm after the soft material was applied and cured, and 250 μm after the hard material was applied and cured.

Drawing speed 180, 360, 720 m / min
Regarding the three levels, coated optical fibers were collected and subjected to the following evaluation.

1. Curing degree 1) Gel fraction The coated optical fiber was cut into a length of 4 cm, and the weight was weighed.
(After initial weight is W ₀And ), Soxhlet extraction
Extraction for 12 hours using methyl ethyl ketone as a solvent
Issued. Thereafter, the coated optical fiber is dried in a vacuum dryer.
After drying at 50 ° C for 12 hours, and then leaving at room temperature for 1 hour
The weight was weighed. (Dry weight W₁And ) Further, the coated optical fiber is heated in an electric furnace at 700 ° C. for 30 minutes.
Baking for a while to remove the coating layer, collect only the optical fiber and weigh it
Was weighed. (Weight of optical fiber is W_FAnd ) The gel fraction of the coating layer of the coated optical fiber is calculated from the following formula.
did.2) Young's modulus (hard layer) The coated layer of the coated optical fiber is longitudinally moved with a cutter knife.
To make a 4 cm long coating layer test piece. Crossing the specimen
The plane is enlarged by a projector, and the cross-sectional area of only the hard layer is obtained.
Prepare 4 aluminum plates 1cm wide, 3cm long, 1mm thick
You. Separate the upper and lower ends of the test piece at intervals of 2 cm in length.
And sandwiched between aluminum plates and fixed with adhesive.
The upper and lower aluminum plates are sandwiched between chucks of a tensile tester
A tensile test was performed. Test at a pulling speed of 1 mm / min.
Rate was determined.

2. Environmental test 1) Light resistance A coated optical fiber drawn at 360 (m / min) was treated under the following conditions and then evaluated as follows. Conditions 30 days under fluorescent light (illuminance: 2000 lux) Evaluation item Appearance change Weight change Hydrogen gas generation amount 2) Moisture / heat resistance The coated optical fiber drawn at 360 (m / min) was treated under the following conditions and then evaluated as follows. . Conditions: Placed in an environment of 65 ° C. and 95% relative humidity for 30 days. Evaluation items Appearance change Weight change --Evaluation method-- a) Observation of appearance The hue was visually observed. The presence or absence of voids, peeling, droplets, and foreign matter at the interface between the coating layer and the fiber / coating layer was observed under a microscope. b) Weight change Weight changes before and after various environmental tests were determined by the following method. Weight of coated fiber before environmental test = Wa Weight of coated fiber after environmental test = Wb The coated fiber after the environmental test was placed in an electric furnace at 700 ° C for 30 minutes.
Baking for 2 minutes to remove the coating layer, and recovering only the optical fiber and calculating the weight = Wf c) Hydrogen gas generation amount measurement method The coated optical fiber was sieved, placed in a vial of known capacity, and heated at 100 ° C for 4 hours. Next, gas was sampled from the headspace portion of the vial using a gas tight syringe, and introduced into gas chromatography to quantify the amount of hydrogen gas generated. The quantification was performed by the absolute calibration curve method.

The compositions of Examples and Comparative Examples are shown in Tables 1 and 2.

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

As described above, the optical fiber of the present invention can be manufactured with a higher productivity than ever before. Further, the optical fiber of the present invention has a small amount of hydrogen gas that adversely affects transmission loss even after an environmental test, and has high long-term reliability.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Katsushi Igarashi 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Brian Hanrahan United States of America 19403 Norristown, Wellington Road 618 (56 References JP-A-59-170155 (JP, A) JP-A-61-98716 (JP, A) JP-A-60-83907 (JP, A) JP-A-55-13794 (JP, A) 60-176953 (JP, A) JOURNAL OB RADIAT ION CURING OCTOBER 1983 October 1983, pp. 16-21 (58) Fields investigated (Int. Cl. ⁶ , DB name) C03C 25/02 C08F 299/06 C08F 2 / 50

Claims (1)

(57) [Claims] (A) 14-70% by weight of a diol having at least one oxyalkylene group structure having 2 to 10 carbon atoms, a (meth) acrylic compound having a hydroxyl group, and a diisocyanate obtained by reacting A polyether polyol-based urethane oligomer having an ethylenically unsaturated group, wherein the polyoxyalkylene structure in the component (A) is 50 to
98% by weight, the number average molecular weight of the component (A) is from 1,000 to 7000
The ratio of the ethylenically unsaturated group in the component (A) is 0.1.
(B) 10-70% by weight. A compound represented by And at least one reaction diluent selected from isobornyl acrylate and vinylpyrrolidone; An optical fiber obtained by applying a resin composition containing the compound represented by the formula (1) to a total amount of 100% by weight on a glass fiber and curing the resin composition.