JPS61185572A - Covering material with high resistance to heat and water - Google Patents

Abstract

PURPOSE:The title material for coating light-transmission glass fiber that is composed of a compound which is prepared by addition reaction of (meth)acrylic groups through urethane bond to a hydroxyl-containing low-molecular-weight polyolefin, thus showing high resistance to heat and water. CONSTITUTION:The objective covering material is obtained by using mainly a compound which is prepared by adding (A) 10-70pts.wt. of a (meth)acrylate such as tetrahydrofurfuryl acrylate through (B) urethane bond or ester bond to (C) 100pts.wt. of terminal hydroxyl-containing polyolefin of low molecular weight, e.g., of 1,000-3,000.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating material with excellent heat resistance and water resistance, and particularly to a coating material with excellent heat resistance and water resistance suitable for coating optical transmission glass fibers.

Glass fibers used for optical transmission are fragile and easily damaged, and break with the slightest external force. Therefore, immediately after spinning the optical fiber, its surface is usually coated with a resin to protect it. Conventionally, thermosetting silicone resins have been mainly used as resin materials for such secondary applications, but due to the high price of the resin and the fact that they are thermosetting, they inherently have a slow curing speed. However, various proposals have been made regarding materials that are cured by ultraviolet rays and then coated as an alternative material.

However, the materials conventionally used as these ultraviolet curable materials are mainly based on polyester polyols or urethane acrylate modified products such as polyester polyols and polybutadiene diol, and these resin compositions are The material was not reliable enough to maintain its initial properties after long-term heat resistance or water resistance tests. In addition, regarding silicone-based ultraviolet curable resin materials, long-term reliability is
Although it maintains sufficient properties, the polysiloxane compound used as the raw material is expensive, and the disadvantage of the high price of thermosetting silicone materials has not been improved.

In view of such circumstances, the present invention aims to provide a coating material that is excellent in long-term heat resistance and water resistance, and is relatively inexpensive, and is suitable as a coating material for a glass fiber for optical transmission. .

That is, the present invention provides a heat-resistant and water-resistant material that is mainly composed of a compound in which an acrylic or methacrylic group is added to a low-molecular-weight polyolefin having a hydroxyl group at the end of the molecule through urethane bonding or ester bonding. It is an excellent next coating material.

Regarding the present invention, a compound in which an acrylic or methacrylic group is added to a low molecular weight polyolefin having a hydroxyl group at the molecular end via a urethane bond or an ester bond can be obtained by the following method. That is, low molecular weight polyolefins having a hydroxyl group at the molecular end are commercially available from Mitsubishi Chemical Industries, Ltd., and are telekilic polymers having a saturated hydrocarbon skeleton. There is no problem even if it is added.

Particularly suitable resins are resins having a molecular weight of 1,000 to a,000 and exhibiting a liquid state at room temperature.

Acrylic or methacrylic groups are added to the above-mentioned low molecular weight polyolefin resin, and the method of addition is, for example, by reacting diisocyanate with the hydroxyl groups contained in the resin, and then reacting the reaction product with diisocyanate. It is obtained by reacting the remaining incyanate with an acrylate or methacrylate compound having a hydroxyl group. As another example, it can be obtained by reacting acrylic acid, methacrylic acid, or derivatives of these acids with the hydroxyl groups of the above-mentioned low molecular weight olefin resin in the presence of a suitable catalyst.

The diisocyanate mentioned here includes tolylene diisocyanate, diphenylmethane diisocyanate), P-phenyl diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like.

In addition, acrylate or methacrylate having a hydroxyl group and 14.2-hydroxyethyl acrylate, 2-
Examples include hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, and the like.

The urethane acrylate or ester acrylate M resin obtained in this way can be used under heat and pressure at the cutting edge using a special coating device, but in general, it can be used with other low-viscosity acrylic compounds or methacrylic compounds. Dilute to lower viscosity before use. The dilution ratio is 10 parts by weight to 70 parts by weight for 100 parts by weight of the above resin. It is normal to do f part souna.

Examples of these reactive diluents include tetrahydrofuracrylacrylate, 2-hydroxy-8-phenyloxyglobyl acrylate, butoxyethyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethylene glycol Diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, l,6-hexanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate etc.

In addition to the above-mentioned components, the coating material according to the present invention may also contain various polymerization initiators, thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, surfactants, and the like.

When curing by ultraviolet curing, it is preferable to use a photopolymerization initiator. The amount added is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the above-mentioned acrylic (or methacrylic) adduct of the low molecular weight olefin resin and the reactive diluent. Examples of the types thereof include acetophenone, benzophenone, chloroacetophenone, propiophenone, thioxanthone, benzoin, benzyl, anthraquinone, and derivatives of these compounds.

In addition, when curing by heating, benzyl peroxide,
A peroxide such as cumyl peroxide may be added.

The amount of addition is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin composition (including diluent).
Parts by weight.

Of course, the method of curing the material of the present invention includes cases in which the above-mentioned ultraviolet ray curing and heat curing are performed alone, and cases in which these curing methods are combined. The coating may be applied to the original fiber by any conventional known method, and it may be applied to the fiber surface by squeezing with a die immediately after spinning and hardened.

Since the alpha material according to the present invention is polyolefin-based, it inherently has a low water absorption rate, and most of the main chain is composed of carbon-carbon bonds, so it is more heat resistant than conventional polyether-based or polyester-based coating materials. Highly sexual.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Weigh out 225f of a polyolefin resin that is liquid at room temperature and has a hydroxyl group at its terminal (hydroxyl value 49, molecular weight approximately 2000) into a flask with a specific capacity of 500 CC equipped with a thermometer, stirrer, gas inflow pipe, and reflux condenser. Then, 0.2 t of tin octylate was added as a catalyst, and m
-Tolylene diisocyanate) 84.8F was added and reacted for 2 hours while nitrogen gas was introduced. Next, 2-hydroxyethyl acrylate 28.2? and 0.8 f of hydroquinone monomethyl ether, and further reacted at a temperature of 70°C for 2 hours. For 100 parts by weight of the thus obtained next product, phenoxyethyl acrylate)
30 parts by weight and 4 parts by weight of benzoin isobutyl ether were added to obtain a material to be α having a viscosity of 6200 centipoise (25°C). (The characteristics are summarized in Table 1.) Example 2 A flask with a specific capacity of 500 cc was equipped with a thermometer, a stirrer, a gas inflow pipe, and a reflux condenser. 225 f (value 49, molecular weight approximately 2000) was weighed out, p-toluenesulfone rRO,2t was used as a catalyst, and benzene 20? , hydroquinone monomethyl ether 0.
2F and acrylic acid 209 were added, and the temperature was 100℃.
Let it react for 5 hours. Thereafter, the reaction product was washed with water to remove the catalyst, excess acrylic acid, and benzene. To 100 parts by weight of the product vIJ thus obtained, 80 parts by weight of phenoxyethyl acrylate and 4 parts by weight of benzoin isobutyl ether were added to obtain a coating material with a viscosity of 1800 centipoise (25° C.). (The characteristics are summarized in Table 1.) Comparative Example 1 Using the same 500 cc four-loaf flask as used in Example 1, polytetramethylene glycol (
Weigh out 2052 pieces of (hydroxyl value: 55, molecular weight: about 2000), add 0.2 f of tin octylate, and heat at 70°C.
While stirring with
4.8 T? was added and heated for about 2 hours under nitrogen gas flow. Then 2-hydroxyethyl acrylate 28.
2 f and hydroquinone monomethyl ether 0.8t
was added, and the reaction was further heated at 70° C. for about 2 hours. To 100 parts by weight of this reaction product, 80 parts by weight of phenoxyethyl acetate and 4 parts by weight of benzoin isobutyl ether were added to give a viscosity of 1200 cp.
(25°C) coating material was obtained.

Next, the coating materials obtained in Examples 1 and 2 and Comparative Example 1 were coated on the release film, and then heated at 80 W.
It was cured to a sheet with a thickness of about 200 μm using a 2 KW high pressure 71 [lamp] and a light irradiation amount of 500 mJ. Mechanical properties of the sheet-like sample thus obtained and 1
Table 1 summarizes the retention rates of mechanical properties after 30 days of heating at 20°C and after 80 days of 80°C water immersion treatment.

As can be seen from Table 1, the coating material according to the present invention exhibits excellent heat resistance and water resistance.

Further, the coating materials of Examples 1 and 2 were coated at 80 m, respectively.
The fibers were spun to a thickness of 125 μm at a speed of 125 μm, coated on the surface of a nine-nine fiber, and cured by irradiation with ultraviolet light using a Fusion Co., Ltd. ultraviolet irradiator (D Bulb) to an outer diameter of about 800 μm. The fiber does not break with in-line screwing (1 inch elongation), and the fiber breaking strength is 6
It was ~7 plums. However, the fiber wire obtained in this way showed no increase in transmission loss. Furthermore, even after heating the fiber wire at 80℃ for 80 days, there is little increase in transmission loss.

As described above, the coating material of the present invention exhibits excellent heat resistance and water resistance, and is extremely useful industrially.

Claims (1)

[Claims] 1. A coating material with excellent heat and water resistance that is mainly composed of a compound in which an acrylic or methacrylic group is added to a low molecular weight polyolefin having a hydroxyl group at the molecular end via a urethane bond or an ester bond. .