JPS5889616A - Curable resin composition for glass fiber coating - Google Patents

Abstract

PURPOSE:To obtain a resin composition for optical fiber coating, capable of high-speed coating, also with outstanding toughness and economical advantage, comprising as an essential component, a specific amount of an alicyclic epoxy resin having epoxy group(s) on the alicyclic ring(s). CONSTITUTION:The objective composition, a cationic-polymerizable, energy beam-curable resin composition containing a compound (photopolymerization initiator) capable of releasing an active catalyst triggering the polymerization by an energy beam irradiation (pref. ultraviolet), comprising, as an essential component, 20-95wt% of an alicyclic epoxy resin having epoxy group(s) on the alicyclic ring(s). The epoxy equivalent of said epoxy resin falls preferably in a range 70-250, and it is recommendable to use an epoxy resin of formulaI, II or III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention No. 111 relates to a curable resin composition for coating glass fibers, and particularly relates to a cationic polymerization type energy ray curable resin composition for use in a place where glass fibers for optical transmission are to be brazed.

In recent years, there has been remarkable progress in the technological development of optical fibers for optical communications, and they are now at the stage of practical application not only for public communications but also for a wide range of private needs, and further development is expected in the future. However, glass fibers (hereinafter referred to as Wako fibers) used as optical transmission media usually have a diameter of 200 μm or less for reasons such as maintaining flexibility.

In addition, the material is extremely brittle, so it is difficult to carry out work during manufacturing, storage, or cable production. [K] has the disadvantage that scratches are likely to occur and the optical fiber easily breaks when external stress is applied. For this reason, using optical fiber as it is as a medium for optical transmission is mechanical.

This is extremely difficult in terms of physical strength. It is also known that, as a property unique to glass fiber, its strength decreases over time due to the influence of moisture and the like.

To solve this problem, we use optical fiber.

The initial strength can be maintained by placing a protective cover such as v77JK plastic on the front of the optical fiber following the pulling process.
Additionally, methods have been proposed for manufacturing optical fibers that are strong enough to withstand long-term use. For example, JP-A-50-1
A liquid resin composition as shown in Publication No. 25754,
Alternatively, a liquid or a dispersion obtained by dissolving or dispersing a liquid or solid resin composition is used as a surface mKj of an optical fiber.
The optical fiber obtained by baking a cloth and then coating it with a thermoplastic resin composition by extrusion has sufficient strength and durability to withstand long-term use. In addition, as shown in British Patent No. 1=571e518, there is a method for improving the strength of an optical fiber by extruding a thermoplastic resin such as polyethylene terephthalate to improve its strength, and A method has been proposed in which a diacrylate polymer or the like is applied to a Hikari 7-IPA and cured.

Hitherto, a hookah coating method has been advantageously used as a plastic coating treatment method for protecting the surface of an optical fiber used to increase its tensile strength from mechanical and physical influences and damage.

In general, this lacquer fabric method uses a solution system, so
Drying section and high drying 1 to obtain effective cure drying rate
In addition, expensive solvent removal equipment is required to prevent environmental pollution of the solvent. Conventional methods for manufacturing optical fibers coated with glassy coating compositions include frequency furnaces, resistance heating furnaces, and acid-water bulk flames.

The method used was to install a coating composition coating device and a drying oven for electric heated shoes directly below a heat source such as a 00□ laser, and to roll the coating composition directly below or at right angles to the heat source. Therefore, in order to apply the composition immediately after spinning in the Hikari 7 EyePa and to dry it completely before it can be applied to the filling machine, the distance from the spinning furnace to the 11th floor should be kept well. It was necessary to install a drying oven or spin at a very uneven linear speed, and large equipment was required to increase productivity. In addition, due to problems with transmission characteristics of optical fibers, it is necessary to control the outer diameter to an accuracy of 1.0μ or less. is needed.

However, the present invention was developed in view of the actual situation as described above.

This was completed as a result of extensive research to eliminate various drawbacks of conventional resin compositions for coating glass fibers.

The purpose of the present invention is to take advantage of the fast-curing characteristics of a cationic polymerization-based energy ray-curable resin composition.

The object of the present invention is to provide an energy ray-curable resin composition for coating glass fibers that can be treated appropriately and has excellent strength.

Another object of the present invention is to
It is an object of the present invention to provide a method for fabricating glass fibers that is highly durable and has excellent strength by taking advantage of the fast-curing characteristics of a curable resin composition.

Hereinafter, the present invention will be explained in more detail.

In other words, the curable resin composition for glass fibers made by IJiK is a cationic polymerizable energy ray curable resin composition containing a compound that releases an active catalyst that initiates polymerization of the cationic polymerizable resin composition upon irradiation with energy rays. A cationically polymerized energy ray curable resin composition for coating glass fibers containing 20 to 95% by weight of an alicyclic epoxy resin having an epoxy group on an alicyclic ring as an essential component of the product. The curable resin composition for glass fibers of the present invention is applied immediately after spinning the optical fiber, and then cured and dried in a very short time by irradiating it with energy rays in a normal atmosphere. So.

The cough resin composition of the present invention is capable of processing at the line speed required for controlling the outer diameter, and can obtain a light 7 eyelid with a practically sufficient intensity. There is no need to cure under an inert gas atmosphere during energy embroidery irradiation, and there is no need for a drying oven, which saves a lot of equipment space.At the same time, since it is a solvent-free type, it reduces the work environment due to the splashing of solvents. The economic and industrial value of this improvement and the significant reduction in operating energy is extremely large.

The curable resin composition for coating glass fibers of the present invention is a compound that releases a substance that initiates cationic polymerization by irradiation with energy rays, which is polymerized or TM to form a coating film when irradiated with energy rays, which is known in the art. (Photopolymerization initiation)
A cationically polymerizable resin composition containing cationically polymerizable resin compositions, such as epoxy resin compositions that are polymerized by cationic ring-opening polymerization of epoxy rings, and cationically polymerizable compositions such as cyclic ethers, dichtons, and vinyl compounds (911 For example, special public service in 1977
-17040, as well as several other catalysts such as photosensitive onium salts described in Japanese Patent Publication No. 52-14278 etc.1, all of which are energy rays such as ultraviolet rays. Some produce Lewis acids when irradiated. ), etc., but it is a cationically polymerizable resin composition containing 20 to 95% by weight of an alicyclic epoxy resin having an epoxy group on an alicyclic ring as an essential component.

First, as the alicyclic epoxy resin having an epoxy group on the alicyclic ring, which is an essential component of the curable resin composition for coating glass fibers of the present invention, cyclohexene or cyclopentene ring-containing compounds are used, such as hydrogen peroxide, peracid, etc. There are cyclohexene oxide or cyclopentene oxide-containing compounds obtained by evaporation with a suitable oxidizing agent. Representative examples of these alicyclic epoxy resins include those represented by the following formulas.

0 0 0 0 The energy-curable resin composition of the present invention may include epoxy resins other than the above-mentioned #cyclic epoxy resins, cyclic ethers, vinyl ethers, tuctones, and thiran compounds.

A cationically polymerizable compound such as a vinyl compound can be used as a main ingredient or can be used in combination, and among these, epoxy resins are preferable. Examples of epoxy resins other than alicyclic epoxy resins having an epoxy group include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Here, preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic Tf@nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts and epichlorohydrin. Examples include glycidyl ether and epoxy novolac resin produced by reaction with Preferred examples of alicyclic epoxy resins other than those mentioned above include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring. Examples include glycidyl ethers produced.

Further preferred as the aliphatic epoxy resin Bit are aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof.

Polyglycidyl esters of aliphatic long chain dibasic acids.

There are homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate.

Representative examples 41 include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hequinanediol, triglycidyl ether of glyceryl,
Triglycidyl ether of trimethylated propane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, and one or more alkylene oxides (ethylene oxide , propylene oxide), and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of aliphatic alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these. Glycidyl esters of quaternary fatty acids can also be blended as diluents.

These aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins can be blended into the resin composition of the present invention depending on the desired performance, but energy ray curability, glass fiber base material From the viewpoint of adhesion, physical strength, etc., alicyclic epoxy resins having an epoxy group on an alicyclic ring such as a compound containing a cyclohexyl-7-oxide group or a cyclopentene oxide group as an essential component are
It is appropriate to contain l1tI in the range of ~95% by weight, and %
The preferred blending amount is 40 to 90% by weight. If the alicyclic epoxy resin is less than 20% by weight, the curing speed due to energy ray irradiation will be uneven, and it will be difficult to maintain the linear velocity in the continuously damaged type of glass fiber spinning, making it difficult to obtain practical productivity. At the same time, a high-strength fiber cannot be obtained.

On the other hand, in the case of a curable resin composition consisting solely of an alicyclic epoxy resin, the cured film tends to become brittle. Furthermore, the alicyclic epoxy resin that can be used is not strictly limited to the epoxy resin.

Although it can be selected from a wide range of materials, generally an epoxy-based cationic polymerizable resin composition mainly composed of an alicyclic epoxy resin having an epoxy i content in the range of 70 to 250 is used for adhesion to the substrate. % is preferable from the viewpoints of properties, physical strength, business handling, etc.

Note: 1) Curable resin composition for coating gas fibers of the present invention*
Unless the effects of the present invention are impaired, olefin resins, acrylic resins, ester resins, petroleum resins, and alkyd resins other than the cationically polymerizable substances listed in Km may be used to improve the properties of paints or coatings. fats, polyether compounds, polyether polyol compounds, vinyl acetate resins, vinyl chloride resins, pudetool resins, rubber resins, vinyl alcohol 411 fats, acid anhydride-based epoxy resin hardeners, epoxy resins, dyes .

It can also be used in combination with various paint additives.

In addition, in order to improve the adhesion between Gal) Sphapa and the resin composition, Kr-methacryloxypropyltrimethoxysilane, r-dalicidquinpropyltrimethoxysilane, vinyltriethoxysilane, r-glycidoxyv-5,5 −
Dimethyl-1-fluorenyltrimethoxy V9, r-p
Loapropyltrimethoxysilane, vinyltrimethoxysilane, β-(5,4-epoxycyclohexyl)ethyltrimethoxy Vlan, etc., and silanes made into polymers by partially hydrolyzing and condensing their alkoxy moieties. Coupling agents can be added to the compositions of the present invention.

Among these silane compounds, epoxyalcoxin compounds having an epoxy group at 41 are preferred, and 1 to 50% by weight is suitable for the compounding lid.

On the other hand, the metal compound (photopolymerization initiator) that releases a substance that initiates polymerization or crosslinking of the cationic polymerizable resin upon irradiation with energy rays, which is contained in the cationic polymerizable resin composition used in the present invention, is not particularly limited; Particularly preferred are double salts, which are onium salts that release Lewis acids capable of initiating polymerization upon irradiation. Such compounds basically have the general formula (II', r, ms, m', z)
Mxnulm"1 [In the formula, the cation is onium.

Zk@H5M * 8 * Jil・#
Ding @ * Pe Mu111 @ l11) *BL
O, halogen (for example! * are a!).

R', R"l R"* R' are organic groups which may be the same or different. atbeotd is an integer from O to black, a+b+o+- is equal to the valence of 2, and 0M is a metal or metalloid (1.talloid) which is the central atom of the /'-logenide complex.

B, P, Mu-, Bb at@Jn
e In e Muj g O& *Xn
sd1 # in # go e V * Or I
Mn reference Go et al. Summer is halogen, m is ^
is the net charge of the agenide complex ion, n is /%a
/1c1 is the number of gen atoms in the genide ion.

].

Such a catalyst precursor is itself omniscient.

For example, a compound in which 2 is 16 is disclosed in U.S. Patent No. 57082.
No. 94, Shima Shima No. 5949145, Shima @5194574, etc. Other onium catalyst precursors are Peru-Yu-Xu-Yu No. 828841 and Peru-J11112846?
No., Tsutsuns patent 1g227024? No. 4, U.S. Pat.
159455 etc.

The above diazoequum compounds are disclosed in the above mentioned US Patent No. 57082.
It can be obtained by the method described in No. 94, No. 5949145, etc. 2 is 8 degrees! Compounds that are l@*T* are J, 1cnaposyk et al.'s J, Mu, 0°! 1. ，
91.145 (194?), mu, t+, vayoooh
J, OrglnlO0Mm1-try #S 5
e A 8 # 2552 (1970), Goeth
1lulloo, ohlm of tls et al.

S.If-e 75a54d (1944), H.M.
Lsic・5tar et al.'s J-ni-0,8-e 51 e
5587 (1929) etc. can be made using the Ke@ method. 2 is p, N, As.

A typical onium salt that is 8b, Bi is J, Go・re
@l・r's M@thod@n dsr Orga
n1sh@n Ohi[se 1 1 /1 2
#591-440 (1?58), 12 of Ward Jam-・
/1.79112 (can be produced by the method described in 19!).A typical onium salt in which 2 is a halogen is 0.mu, ptitsyna et al. DOkl@mu (!ad, Nau
k-sBI5Rt 165 m 585 (1945)
, 1, Dr@Xi@r et al. J, Mu, a, s, e 75
It can be manufactured by the method described in #2705 (195!S) etc. In addition, Onium #IiK referred to here is the U.S. Patent No. 4
Bylylium salts such as thiopyrylium described in No. 159655 and I! #Oxonium salts such as aryloxysulfoxonium salts described in Publication #B54-8428 4. I get caught.

Examples of other compounds that can be used to initiate the polymerization of epoxy equivalents are iodoform, alpha, alpha-dibromoparaxylene, bromoform, carbon tetrachloride, hexachloroparaxylene, and U.S. Pat. Other catalysts listed in.

These are organic halogen compounds such as bis(per7σ loalkylsulfonyl) methane salts and diazonium salts of methane described in US Pat. No. 5,551,4416.

Furthermore, as proposed in U.S. Pat. No. 4,415,4055, the cationically polymerizable 4# resin composition used in the present invention may be blended with an acrylate or methacrylate compound and a carbonyl photosensitizer to improve coating film performance and curability. Improvements are also possible.

To coat the glass fiber base material table WJK*IA Ming's resin composition, conventionally known methods such as IpH, a method of passing a small hole at the tip of a tapered metal tip, a dipping method, etc. are used. Fiber can be spun directly fK&cloth. At that time, in order to improve the paintability and adhesion to the base material, the resin composition may be coated after the base material, l1II]1VcIII treatment has been dissolved, or the resin composition may be coated with the resin composition to the extent that there is no adverse effect such as deterioration of performance. It can be applied with the addition of an anti-warming agent. &
The thickness of the 1 value version varies widely depending on the type of S material and required performance.
Although iIK can be varied, a range of approximately 5 to 100 μι is generally appropriate.

The scissors-curable resin composition of the present invention was applied to a glass fiber substrate Km.
Energy rays for forming a hardened coating include ultraviolet rays, electron beams, and radiation, and among these, ultraviolet irradiation is the simplest method from a practical point of view.

Furthermore, the formation of a cured film using the IIi-supporting resin composition can be performed by applying heat to the base material or while applying heat, or by applying a combination of heat treatment and energy ray irradiation after applying the coating resin composition to the base material. In this way, it can be promoted even more effectively.

The curable resin composition of the present invention is glass fiber (.

Spinning and coating continuous glass fiber for optical transmission in 4%! !
It can be applied as a coating treatment agent for primary coating and secondary coating.

Hereinafter, representative examples of the present invention will be explained in detail using actual examples, but the present invention is not limited by the following examples. do.

Practical Example 1 An optical fiber manufacturing device was used to spin a graded optical fiber whose main component was quartz glass, and the diameter was approximately 1.
A 50μ optical fiber was manufactured. Next, 5,4-epoxycyclohexylcarboxylate (epoxy equivalent: 151-14)
0 parts, 15 parts of 1,4-butanediol diglycidyl ether (11125-143 per epoxy), 5 parts of dipropyltrimethoxysilane in r-glycid, 0.5 parts of silicone surfactant and photopolymerization initiator pp- 35 (Asahi Denka Kogyo H4) 5 parts was applied to the optical fiber immediately after spinning, and irradiated with ultraviolet rays using 5 ultraviolet lamps with an output of 2 mm.
The maximum linear velocity possible in this case is 100 IlZ, and the obtained light? Aipa's tensile strength to break was 490 kp/-.

Iso 912 Heat the optical fiber base material to approximately 2,000°C and draw at a drawing speed of 8
A monofilament optical 7-iper with a fiber diameter of 150 μm was produced by drawing at a speed of 0 μm/min.
Epoxycyclohexylmethyl-5,4-epoxycyclohexylcarboxylate (epoxy equivalent 151-1
45) 60 parts, Tts(5,4-epoxycyclohexylmethyl)adipate (epoxy equivalent 180-200)
15 parts, trimethylolpropane triglyphdyl ether (epoxy equivalent weight 155-165) 15m, β-(5#
4-, :C7N xylp.

10 parts of ethyltrimethoxy 7ran.

0.5 part of silicone surfactant and photopolymerization initiator pp
-5s (regional chemical industry 11M) Energy I consisting of sM
The Li curable resin composition was applied to the optical fiber immediately after spinning using a die, and then cured by irradiation with ultraviolet rays (output 21 CW x 5). This coating composition was completely cured, and a uniform film with an average thickness of 15 μm was obtained. The average breaking strength of the optical fiber obtained by Tonoyo 5C is 505k.
g/w2.

Example 3 Bisphenolm siglycidyl ether (epoxy fiJ1180-200) 10@, 5,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl was deposited on an optical fiber with a diameter of about 1JO#m mainly composed of quartz glass. Carboxylate (epoxy equivalent weight 131-145)
70 parts, 1,4-butanediol diglycidyl ether (t125-145 per epoxy), 10 parts, β-(5,4
Energy ray curing consisting of 1 part of epoxycyclohetertrimethoxysilane, 1 part of silicone surfactant, and 4 parts of photopolymerization initiator TO-508 (manufactured by Nesota Mining and Manufacturing Co., Ltd.) Immediately after spinning, the resin composition is applied using die JK, and then exposed to ultraviolet rays (
The product was cured by irradiation with a power of 2 KW The maximum possible linear velocity in this case was 120 ml/min, and the average #im breaking velocity of the obtained optical fiber was 510:11/2. Also,
Even when this optical fiber was wound around a rod having a diameter of 2 m, it did not break.

Comparative Example 1 75 parts of bisphenol cyglycidyl ether (epoxy equivalent: 180-20G), 10 parts of 5#4-epoxycyclohexylmethyl-5,4-epoxycyclohexylcarboxylate (epoxy equivalent: 151-145), 1.
4-butanediol diglycidyl ether (epoxy equivalent weight 125-145) 1 part 5 parts, v9 co-y system rMw7
When a comparative example composition other than the present invention consisting of 0.5 parts of i-type agent and 5 parts of photopolymerization initiator PP-33 (manufactured by M Denkako Jl) was cured with energy rays in the same manner as in Example 1, The maximum possible linear velocity was about 15-/min, which was insufficient for practical linear velocity. Further, the average breaking strength of this coated optical fiber was 520 k)/-, which was lower than that of the optical fiber coated with the resin composition of the present invention.

Comparative Example 2 Phenol novolak epoxy resin (epoxy equivalent: 1
70-18G) 50 parts, bisphenolmuciglycidyl ether (epoxy equivalent 180-200) f5 parts, bis(3,4-epoxycyclohexylmethyl)adipate (epoxy equivalent 180-200) 15 parts, trimethylolp O/<triglycidyl Ether (epoxy equivalent 1
55-145) 20 parts, silicone surfactant 0.5
A comparative example composition other than the present invention consisting of 1 part and 4 parts of photopolymerization initiator FO-508 (Kenneso I-Mining & Mani 7 Acteering Co., Ltd. J1) was irradiated with ultraviolet rays in the same manner as in Example N5. However, the maximum linear speed was 20 min/min, and the curing speed was much slower than that of the composition of the present invention. Moreover, the minimum bending diameter of this coated optical fiber is 5-
The bending strength was inferior to that of the optical fiber coated with the resin composition of the present invention.

Claims (1)

[Scope of Claims] t A cationic polymerization type energy ray curable resin composition containing a compound that releases an active catalyst that initiates polymerization of the cationic polymerization type resin composition upon energy irradiation, an alicyclic resin composition as an essential component. A cationically polymerized energy ray-curable resin composition for coating glass fibers, which contains 20 to 95% by weight of an alicyclic epoxy resin having an epoxy group on the formula ring. 2. Containing 40 to 90% by weight of an alicyclic epoxy resin having an epoxy group on the alicyclic ring is 1! #Imitate 4
? A cationic polymerizable energy ray curable resin composition for use in gas 7 aiper as described in item 1 of the scope of the invention. (5) Claim 1st or 2nd claim, characterized in that it contains 191-1 to 50% by weight of the eboxyalkoxycycne compound 191-1. ! The cationic polymerizable energy ray-curable resin composition for coating glass fibers described in J. 4. The glass 7 eyelid according to claim 11 or 112, characterized in that the alicyclic epoxy resin having an epoxy group on the alicyclic ring has an epoxy content in the range of 70 to 250. A thionic polymerized 5-based energy curable resin composition.