JPH06138355A - Composite reinforced material for optical fiber cable and production thereof - Google Patents

Abstract

PURPOSE:To provide a composite reinforced material for the optical fiber cable having high strength, high toughness and excellent moisture resistance by improving the adhesive property of an impregnating resin to a fiber reinforced material, also reducing the contraction at the time of curing the resin, and particularly compounding the resin with an ultraviolet-ray transmitting fiber reinforced material. CONSTITUTION:The resin composition comprises (a) a 30 to 70 pts.wt. acid anhydride modified epoxy-(meth)acrylate obtained by allowing an epoxy-(meth) acrylate oligomer to react with a cyclic organic acid anhydride and (b) a 30 to 70 pts.wt. reactive diluent consisting of monofunctional and/or polyfunctional (meth)acrylate as the essential components, and further comprises preferably (c) a 1 to 10 pts.wt. ultraviolet sensitive polymerization initiator based on the 100 pts.wt. of the total of the above component (a) and (b). The ultraviolet ray transmitting fiber reinforced material is impregnated with the above resin composition and thereafter the resin composition in the resulting material is cured by ultraviolet irradiation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite reinforcing material for an optical fiber cable, which is obtained by combining a specific impregnating resin with a fiber reinforcing material and has high strength, high toughness and excellent moisture resistance, and a method for producing the same. Is.

[0002]

2. Description of the Related Art As a reinforcing material for an optical fiber cable, for example, a composite of a fiber reinforcing material and a thermosetting resin is formed by drawing, and a composite of an ultraviolet transmitting reinforcing material and an ultraviolet curable resin is shaped. It is known that after that, it is cured with ultraviolet light.

As an example of the former improvement, Japanese Patent Laid-Open No. 62-90229 is available.
In this method, a reinforcing material impregnated with a thermosetting resin is coated with a thermoplastic resin, the thermosetting resin is heat-cured, and then the coated thermoplastic resin is removed. . Although this method can significantly increase the production rate compared to the ordinary pultrusion method, it requires an extra step of coating the thermoplastic resin and removing it after heat curing, which not only complicates the production equipment but also speeds up the production. Not suitable for production.

On the other hand, there is known a technique of using an ultraviolet curable resin as a coating agent for an optical fiber cable, as disclosed in, for example, JP-A-63-225563. However, there is no example in which an ultraviolet curable resin is compounded with a reinforcing fiber and used as a reinforcing material for an optical fiber cable.

Epoxy resins and (meth) acrylic resins are known as typical ultraviolet curable resins. Epoxy resins have a low curing rate due to ultraviolet rays and thus have poor productivity. Since the system resins have a large amount of curing shrinkage and poor adhesion to the reinforcing fibers, all of them are significantly inferior in performance to the thermosetting type composite reinforcing material for optical fiber cables.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art as described above, and its purpose is to exhibit excellent curing characteristics in a state of being compounded with a fiber reinforcement. In addition, we searched for a curable resin that has little shrinkage during curing and shows excellent adhesiveness with fiber reinforcement, thereby providing a composite reinforcement for optical fiber cables with excellent strength and moisture resistance. It is the one we are trying to provide. Another object of the present invention is to provide a method capable of producing such a high performance composite reinforcing material for optical fiber cables with high productivity.

[0007]

The composite reinforcing material for an optical fiber cable according to the present invention, which has been able to solve the above problems, comprises (a) reacting an epoxy (meth) acrylate oligomer with an organic acid intramolecular anhydride. Resin containing the acid anhydride-modified epoxy (meth) acrylate to be obtained: 30 to 70 parts by weight, (b) a reactive diluent comprising monofunctional and / or polyfunctional (meth) acrylate: 30 to 70 parts by weight as an essential component The composition is made by impregnating and curing the fiber reinforced material, or together with the above components (a) and (b) (c) UV-sensitive polymerization initiator: 100 parts by weight of the above components (a) and (b) The resin composition containing 1 to 10 parts by weight of the resin composition is impregnated in a fiber reinforced material which is transparent to ultraviolet rays, and then irradiated with ultraviolet rays to cure the resin. For such optical fiber cable The compound reinforcing agent is (a) an acid anhydride-modified epoxy (meth) acrylate obtained by reacting an epoxy (meth) acrylate oligomer with an organic acid intramolecular anhydride: 30 to 70 parts by weight, (b) monofunctional and / or Alternatively, a reactive diluent comprising a polyfunctional (meth) acrylate: 30 to 70 parts by weight (c) UV-sensitive polymerization initiator: 1 to 10 parts by weight based on 100 parts by weight of the total of the above components (a) and (b) After impregnating the resin composition consisting of a part of the resin composition into a fiber reinforced material which is transparent to ultraviolet rays, and then irradiating it with ultraviolet rays to cure the resin, the resin composition can be industrially produced with high productivity.

[0008]

In the present invention, the acid anhydride-modified epoxy (meth) acrylate oligomer (a) and the reactive diluent (b) consisting of a monofunctional and / or polyfunctional (meth) acrylate are essential components as described above. A resin composition containing a specific ratio or further containing an ultraviolet-sensitive polymerization initiator (c) as another component, which is obtained by impregnating and curing a fiber reinforcing material, and in particular as an essential component of the impregnating resin. By using the acid anhydride-modified epoxy (meth) acrylate oligomer (a), the shrinkage during curing is reduced and the adhesiveness with the fiber reinforcement is enhanced, which results in mechanical properties such as tensile strength and tensile modulus. And a composite reinforcing material for an optical fiber cable having excellent water resistance.

Further, in the production method of the present invention, the above-mentioned components (a) and (b)
And a resin composition having a specific composition consisting of a UV-sensitive polymerization initiator (c), which is impregnated into a UV-permeable fiber reinforcing material and UV-cured, and is required for curing by specifying these constituent requirements. The time can be shortened, which makes it possible to obtain a high-performance composite reinforcing material for optical fiber cables with high productivity.

The constituent features of the present invention will be described in detail below. First, an acid anhydride-modified epoxy (meth) acrylate oligomer [component (a)] has two or more (meth) acryloyl groups in the molecule formed by adding (meth) acrylic acid to an epoxy compound, Average molecular weight 50
It is obtained by reacting an oligomer of about 0 to 5000 with an intramolecular anhydride of an organic acid. Examples of the epoxy compound used here include a bisphenol A type epoxy compound synthesized from bisphenol A and epichlorohydrin, a phenol / novolak type epoxy compound, a bisphenol F type epoxy compound, and the like (meta). When acrylic acid is added, the epoxy group is opened to introduce a (meth) acryloyl group and a hydroxyl group is generated. Therefore, when this is reacted with an organic acid anhydride, the above-mentioned hydroxyl group and acid anhydride react to introduce an ester carboxylic acid, but when an intramolecular acid anhydride is used as the acid anhydride used at this time, Bulky ester carboxylic acid will be introduced into the epoxy (meth) acrylate oligomer,
As a result, it is possible to suppress the curing shrinkage at the time of ultraviolet curing and to improve the adhesiveness with the fiber reinforcing material.

Preferred organic acid intramolecular anhydrides used here are maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride or Examples thereof include related acid anhydrides in which various substituents are introduced into these basic skeletons, and these may be used alone or, if necessary, two or more kinds may be used in combination. In this case, in order to effectively exert the curing shrinkage reducing effect and the adhesiveness improving effect by the acid anhydride modification, 30 mol% or more, more preferably 50 mol% or more of the hydroxyl groups in the epoxy (meth) acrylate oligomer is acid anhydride. Those which are modified are preferable.

Next, monofunctional and / or polyfunctional (meta)
The acrylate [component (b)] is used as a reactive diluent, and acts as a diluent (or solvent) in the resin composition before curing, and at the same time, is exposed to the above-mentioned acid anhydride-modified epoxy (meth). ) It is a component of a cured product that is copolymerized with the acrylate oligomer (a), and has a low viscosity and a high dilution effect to improve the impregnation property of the resin composition, and has a small shrinkage at the time of curing. Those which give a cured product with high strength are preferred.

Examples of monofunctional (meth) acrylates that meet these requirements include monohydric groups such as isoamyl alcohol, isooctyl alcohol, lauryl alcohol, stearyl alcohol, methoxydipropylene glycol, phenoxyethyl alcohol, phenoxypropylene glycol and isobornyl alcohol. Examples thereof include (meth) acrylic acid ester of alcohol, mono (meth) acrylic acid ester of polyhydric alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and (meth) acryloyloxyethyl phthalic acid.

As the polyfunctional (meth) acrylate, polyalkylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol,
(Meth) acrylic acid diesters of diols such as dimethylol tricyclodecane and neopentyl glycol; 2 or 3 or more (meth) acrylics in divalent or higher alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol Acid reacted (meta)
Examples thereof include acrylates and alkoxy modified products thereof. These monofunctional or polyfunctional (meth) acrylates may be used alone or in combination of two or more kinds at any ratio.

Although the essential constituents of the resin composition used in the present invention are the above-mentioned two components, a phenolic resin, an acrylic resin, and a silicone can be used as long as they do not impair their curing characteristics and physical properties of the cured product. It is also possible to add a small amount of a system resin or the like. However, if these resins are insoluble in the above components (a) and (b), the physical properties of the cured product may deteriorate, so resins that are compatible with the components (a) and (b) should be used. Should be used selectively.

The composite reinforcing material for an optical fiber cable of the present invention contains 30 to 70% by weight of the above-mentioned component (a) and 70 to 30% by weight of the component (B) as essential components. As described above, the fiber reinforcing material is impregnated and cured by adding other components such as those mentioned above, and as a curing agent, an ordinary radical polymerization initiator or an ultraviolet polymerization initiator is used, but it is particularly preferable. Is a UV-sensitive polymerization initiator. Examples of the fiber reinforcing material include, but are not limited to, glass fiber, polyolefin fiber, polyacrylate fiber, nylon fiber, aramid fiber and the like.

At this time, if the amount of the component (a) is insufficient or the amount of the component (b) is too large, not only the adhesion of the resin composition to the fiber reinforced material deteriorates but also the curing shrinkage increases. However, it becomes impossible to obtain satisfactory strength as a composite reinforcing material. On the contrary, when the amount of the component (a) is excessive or the amount of the component (b) is insufficient, not only the resin composition before curing becomes highly viscous but the impregnation becomes poor.
The cured resin becomes too hard and becomes insufficient in flexibility, and again the suitability as a composite reinforcing material for an optical fiber cable decreases.

In the present invention, by using the above-mentioned acid anhydride-modified epoxy (meth) acrylate oligomer (a) as an essential constituent component of the impregnating resin, it is possible to suppress the curing shrinkage at the time of curing and to form the fiber reinforcing material. It is possible to obtain a composite reinforcing material for an optical fiber cable having improved adhesiveness and excellent mechanical properties and water resistance.

As described above, the present invention is most characterized in that the above-mentioned acid anhydride-modified epoxy (meth) acrylate oligomer (a) is used as an essential constituent of the impregnating resin. The type and the like are not particularly limited, but in order to increase the curing speed and improve the productivity, it is particularly preferable that the curing agent is a UV-sensitive polymerization initiator (c).
Is the method to use.

UV-sensitive polymerization initiator used here
The type of (c) is not particularly limited as long as it can be cleaved by ultraviolet rays to generate a radical, but typical examples include benzoin, benzoin alkyl ether, benzyl dimethyl ketal, phenoxydichloroacetophenone, and 2). -Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, benzoylbenzoic acid, hydroxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, acylphysphine oxide, phenanthrene Examples thereof include quinone, camphor quinone and anthraquinone. It is also possible to further improve the reaction rate by using an appropriate amount of an ultraviolet sensitizer together with the ultraviolet sensitive polymerization initiator (c).

In carrying out the method of the present invention, the above components (a), (b) and (c) are blended in the following ratios to prepare an acid anhydride-modified epoxy (meth) acrylate oligomer (a): 30 to 70 parts by weight Monofunctional and / or polyfunctional (meth) acrylate (b): 30 to 70 parts by weight UV-sensitive polymerization initiator (c): 100 parts by weight of the total of the above components (a) and (b) 1 to 10 parts by weight of these, for example, glass fiber, polyolefin-based fiber,
After impregnated with an ultraviolet ray transmissive fiber reinforcement such as polyacrylate fiber or nylon fiber, the resin is cured by irradiating with ultraviolet rays.

At this time, if the amount of the component (a) is insufficient or the amount of the component (b) is too large, not only the adhesion of the resin composition to the fiber reinforced material deteriorates but also the curing shrinkage increases. However, it becomes impossible to obtain satisfactory strength as a composite reinforcing material. On the contrary, when the amount of the component (a) is excessive or the amount of the component (b) is insufficient, not only the resin composition before curing becomes highly viscous but the impregnation becomes poor.
As described above, the cured resin becomes too hard and becomes insufficient in flexibility, and the suitability as a reinforcing material for an optical fiber cable is deteriorated.

When the component (c) is insufficient, it takes a long time to cure the ultraviolet rays or the curing becomes poor, and it becomes difficult to obtain a composite reinforcing agent having satisfactory physical properties. On the other hand, even if compounded in excess of 10 parts by weight, the curing rate will not be further increased,
Rather, since the amount of low molecular weight substances in the cured product increases and the strength rather deteriorates, it was determined to be 10 parts by weight or less.

When the above components (a) to (c) are compounded, in order to facilitate the impregnation into the fiber reinforcement, the compounding amount is adjusted so that the viscosity of the resin composition before curing becomes 10 poise or less at room temperature. It is desirable to adjust.

The fiber reinforced material to be impregnated with the resin when carrying out the method of the present invention has sufficient strength as a reinforcing fiber and has a UV transparency so as not to hinder the UV curing of the impregnated resin. It is not particularly limited as long as it has it, but preferable examples include glass fiber, polyolefin fiber, polyacrylate fiber, nylon fiber and the like. The amount of the resin composition impregnated into these fiber reinforcements is not particularly limited, but is preferably in the range of 20 to 50 parts by weight in the total amount of the composite reinforcement.

When this fiber reinforced material is impregnated with the above-mentioned resin composition, and if necessary, shaped and then irradiated with ultraviolet rays to be cured, the fiber reinforced material and the resin cured material are firmly combined and integrated in a short time, A composite reinforcing material for optical fiber cables having excellent physical properties such as tensile strength and flexural elasticity and excellent moisture resistance and chemical resistance can be obtained with high productivity.

[0027]

EXAMPLES Hereinafter, the constitution and effects of the present invention will be described more specifically with reference to examples, but the present invention is not limited by the following examples. Example 1 40 parts by weight of a maleic anhydride modified product of a bisphenol A type epoxy acrylate oligomer (average molecular weight: about 500) as the component (a) (modified with maleic anhydride corresponding to 50 mol% of hydroxyl groups in the molecule). And 60 parts by weight of isobornyl acrylate (reactive diluent) are mixed with 3 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba-Geigy) as an ultraviolet-sensitive polymerization initiator. And mix evenly at 25 ℃
A resin composition having a viscosity of 500 centipoise was obtained.

E glass roving was dipped in this resin composition to impregnate the resin (the resin impregnation amount was 32% by weight in the total amount of the cured composite reinforcement), and then an ultraviolet lamp (output: 160 W / cm) By irradiating the resin with ultraviolet rays to cure the resin, a composite reinforcing material for an optical fiber cable having a diameter of 2.3 mm was obtained. Table 1 shows the physical properties of the obtained composite reinforcing material. In addition, Table 2 shows the amount of polymerization shrinkage when the resin composition was solely UV-cured.

Further, a composite reinforcing material was prepared in the same manner as in Example 1 except that the kinds and blending amounts of the acid anhydride-modified epoxy (meth) acrylate oligomer and the reactive diluent were changed as follows. Along with the production, the physical properties thereof were examined, and the amount of polymerization shrinkage when the resin composition was cured alone was examined, and the results shown in Tables 1 and 2 were obtained together.

Example 2 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 70 mol% of maleic anhydride with respect to the hydroxyl groups in the oligomer: 50 parts by weight Component (b) ): Isobornyl acrylate: 50 parts by weight Component (c): "Irgacure 651": 3 parts by weight

Example 3 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 50 mol% of succinic anhydride with respect to the hydroxyl groups in the oligomer: 40 parts by weight Component ( b): Isobornyl acrylate: 60 parts by weight Component (c): "Irgacure 651": 3 parts by weight

Example 4 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 50 mol% of maleic anhydride with respect to hydroxyl groups in the oligomer: 40 parts by weight Component (b) ): Isobornyl acrylate: 50 parts by weight Pentaerythritol tetraacrylate: 10 parts by weight Component (c): "Irgacure 651": 3 parts by weight

Example 5 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 50 mol% of maleic anhydride with respect to hydroxyl groups in the oligomer: 40 parts by weight Component (b) ): 1,6-hexanediol diacrylate: 60 parts by weight Component (c): "Irgacure 651": 3 parts by weight

Comparative Example 1 Component (a): Unmodified bisphenol A type epoxy acrylate oligomer (Mw: about 500): 40 parts by weight Component (b): 1,6-hexanediol diacrylate: 60 parts by weight Component (c) : "Irgacure 651": 3 parts by weight

Comparative Example 2 Component (a): Unmodified bisphenol A type epoxy acrylate Oligomer (Mw: about 500): 50 parts by weight Component (b): Isobornyl acrylate: 40 parts by weight Pentaerythritol tetraacrylate: 10 parts by weight Ingredient (c): "Irgacure 651": 3 parts by weight

Comparative Example 3 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 50 mol% of maleic anhydride with respect to hydroxyl groups in the oligomer: 20 parts by weight Component (b) ): Isoborinyl acrylate: 20 parts by weight 1,6-hexanediol diacrylate: 60 parts by weight Component (c): "Irgacure 651": 3 parts by weight

Comparative Example 4 Component (a): Bisphenol A type epoxy acrylate oligomer (Mw: about 500) modified with 50 mol% of maleic anhydride to hydroxyl groups in the oligomer: 80 parts by weight Component (b) ): Isoborinyl acrylate: 20 parts by weight Component (c): "Irgacure 651": 3 parts by weight

[0038]

[Table 1]

[0039]

[Table 2]

As is clear from Tables 1 and 2, Examples 1 to 5 satisfying the specified requirements of the present invention have little polymerization shrinkage during curing and have good values in both tensile strength and tensile modulus. Has been obtained. On the other hand, in Comparative Examples 1 to 3 lacking any of the essential requirements specified in the present invention, the polymerization shrinkage rate during curing is large, and the tensile strength and the tensile elastic modulus of the obtained composite reinforcement are relatively low. . In Comparative Example 4, the viscosity of the resin before impregnation became too high, and the viscosity could not be sufficiently reduced even by heating, and impregnation of the reinforcing fiber itself was extremely difficult and could not be put to practical use.

[0041]

EFFECTS OF THE INVENTION The present invention is configured as described above, and by using an acid anhydride-modified epoxy (meth) acrylate oligomer as the main curing component of the impregnating resin, the adhesiveness with the fiber reinforcement is enhanced. At the same time, it is possible to provide a composite reinforcing material for an optical fiber cable, which can reduce curing shrinkage and thereby has high strength, high toughness, and excellent moisture resistance.

[Procedure amendment]

[Submission date] October 8, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication H01B 7/18 Z 7244-5G

Claims (3)

[Claims] 1. An acid anhydride-modified epoxy (meth) acrylate obtained by reacting an epoxy (meth) acrylate oligomer with an organic acid intramolecular anhydride (a): 30 to 70 parts by weight, (b) monofunctional and / or Alternatively, a composite for an optical fiber cable, characterized in that a resin composition containing 30 to 70 parts by weight of a reactive diluent composed of a polyfunctional (meth) acrylate as an essential component is impregnated and cured in a fiber reinforcement. Reinforcement material. 2. An acid anhydride-modified epoxy (meth) acrylate obtained by reacting (a) an epoxy (meth) acrylate oligomer with an organic acid intramolecular anhydride: 30 to 70 parts by weight, (b) monofunctional and / or Alternatively, a reactive diluent comprising a polyfunctional (meth) acrylate: 30 to 70 parts by weight (c) UV-sensitive polymerization initiator: 1 to 10 parts by weight based on 100 parts by weight of the total of the above components (a) and (b) A composite reinforcing material for an optical fiber cable, which is obtained by impregnating a resin composition consisting of two parts with an ultraviolet-transparent fiber reinforcing material and then irradiating it with ultraviolet rays to cure the resin. 3. An acid anhydride-modified epoxy (meth) acrylate obtained by reacting (a) an epoxy (meth) acrylate oligomer with an organic acid intramolecular anhydride: 30 to 70 parts by weight, (b) monofunctional and / or Alternatively, a reactive diluent comprising a polyfunctional (meth) acrylate: 30 to 70 parts by weight (c) UV-sensitive polymerization initiator: 1 to 10 parts by weight based on 100 parts by weight of the total of the above components (a) and (b) A process for producing a composite reinforcing material for an optical fiber cable, which comprises impregnating a resin composition consisting of a part with an ultraviolet-transparent fiber reinforcing material and then irradiating it with ultraviolet rays to cure the resin.