KR100312041B1 - UV curable matrix compositions for optical fiber ribbons - Google Patents

Abstract

This invention relates to the resin composition for ultraviolet curable ribbons used for manufacture of an optical fiber ribbon. Important properties required for resins for ribbons include high Young's modulus (tensile modulus) and high elongation, and the present invention synthesizes two or more new oligomers having a large number of urethane bonds or urea bonds in a molecule, and synthesizes them. The required physical properties were achieved by mixing two or more kinds. According to the present invention (1) polyether polyol; Diisocyanate compounds; And polyurethane (meth) acrylate oligomer (A) and diisocyanate compound synthesize | combined from the (meth) acrylate compound containing a hydroxyl group; At least one monomolecular diol or diamine having a molecular weight of less than 400 and a mixture of polyether polyols; And 30 to 70% by weight of a mixture of the polyurethane (meth) acrylate oligomer (B) synthesized from a hydroxyl group-containing (meth) acrylate compound, (2) 30 to 50% by weight of a photocurable (meth) acrylate monomer diluent, ( And 3) 1 to 10% by weight of one or more types of photoinitiators that can be initiated by ultraviolet light. By mixing an appropriate amount of oligomers (A) and (B) in the present invention, a resin composition for an optical fiber ribbon having characteristics of high tensile modulus (Young's modulus) and high elongation was obtained.

Description

UV curable matrix compositions for optical fiber ribbons

The present invention relates to a composition of an ultraviolet curable ribbon coating resin used in the manufacture of a ribbon optical cable, and more specifically, a polyurethane (meth) acrylate, a reactive monomer diluent, and a photoinitiator in a predetermined ratio. It relates to the blended photocurable resin composition.

The cross section of an optical fiber ribbon is shown in FIG.

In the manufacture of the optical fiber, the fused spun glass fiber 1 reacts with moisture or the like to rapidly decrease its strength. Therefore, the protective reinforcement and microbending of the glass fiber 1 immediately after the hot melt spinning, that is, the occurrence of minute bending due to external pressure and the clad mode, that is, the incident light is not totally reflected in the clad layer. The primary coating 2 and the secondary coating 3 are performed for the purpose of eliminating the phenomenon of falling out to the outside.

In particular, the primary coating consists of a flexible resin with low glass transition temperature (below 0 ℃) and low tensile modulus (below 5MPa) in order to reduce the light transmission loss due to micro bending, and the secondary coating is made of the primary coating from external impact. And a hard resin having excellent mechanical properties with high tensile modulus of elasticity (25 ° C., 1000 MPa or more) for protecting glass fibers. In addition, the color coating (4) to the outside of the secondary coating (3) in order to facilitate the separation during the operation of the optical fiber connection.

A ribbon type optical cable (see US Patent No. 5561730, US Patent No. 3411010) is used to fabricate the cable by integrating the optical fiber with high density, and at this time, an optical fiber ribbon 7 is manufactured as a unit assembly of the optical fiber. To be laminated and cabled.

The optical fiber ribbon is a band-shaped optical fiber assembly in which several optical fibers are arranged in parallel and fixed by ribbon coating (6 of FIG. 1) with a photocurable resin. In general, the following properties are required as the resin composition for ribbon coating.

(1) Fast curing speed

(2) The cured product should have sufficient hardness and flexibility, ie high Young's modulus (tensile modulus) and elongation.

(3) There should be little change in physical properties with temperature

(4) have long-term reliability

(5) It has chemical resistance and water resistance.

In particular, it is a characteristic that is required in order to sufficiently cope with the external pressure, that is, side pressure and bending appearing in the cabling operation of the optical fiber ribbon and the cable installation work, and the cured coating film should have sufficient hardness and flexibility.

In general, as a method for increasing hardness, bifunctional and trifunctional monomers of the reactive monomer diluent are added to the composition to cure, but elongation tends to decrease with increasing hardness of the cured coating film, and the elongation rate is increased. The hardness tends to be poor. Therefore, a method of synthesizing bifunctional or trifunctional special acrylate oligomers and the like has been proposed as a method of reducing the elongation rate and increasing the hardness (US Patent No. 4690501, US Patent 4690502, US Patent No. 4472019). Japanese Patent Application Laid-Open No. 3-166217, Japanese Patent Laid-Open No. 62-78132, Japanese Patent Laid-Open No. 62-78131, Japanese Patent Laid-Open No. 61-227948), solvent resistance, water resistance, shrinkage rate, miscibility, etc. It is accompanied by a deterioration of the properties, and the method of freely increasing the properties of high hardness and high elongation rate, i.e., has not reached a sufficient degree.

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and aims to provide a resin composition having a high tensile modulus (750 MPa or more) and having a relatively high elongation, which is suitable for a resin composition for an optical fiber ribbon. The above object can be achieved by synthesizing two or more new oligomers having a large number of urethane bonds or urea bonds, that is, oligomers having different densities of hard segments, and mixing two or more of these oligomers. have. That is, isocyanate, diol, and hydroxyl group-containing (meth) acrylates are reacted, and thus, polyurethane polyurethane (meth) acrylate (A) and urethane (meth) acrylate oligomers having different number average molecular weights and hard segment numbers ( By synthesizing B) and mixing the polyurethane (meth) acrylate (A) and the urethane (meth) acrylate oligomer (B) in an appropriate ratio, a resin composition having suitable physical properties for an optical fiber ribbon can be obtained.

1 is a cross-sectional view of an optical fiber ribbon

Explanation of symbols on the main parts of the drawings

1 ... glass fiber 2 ... 1st coating 3 ... 2nd coating 4 ... color coating 5 ... fiber 6 ... ribbon coating 7 ... fiber ribbon

The ultraviolet curable resin composition for an optical fiber ribbon which concerns on this invention is comprised from the following compounds. This invention is polyurethane (meth) acrylate; Photocurable (meth) acrylate monomer diluents; In the resin composition for an optical fiber ribbon which consists of a photoinitiator and other additives, the said polyurethane (meth) acrylate has 6-22 urethane bonds (hard segment) in a molecule, and has a number average molecular weight of 3,000-30,000 polyurethane (meta It is characterized in that it is a mixture of an acrylate (A) and a urethane (meth) acrylate oligomer (B) having 4 to 12 urethane bonds in a molecule and having a number average molecular weight of 800 to 5,000. Rate (A) has a low tensile modulus (1.2 MPa or less) and a high elongation (150% or more), and the urethane (meth) acrylate oligomer (B) has a high tensile modulus (25 ° C, 1000 MPa or more) and a relatively low It has elongation (10-20%). This is described in detail in Application Nos. 10-1999-0007589 and 10-1999-0007590 filed by the applicant of the same application.

The resin composition for an optical fiber ribbon of the present invention comprises 50 to 70% by weight of a mixture of the polyurethane (meth) acrylate (A) and the urethane (meth) acrylate oligomer (B); 30-50 weight% of photocurable (meth) acrylate monomer diluents; And 1 to 10% by weight of photoinitiator.

The synthesis | combination of the said polyurethane (meth) acrylate (A) is synthesize | combined by reacting 2 mol of hydroxyl-containing (meth) acrylates, 2 mol of diisocyanate compounds, and 1 mol of polyether polyols.

Here, in hydroxyl-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxy alkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6- Hexanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylol ethanedi (meth) acrylate, and the like. It can be used together.

And the diisocyanate compound is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate , P-phenylene diisocyanate, 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, 4.4'-bisphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. And 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, etc. are mentioned, Alone or You may use together 2 or more types.

In addition, polyether polyols having a molecular weight of 400 to 3,000 obtained by ring-opening (co) polymerizing alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like to polyether polyols (for example, polyethylene glycol, poly Propylene glycol, polytetramethylene glycol, polybutylene glycol, copolymer polyol of propylene oxide and tetrahydrofuran, copolymer polyol of ethylene oxide and tetrahydrofuran, copolymer polyol of ethylene oxide and butylene oxide, and the like. ), Alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthoquinone, alkylene oxide addition diol of hydrogenated bisphenol A , Alkylene oxide addition of hydrogenated bisphenol F Dior etc. can be mentioned. Among the above polyols, polypropylene glycol, polytetramethylene glycol, ring-opening copolymer of tetrahydrofuran and propylene oxide, alkylene oxide adduct of bisphenol A or bisphenol F, polycarbonate diol and polycaprolactone diol using the same are suitable. Do.

The urethane (meth) acrylate oligomer (B) is a mixture of 2 moles of diisocyanate compound, 0.67-2 moles of hydroxyl group-containing (meth) acrylate, a polyether polyol having a molecular weight of 400 to 3,000, and a monomolecular diol having a molecular weight of less than 400 1 It synthesize | combines by reacting -1.67 mol. The hydroxyl group-containing (meth) acrylate, the diisocyanate compound, and the polyether polyol are the same as those used in the synthesis of the polyurethane (meth) acrylate oligomer A, and the monomolecular diols having a molecular weight of less than 400 are ethylene glycol and propylene. Glycol, tetramethylene glycol, 1,6-hexanediol pentamethylene glycol, neopentyl glycol, hexamethylene glycol, 1,4-cyclonucleodimethanol, bisphenol A, bisphenol F and the like. In addition to monomolecular diols, monomolecular triols and diamines or triamines may be used alone or in combination. For example, glycerol, 1,2,3-pentanetriol, hexanetriol, 1.2.3-butanetriol, Trimethylolpropane, 1,2,4-benzenetriol, ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4, 4'-diaminodiphenylmethane, benzidine, 3,3'-dimethylbenzidine, 3,3'-dichlorobenzidine, diethylenetriamine, 1,2,3-triaminepropane and the like.

The production of the polyurethane (meth) acrylate (A) used in the present invention is a conventional method, by reacting diisocyanate and diol to synthesize a polyurethane prepolymer having an isocyanate group at the end of the sock, and a hydroxyl group A method of producing by reacting a (meth) acrylate having a compound and a (meth) acrylate having a hydroxyl group with an excess of diisocyanate to synthesize a polyurethane prepolymer having an isocyanate group remaining at one end thereof, and a polyether-based It can manufacture by the method of making the mixture of a polyol and monomolecular diol react.

The characteristic of this invention is a mixture of polyurethane (meth) acrylate (A) and urethane (meth) acrylate oligomer (B).

Increasing the coating film hardness using only the polyurethane (meth) acrylate (A) results in a decrease in elongation rate and a decrease in toughness, but according to the present invention, polyurethane (meth) acrylate (A) and urethane (meth) When the acrylate oligomer (B) is mixed and used, hardness and toughness can be increased without decreasing elongation.

Moreover, the mixing ratio of the polyurethane (meth) acrylate (A) and the urethane (meth) acrylate oligomer (B) used in the present invention is in the range of 0.1 to 10 weight ratio relative to the weight of the above (A). It is mixed and used, Preferably it mixes and uses in the range of 0.2-5 weight ratio. Since a polyurethane (meth) acrylate (A) and a urethane (meth) acrylate oligomer (B) have a high viscosity and coating property is bad A reactive monomo diluent, that is, a photocurable (meth) acrylate monomer diluent is used in combination, and the reactive monomer diluent serves to lower the viscosity of the oligomer and to control the physical properties of the cured coating film by using a crosslinkable monomer.

Reactive monomer diluents include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxy ethyl (meth) acrylate, ethyldiethylene glycol (Meth) acrylate, 2-ethyl texyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadiene (meth) acrylate, polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylate, methyl triethylene diglycol (meth) acrylate, isobornyl (meth) acrylate, N-vinylpyrrolidone, N-vinyl caprolactam, diacetone acrylamide, isobutoxymethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, acryloylmorpholine, dicy Lofentenyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycol di (meth) acrylate , Trimethylolpropanetrioxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclodecane dimethanol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dicyclopentane Di (meth) acrylate, dicyclopentadiene di (meth) acrylate, etc. are mentioned.

Preferred among these are 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinylpyrrolidone and N-vinyl capro Lactam, dimethylaminoethyl (meth) acrylate, tripropylene glycol di (meth) acrylate, cyclopentenyl (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, trimethylolpropane tree (meth) Acrylates and the like, and these may be used alone or in combination of two or more thereof.

Photoinitiator is required when ultraviolet curing the resin composition of the present invention, for example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxy benzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, 1- (4-isopropyl- Phenol) -2-hydroxy-2-methyl propane-1-one, thioxanthone, and the like. Irgacure184, 369, 651, 819, 907, 1700, 1800 (Shibagai Corp.) And Darocure 1173, 1116 (Merck), Lucirine LR8728 (Basp), and Ubecyl-936 (YC). These can be used individually by 1 type or in mixture of 2 or more types.

Small photosensitizers such as diethyl amine can also be added but are not necessary.

In addition, in the present invention, additives may be added to adjust the solution properties, curing properties, coating properties, etc. of the resin composition, including antioxidants, light stabilizers, plasticizers, coupling agents, thermal polymerization inhibitors, leveling agents, and surfactants. Etc.

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

Synthesis Example 1.

348.0 g (2 mole) of 2,4-toluene diisocyanate is placed in a 3-liter reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooler, and 0.08 g of dibutyltin dilaurylate is added, followed by reaction temperature. 1000.0 g (1 mole) of polytetramethylene glycol having a number average molecular weight of 1000 was added dropwise for 2 hours while maintaining the temperature at 70 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 ° C for 7 hours, and then a small amount of methylhydroquinone, a polymerization inhibitor, was added and 232.0 g (2 mole) of hydroxyethyl acrylate was added dropwise for 3 hours, followed by further reaction for 5 hours. Polyurethane acrylate (A) was obtained. The urethane acrylate oligomer (B) was synthesized by adding 400.0 g (0.4 mole) of polytetramethylene glycol and 94.5 g (0.6 mole) of hexanediol instead of 1000.0 g of the polytetramethylene glycol.

Next, the Example and comparative example of the ultraviolet curable resin composition for optical fiber ribbon coating of this invention are shown.

Example 1.

10 weight% of 50 weight% oligomer (B) synthesized in Synthesis Example 1 was added to a reactor equipped with a stirrer, and then dimethylaminoethyl methacrylate 10 weight% phenoxyethyl acrylate 15 as a reactive monomer diluent. 5% by weight Tripropylene glycol diacrylate 3% by weight Pentaerythritol tetraacrylate 3% by weight 3% by weight of silicone diacrylate (TEGORad 2100, manufactured by Tego Corporation), 0.5% by weight of antioxidant (Iganox of Shivagaigi Co., Ltd.) 1035), 0.5% by weight of methylhydroquinone and 2.5% by weight of Irgacure 1700 (Shibagai Co., Ltd.) as photoinitiators and 0.5% by weight of dimethylamine, a photosensitizer, were stirred at 400 rpm for 2 hours at room temperature to give a viscosity of 1100 cps. A mixed liquid was obtained. The obtained liquid composition was molded into a film by the following method and the physical properties thereof were measured.

① Film forming

After coating the resin of Example 1 to a thickness of 0.1 mm using a bar coater on a glass plate, it was irradiated at 1.0 J / cm ² in a curing machine to prepare a cured film.

② Tensile Characteristics

Using a tensile tester, the film was taken at a size of 10 mm x 80 mm at 25 ° C. and 50% relative humidity, and measured at a speed of 5 mm per minute with a gauge distance of 50 mm.

③ shrinkage

The specific gravity of the liquid phase and the film phase is measured at room temperature, and calculated by the following equation.

④ viscosity

Measurements are made using a Brookfield viscometer in the usual rotary form and a thermostat is used in parallel.

Example 2.

40 wt% of the oligomer A synthesized in Synthesis Example 1 was added to the reactor with a stirrer, 20 wt% of the oligomer B was added thereto, and the other compositions were added in the same manner as in Example 1 at 400 rpm for 30 minutes at room temperature. It stirred with and obtained the transparent viscous liquid. Film molding and physical property measurement were performed in the same manner as in Example 1.

Example 3.

30 wt% of the oligomer A synthesized in Synthesis Example 1 was added to the reactor with a stirrer, and 30 wt% of the oligomer B was added thereto. The other composition was added in the same manner as in Example 1, and then 400 rpm at room temperature for 30 minutes. It stirred with and obtained the transparent viscous liquid. Film molding and physical property measurement were performed in the same manner as in Example 1.

Example 4.

20 wt% of the oligomer A synthesized in Synthesis Example 1 and 40 wt% of the oligomer B were added to a reactor equipped with a stirrer, and other compositions were added in the same manner as in Example 1 at 400 rpm for 30 minutes at room temperature. Stirring and transparent viscous liquid were obtained. Film molding and physical property measurement were performed in the same manner as in Example 1.

Example 5.

10 wt% of the oligomer A synthesized in Synthesis Example 1 and 40 wt% of the oligomer B were added to a reactor equipped with a stirrer, and other compositions were added in the same manner as in Example 1 at 400 rpm for 30 minutes at room temperature. Stirring and transparent viscous liquid were obtained. Film molding and physical property measurement were performed in the same manner as in Example 1.

Comparative Example 1.

60 wt% of the oligomer A synthesized in Synthesis Example 1 was added to the reactor to which the stirrer was attached, and the oligomer B was not added. The other composition was added in the same manner as in Example 1, and stirred at 400 rpm for 30 minutes at room temperature, and transparent. A viscous liquid was obtained. Film molding and physical property measurement were performed in the same manner as in Example 1.

Comparative Example 2.

3 wt% phenoxy ethyl acrylate and 15 wt% pentaerythritol tetraacrylate in a reactive monomer diluent were added to a reactor equipped with a stirrer, and other reactive monomer diluents and oligomers were added in the same manner as in Comparative Example 1. After stirring at 400 rpm for 30 minutes, a clear viscous liquid was obtained. Film molding and physical property measurement were performed in the same manner as in Example 1.

a) 3% by weight of phenoxyethyl acrylate and 15% by weight of pentaerythritol tetraacrylate in the reactive monomer diluent

As the amount of oligomer (B) increased in Examples 1 to 5, the Young's modulus increased greatly but the decrease in elongation was small (relatively large in Example 5), and the amount of polyfunctional monomer diluent in Comparative Example Increasing (Comparative Example 2) increases the Young's modulus, but it can be seen that the elongation decreases significantly. In addition, at a similar Young's modulus, it can be seen that the value of the shrinkage rate and the change of the Example are smaller than those of the Comparative Example. As can be seen from the above results, the present invention using a mixture of oligomers (B) having a large number of urethane bonds in one molecule, that is, a high-density oligomer of hard segment, easily increases the Young's modulus while minimizing the decrease in the elongation and the increase in the shrinkage. It can be seen that it is an excellent ultraviolet light-curable resin composition that can ensure the reliability of the optical fiber ribbon in a very excellent way to improve the toughness of the coating film and to improve the toughness of the coating film.

Claims (3)

Polyurethane (meth) acrylates; Photocurable (meth) acrylate monomer diluents; In the resin composition for an optical fiber ribbon comprising a photoinitiator, Polyurethane (meth) acrylate (A) which the said polyurethane (meth) acrylate has a number average molecular weight of 3,000-30,000, and the number average urethane bond per molecule is 6-22; A resin composition for an optical fiber ribbon, wherein the mixture has a urethane (meth) acrylate oligomer (B) having a number average molecular weight of 800 to 5,000 and a number average urethane bond of 4 to 12 per molecule. The resin for an optical fiber ribbon according to claim 1, wherein the polyurethane (meth) acrylate (A) and the urethane (meth) acrylate oligomer (B), which are the mixtures, are mixed at a weight ratio of 1: 0.2 to 5. Composition. The resin composition for an optical fiber ribbon according to claim 1 or 2, comprising: 50 to 70% by weight of a mixture of a polyurethane (meth) acrylate (A) and a urethane (meth) acrylate oligomer (B); 30-50 weight% of photocurable (meth) acrylate monomer diluents; And 1 to 10% by weight of photoinitiator.