JP3345931B2 - UV curable resin composition and optical fiber using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a UV-curable resin composition containing a polymerizable unsaturated polyurethane <br/> data down, more particularly an optical fiber for coating an ultraviolet-curable resin composition, especially
Light off with useful optical fiber coating an ultraviolet-curable resin composition and that as the primary coating material of the optical fiber to
About fiber .

[0002]

2. Description of the Related Art An optical fiber is very brittle and easily damaged. For protection and reinforcement, a glass surface is coated with a material having a low elastic modulus immediately after spinning of the optical fiber, and then a high elastic modulus is applied. The secondary coating is performed with a material having the following.

[0003] In recent years, ultraviolet curable resins have been used from the viewpoint of productivity. Ultraviolet-curable resins are also used for bundling optical fibers with primary and secondary coatings into tapes.

[0004] Polyether urethane acrylate is widely used as the polymerizable unsaturated polyurethane used in the ultraviolet curable resin. Examples of the polyether polyol component constituting the known polyether urethane acrylate include, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, a random copolymer of propylene oxide and ethylene oxide, a random copolymer of tetrahydrofuran and propylene oxide. Copolymers, random copolymers of tetrahydrofuran and ethylene oxide, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, and the like can be given. Among these, polypropylene glycol (PPG) and polytetramethylene glycol (PTG) are used as the ultraviolet curing resin for coating optical fibers.
Is widely used as a polyether polyol component.

[0005]

The properties required for an ultraviolet-curable resin for coating an optical fiber include (1) a low-viscosity, room-temperature liquid and excellent workability, and (2) sufficient curing even at a low ultraviolet irradiation dose. And (3) excellent long-term reliability such as heat resistance, jelly resistance and hydrolysis resistance of the cured coating film. Furthermore, when used for primary coating, (4) low Young's modulus is required.

When the above-mentioned general-purpose polyether is used as the polyether component of the polyether urethane acrylate, for example, when PPG is used, the viscosity is low and the workability is excellent, but the long-term properties such as curability and heat resistance are long. It has both advantages and disadvantages, such as poor reliability. In addition, when polyether urethane acrylate is used as a primary coating for which a Young's modulus of 1.0 kg / mm ² or less is required for primary coating, the usable polyether component is restricted, and the above properties are satisfied. It is actually difficult to do. On the other hand, in Japanese Patent Application No. 184139/1990, the present inventors, as a polyether component, for example,
By using polybutylene glycol, an ultraviolet curable resin for coating an optical fiber, which is excellent in curability, heat resistance and hydrolysis resistance, and can obtain a coating film having a low Young's modulus, was proposed.

[0007] However, this material is excellent in hydrolysis resistance due to its high hydrophobicity, but on the other hand, when a petroleum jelly is filled in a cable as a waterproof material, the jelly swells and the jelly resistance is low. The point became clear.

The present invention has been made in view of such circumstances, and it is intended to provide a coating film having excellent curability, heat resistance and hydrolysis resistance and a low Young's modulus. An object of the present invention is to provide an ultraviolet-curable resin composition for coating an optical fiber, which exhibits the properties of polybutylene glycol, improves the jelly resistance which is a drawback thereof, and has excellent long-term reliability.

[0009]

In order to solve the above-mentioned problems, the present invention provides (1) (a) a polyether component as a polyether component.
(1,2-butylene glycol)及beauty polyether polyester polyols containing ring opening polymer of a lactone compound as a constituent unit as a port Riesuteru component, active hydrogen and a polymerizable that reacts with the polyisocyanate (b) and (c) an isocyanate group compound having an unsaturated group, a polymerizable unsaturated polyurethane obtained by reacting (hereinafter, referred to as polymerizable unsaturated polyurethanes of the present invention) and, (2) monomer and (3) having an ethylenically unsaturated bond photopolymerization UV curable resin composition containing an initiator and its cured product
Provided is an optical fiber that is coated .

The polymerizable unsaturated polyurethane used in the present invention has a polyether polyester polyol, a polyisocyanate, and an acryloyl group containing, as constituent units, polybutylene glycol as a polyether component and a ring-opening polymer of a lactone compound as a polyester component. It can be obtained by reacting a hydroxy compound.

The polyol used in the present invention is a block copolymer comprising a polybutylene glycol block and a ring-opening polymer block of a lactone compound, and is synthesized by a known method such as cationic ring-opening polymerization and anionic ring-opening polymerization. be able to. For example, by ring-opening polymerization of 1,2-butylene oxide and further ring-opening polymerization of a lactone compound, a polyol having a polyester block at the end can be synthesized, and after ring-opening polymerization of the lactone compound, By ring-opening polymerization of 1,2-butylene oxide, a polyol having a polyether block at the end can be synthesized. The terminal block may be either a polybutylene glycol block or a ring-opening polymer block of a lactone compound. As the lactone compound,
For example, β-propiolactone, δ-valerolactone,
β-methyl-δ-valerolactone, α, β, γ-trimethoxy-δ-valerolactone, ε-caprolactone, β
-Methyl-ε-isopropyl-ε-caprolactone, lactide, glycolide and the like. These may be used in combination of two or more. Among these, a polyether polyester polyol obtained by combining butylene glycol and ε-caprolactone is particularly suitable as a material constituting a polymerizable unsaturated polyurethane for coating an optical fiber.

A commercially available polyether polyester polyol obtained by block copolymerizing ε-caprolactone with polybutylene glycol as a backbone polymer is, for example, “PLACCEL PBG.CL3000” (manufactured by Daicel Chemical).

Examples of the polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, and trimethyl hexamethylene diisocyanate. 1,5-naphthalenediisocyanate, tolidine diisocyanate, p-phenylenediisocyanate,
Lysine diisocyanate and the like can be mentioned.

Examples of the hydroxy compound having an acryloyl group include hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, 2-hydroxybutyl acrylate, phenoxyhydroxypropyl acrylate, butoxyhydroxypropyl acrylate,
Pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane diacrylate, dipropylene glycol monoacrylate, 1,6-hexanediol monoacrylate, glycerin diacrylate, caprolactone-modified 2-hydroxyethyl acrylate, stearic acid-modified penta Erythritol diacrylate and the like.

As the monomer having an ethylenically unsaturated bond used in the present invention, an acrylate compound is mainly used. In the case of the UV-curable resin for primary coating, when a cured film needs to be soft, a monofunctional (meth) acrylate compound is mainly used to improve the curability or toughen the cured film. For the purpose of improving the properties, a bifunctional or higher polyfunctional acrylate compound is generally used in combination.

Specific examples of the monomer having an ethylenically unsaturated bond used in the present invention include, as a substituent, methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, hexadecyl,
Octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, tetrahydrofurfuryl, allyl, methallyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylamino Acrylate, methacrylate or fumarate having a group such as ethyl, diethylaminoethyl, nonylphenoxyethyltetrahydrofurfuryl; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,
3-butylene glycol, tetramethylene glycol,
Hexamethylene glycol, trimethylolpropane,
Mono (meta) such as glycerin and pentaerythritol
Acrylate or poly (meth) acrylate; vinyl acetate, vinyl butyrate or vinyl benzoate, acrylonitrile, cetyl vinyl ether, limonene, cyclohexene, diallyl phthalate, 2-, 3- or 4-vinylpyridine, acrylic acid, methacrylic acid, acrylamide,
Methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethylacrylamide and their alkyl ether compounds, neopentyl glycol 1
Di (meth) acrylate of diol obtained by adding 2 moles or more of ethylene oxide or propylene oxide to mole, triol di or obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, or Tri (meth) acrylate, di (meth) acrylate of diol obtained by adding at least 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, 1 mol of 2-hydroxyethyl (meth) acrylate, and phenylisocyanate or n-butyl Reaction product with 1 mol of isocyanate, poly (meth) acrylate of dipentaerythritol, N-vinyl-2-pyrrolidone, acryloylmorpholine, vinylimidazole, vinylcaprolactam, vinyl- -tert- butyl benzoate,
At least one selected from the group consisting of cyclohexyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, and dicyclopentenyl acrylate
Different monomers can be used.

The photopolymerization initiator used in the present invention includes:
Any material may be used as long as it generates a radical by light and the radical efficiently reacts with the polymerizable unsaturated compound. There are a type in which a molecule is cleaved to generate a radical and a type in which a compound such as a combination of an aromatic ketone and a hydrogen donor is used in combination.

Examples of the former include, for example, benzoin ethyl ether, benzoin isobutyl ether,
Benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1
-Phenyl-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one and 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 and the like.

Examples of the latter aromatic ketones include, for example, benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 2,4-diethylthioxanthone, 2-isopropyl Thioxanthone, 2-chlorothioxanthone and the like can be mentioned, and as a hydrogen donor to be combined therewith, for example, a mercapto compound and an amine compound can be mentioned, but an amine compound is generally preferable.

Examples of the amine compound include triethylamine, methyldiethanolamine, triethanolamine, diethylaminoethyl (meth) acrylate, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, , N-dimethylbenzylamine and 4,
4'-bis (diethylamino) benzophenone and the like.

These photopolymerization initiators may be used alone or in combination of two or more.

Further, as other additives, a thermal polymerization inhibitor, an antioxidant, a light stabilizer, a plasticizer, a silane coupling agent and the like can be added for the purpose of improving various properties.

The ultraviolet resin composition for coating an optical fiber of the present invention comprises (1) 10 to 80% by weight of a polymerizable unsaturated polyurethane, (2) 10 to 80% by weight of a monomer having an ethylenically unsaturated bond, and 0.1 to 10% by weight of polymerization initiator
It is preferable to mix | blend from the range of.

[0024]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.

First, a synthesis example of the polymerizable unsaturated polyurethane of the present invention will be described.

(Synthesis Example 1) Polyether polyesterdiol (number average molecular weight: 3,000) obtained by block copolymerizing ε-caprolactone using poly (1,2- butylene glycol ) as a backbone polymer.
0, ε-caprolactone content: about 30%) 1 mol and 2,4-tolylene diisocyanate 2 mol were charged into a reaction vessel equipped with a nitrogen gas inlet tube, a stirrer and a cooling tube, and 100 ppm of dibutyltin dilaurate was added as a catalyst. Then, the mixture was reacted at 70 ° C. for 2 hours.

Next, 2 mol of 2-hydroxypropyl acrylate, 100 ppm each of t-butylhydroquinone as a polymerization inhibitor and 100 ppm of dibutyltin dilaurate as a catalyst were added to the reaction mixture, and the mixture was further reacted at 70 ° C. for 20 hours to give an acryloyl group. (A-1) was obtained. Physical properties of the obtained polymerizable unsaturated polyurethane (A-1) were as follows. Gardner dilution viscosity: YZ (70% solid content in toluene solution) Residual isocyanate: 0.03%

(Synthesis Example 2) Poly (1,2- butylene glycol ) (Number average molecular weight:
3,000) and 3 mol of 2,4-tolylene diisocyanate were charged into a reaction vessel equipped with a nitrogen gas inlet tube, a stirrer and a cooling tube, and 100 ppm of dibutyltin dilaurate was added as a catalyst, followed by a reaction at 70 ° C. for 2 hours. I let it.

Next, 2 mol of 2-hydroxypropyl acrylate, 100 ppm of t-butylhydroquinone as a polymerization inhibitor and 100 ppm of dibutyltin dilaurate as a catalyst were added to the reaction mixture, and the mixture was further reacted at 70 ° C. for 15 hours to give an acryloyl group. The polymerizable unsaturated polyurethane (A-2) having the following formula was obtained. Physical properties of the obtained polymerizable unsaturated polyurethane (A-2) were as follows. Gardner dilution viscosity: UV (70% solid content in toluene solution) Residual isocyanate: 0.02%

Examples and comparative examples of the ultraviolet-curable resin composition for coating an optical fiber of the present invention are shown below.

Example 1 50 parts of the polymerizable unsaturated polyurethane (A-1) obtained in Synthesis Example 1, 50 parts of nonylphenoxy polypropylene glycol monoacrylate and 2,
2 parts of 4,6-trimethylbenzoyldiphenylphosphine oxide was mixed and dissolved at 60 ° C. for 1 hour,
A 1.2-poise (25 ° C.) liquid UV-curable resin composition was obtained.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polymerizable unsaturated polyurethane (A-2) was used instead of the polymerizable unsaturated polyurethane (A-1). A liquid UV-curable resin composition having a viscosity of 64.0 poise (25 ° C.) was obtained.

The following evaluation was carried out using each of the ultraviolet-curable resin compositions obtained in Example 1 and Comparative Example 1, and the results are shown in Table 1.

(Evaluation of Curability) Each of the ultraviolet-curable resin compositions was applied on a glass plate so that the dry coating thickness was 140 ± 20 μm, and nitrogen was applied thereto using a 80 W / cm metal halide lamp. The composition was cured by changing the irradiation light amount in an atmosphere. The tensile modulus of the cured film was measured.

The tensile modulus was measured according to JIS K7
113. As an index of curability, the ratio of the tensile modulus at the time of irradiation of 25 mJ / cm ² and 500 mJ / cm ² was taken, and the curing speed is shown in Table 1.

(Evaluation of Heat Resistance) The UV-curable resin composition was applied on a glass plate so that the dry coating thickness became 140 ± 20 μm, and then, using a metal halide lamp of 80 W / cm, in a nitrogen atmosphere. Curing was performed at an irradiation light amount of 100 mJ / cm ² . The cured film was stored in air at 120 ° C. for one week, and then the tensile modulus was measured in the same manner as described above.
The ratio of this measured value to the initial value was used as an index of heat resistance.

(Evaluation of jelly resistance) The ultraviolet curable resin composition was applied on a glass plate so that the thickness of the dried coating film became 200 ± 20 μm, and then, using a metal halide lamp of 80 W / cm, in a nitrogen atmosphere. 200mJ / cm
Cured in ² . The cured film is conditioned at 23 ° C. and 50% RH, and the weight M1 is measured. Next, after immersing in Jerry Grandic J2000 (manufactured by Dainippon Ink and Chemicals, Inc.) for one day at 85 ° C., the sample is taken out, the jelly on the surface is wiped off, and the weight M2 is measured. Weight change = M
2 / M1 × 100 (%) was used as an index of jelly resistance.

[0038]

[Table 1]

[0039]

From Table 1, it can be understood that the polymerizable unsaturated polyurethane of the present invention is excellent in curability, heat resistance and jelly resistance. Therefore, the ultraviolet curable resin composition for coating an optical fiber using the polymerizable unsaturated polyurethane of the present invention is excellent in workability and productivity.
Further, the optical fiber coated with the ultraviolet-curable resin composition for coating an optical fiber of the present invention can obtain high reliability even when used for a long time.

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Claims (4)

(57) [Claims] 1. A (1) (a) Poly as polyether component (1,2-butylene glycol)及beauty polyether polyester polyols containing ring opening polymer of a lactone compound as a constituent unit as a port Riesuteru component, (b) polyisocyanate, and (c) a polymerizable unsaturated polyurethane obtained by a compound having an active hydrogen and a polymerizable unsaturated group which reacts with isocyanate groups, is reacted, monomers and (3 having (2) an ethylenically unsaturated bond ) UV curable resin composition containing photopolymerization initiator
object. 2. (1) 10 polymerizable unsaturated polyurethanes
(2) a monomer having an ethylenically unsaturated bond in an amount of 10 to 10 % by weight;
80% by weight, and (3) 0.1 to 10% by weight of a photopolymerization initiator.
The ultraviolet-curable resin composition according to claim 1. 3. An ultraviolet-curable resin composition for coating an optical fiber, comprising the ultraviolet-curable resin composition according to claim 1 . 4. The ultraviolet-curable resin according to claim 1 or 2.
An optical fiber coated with a cured product of the composition.