KR100596492B1 - Photocurable polymeric resin composition for optical fiber in-line coating - Google Patents

Abstract

The present invention relates to a photocurable polymer resin composition for optical fiber inline coating, wherein the coating composition of the present invention comprising a relatively high content of a photopolymerizable urethane acrylate oligomer and a low content of a photopolymerizable monomer, a photoinitiator, and a pigment is used for a horizontal inline. Colored fiber coatings can give high viscosity and relatively low curing properties.

Description

Photocurable polymer resin composition for optical fiber in-line coating {PHOTOCURABLE POLYMERIC RESIN COMPOSITION FOR OPTICAL FIBER IN-LINE COATING}

The present invention relates to a photocurable polymer composition for optical fiber inline coating.

In recent years, coating methods using UV curable resins have shorter reaction times, higher energy efficiency, higher temperatures during curing, and simplified equipment and equipment. As there are many advantages, research on this is being actively conducted.

Primary, secondary, and ink coating technologies have been developed as coating processes for optical fibers, and some fields require inks that have high viscosity (6,000 to 9,000 cps) and low curing properties.

For example, ink coatings are classified into off-line coloring and in-line coloring. Off-line coloring refers to a method in which a coloring system is configured separately. (In-Line) The coloring method is a method in which a coloring system is installed in a loose tubing machine or a ribbon manufacturing facility, that is, a loose tubing or ribbon work while fiber coloring.

In the in-line coloring method, the speed of the loose tubing and the ribbon work is considerably slow, so it is necessary to slow the speed of the coloring work performed simultaneously. Thus, in contrast to the offline method, the inline method requires high viscosity and relatively low curing properties of the coloring ink.

However, as the optical fiber coating industry demands rapid curing speed, the resin for optical fiber coatings, which has been used in the past, exhibits a low viscosity of about 2,000 to 4000 cps and a high degree of curing, and thus is applied to a field requiring such high viscosity and low curing properties. There is a problem that is difficult to do.

Therefore, in order to solve the problem, the present invention gives a low curing property while increasing the viscosity of the resin for optical fiber ink coating, and also the coating thickness of the ink according to high viscosity is thickened from the existing 3 to 6 ㎛ from 6 to 8 ㎛ It aims at providing the resin composition for optical fiber coatings which make the color of a colored optical fiber meet the EIA-359-A standard in view of losing.

In order to achieve the above object, the present invention (A) 70 to 90% by weight of the photopolymerized urethane acrylate oligomer, (B) 5 to 20% by weight of the reactive monomer, (C) 0.5 to 10% by weight of the photoinitiator, and (D It provides a resin composition for optical fiber in-line coating, characterized in that it comprises 1 to 10% by weight of the pigment.

Hereinafter, the present invention will be described in detail.

(A) photopolymerizable urethane acrylate oligomer

The photopolymerized urethane acrylate oligomer (A) used in the present invention is (i) polyol copolymer, (ii) polyisocyanate, (iii) acrylate alcohol, (iv) urethane reaction catalyst and ( v) can be synthesized from a composition comprising a polymerization initiator.

The photopolymerizable urethane acrylate oligomer (A) is preferably used in an amount of 70 to 90% by weight, preferably 80 to 90% by weight of the photocurable coating resin composition. In the case of 70 wt% or less, there is a problem in that the curing shrinkage of the resin composition is increased and the viscosity is low, resulting in uneven coating during operation, thereby increasing light loss due to micro bending, and in the case of exceeding 90 wt%, the work viscosity becomes too high. There is a problem in workability.

The components constituting the oligomer (A) are as follows.

(i) polyol copolymer

The polyol copolymer (i) has a molecular weight of 100 to 10,000 and preferably includes a repeating unit of -CH ₂ CH ₂ O- or -CH ₂ CH (CH ₂ CH ₃ ) O-.

Preferred examples of the polyol copolymer (i) include a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, and a ring-opening tetrahydrofuran Tetrahydrofurane propyleneoxide ring opening copolymer and the like, the polyol copolymer is preferably used in an amount of 5 to 50% by weight of the photopolymerizable urethane acrylate oligomer composition.

(ii) polyisocyanates

Preferred examples of polyisocyanate (ii) include 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 1,3-xylenediisocyanate, 1 , 4-xylenediisocyanate, 1,5-naphthalenediisocyanate, 1,6-hexanediisocyanate, isophoronediisocyanate (IPDI) and mixtures thereof It is selected from the group consisting of. The polyisocyanate (ii) is preferably used in an amount of 20 to 40% by weight of the oligomer (A).

(iii) acrylate alcohol

The acrylate alcohol (iii) comprises one or more (meth) acrylates and hydroxy groups, preferred examples of which are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meta) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4- Hydroxybutyl acrylate, neopentyl glycomono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, Dipentaerythritol penta (meth) acrylate and mixtures thereof. The acrylate alcohol (iii) is preferably used in an amount of 20 to 35% by weight of the oligomer (A).

(iv) urethane reaction catalyst

The urethane reaction catalyst (iv) is a catalyst which is added in a small amount during the urethane reaction, and examples thereof include copper naphthenate, cobalt naphthenate, zinc naphate, n-butyltinlaurate and tristilamine ( tristhylamine), 2-methyltriethylenediamide and mixtures thereof. The reaction catalyst (iv) is preferably used in an amount of 0.01 to 1% by weight of the oligomer (A).

(v) polymerization initiator

Preferred examples of the polymerization initiator (v) are selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, para-benzoquinone, phenothiazine and mixtures thereof, and 0.01 to 1 weight of the oligomer (A). Preference is given to using in amounts of%.

The photopolymerized urethane acrylate oligomer (A) can be synthesized from the respective components as follows:

After the polyol copolymer (i) and the polymerization initiator (v) are put in the reactor, the vacuum is reduced for 30 minutes to 1 hour, and water is removed to prevent side reactions between water and isocyanate. After maintaining the water-free mixture at a temperature of 40 to 65 ° C. for 30 minutes to 1 hour, 1 part of the total catalyst (iv) used was added with polyisocyanate (ii) in a split form and stirred at 200 to 300 rpm. Add about 3 At this time, the fever is severe, so be careful. After the exotherm is terminated, the temperature is maintained at 50 to 75 ° C until the -OH peak disappears on the IR. The reaction time is about 2 to 3 hours. After completion of the reaction, acrylate alcohol (iii) is added. At this time, too much heat is necessary to pay attention. After completion of the exotherm, the temperature was raised to 60 to 80 ° C., and the remaining catalyst (iv) was added to react until the -NCO peak disappeared on the IR to obtain a photopolymerizable urethane acrylate oligomer (A).

(B) photopolymerizable monomer

The photopolymerizable monomer (B) used in the present invention uses a low molecular weight monomer in order to match the working viscosity with the oligomer (A) having a polymer structure. In addition, in order to improve the adhesion with the surface to be coated, a monomer having an adhesive force increasing effect is additionally used. The monomer has one or more acrylate groups, methacrylate groups or vinyl groups in the molecular structure, and monomers having 1 to 3 or more various functional groups can be used, and particularly low curing with high tensile strength in the film state. It is desirable to have a shrinkage rate. Preferred examples thereof include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate, isobornyl acrylate (IBOA), isobornyl methacrylate, N-vinyl Pyrrolidone (N-VP), bisphenol ethoxylate diacrylate, ethoxylate phenol monoacrylate, polyethyleneglycol 200 diacrylate, tripropylene glycol diacrylate, trimethylpropane triacrylate ( TMPTA), polyethylene glycol diacrylate, ethyleneoxide-addition triethylolpropanetri acrylate (Eo-TMPTA), pentaerythritol tetraacrylate (PETA), 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated pentaerythritol Ethoxylated pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, 2-phenoxyethyl acrylate, ethoxylated bisphenol A diacrylate and mixtures thereof.

Other alkoxylated nonylphenol acrylates, alkoxylated trifunctional acrylate esters, metallic diacrylates, trifunctional acrylate esters other than the above components ), Trifunctional methacrylate esters and mixtures thereof may be used.

The photopolymerizable monomer (B) is preferably used in the range of 5 to 20% by weight, preferably 5 to 15% by weight of the resin composition for optical fiber coating. If it is less than 5% by weight, it is difficult to dilute the high-viscosity oligomer composite (A) to a working viscosity of 6,000 to 9,000 cps (25 ° C), and when it exceeds 20% by weight, the curing shrinkage rate of the film is increased during curing. There is a problem of light loss.

(C) photoinitiator

The photoinitiator (C) used in the present invention is added in an amount suitable to maintain the slow curing speed of the resin itself, since the optical fiber inline coating is made while maintaining a slow line speed of 500 m / min or less. The photoinitiator (C) receives ultraviolet energy to form free radicals and attack double bonds in the resin to induce polymerization. Preferred examples thereof include commercially available Irgacure # 184 (hydroxycyclohexylphenylketone) from Ciba Geigy, Irgacure # 907 (2-methyl-1 [4- (methylthio) phenyl] -2-mo Polyno-propan-1-one), Irgacure # 500 (hydroxyketone and benzophenone), Irgacure # 651 (benzyldimethylketone), Darocure # 1173 (2-hydroxy-2-methyl-1-phenyl-propane- 1-one), Darocure # 116, CGI # 1800 (bisacylphosphineoxide) and CGI # 1700 (bisacylphosphineoxide and benzophenone). The photoinitiator (C) is preferably used in an amount of 0.5 to 10% by weight, preferably 0.5 to 5% by weight of the resin composition for optical fiber coating.

(D) pigment

The composition of the present invention includes a pigment for coloring, wherein the pigment is Paliotol Black L 0080 (aniline-based), Paliogen Black L 0086 (perylene-based), Paliotol Yellow L 0962 HD (quinophthalone-based) manufactured by BASF , Paliotol Yellow L 1772 (nickel complex), Paliotol Orange L 2930 HD (pyrazolo-quinazolone series), Paliogen Red L 3880 HD (perylene series), Paliogen Red L 4120 (perylene series), Heliogen Blue L 7101F (copper- Phthalocyanine-beta, Heliogen Green L 8731 (copper-phthalocyanine-chlor), Irgalite Yellow G0 (arylamide-based) by Ciba-Geigi, Cromopthal Red BRN (azo condensate), Irgalite Red FBL, Irgalite Blue GLNF (copper -Phthalocyanine-beta), Irgazin Blue A3RN (Indanstron system), Daihan Yellow D525 (Diarylide anilide system), Daihan Yellow D581 (Diarylide dimethoxychloroanilide) from Korea Swiss Chemical, Daihan Orange D513 (Diaryl) De pyrazolone), Daihan Red C140, Daihan Red 2B235 (Azo), Daihan Blue 3700 (Copper-phthalocyanine-alpha), Daihan Blue 8700 (copper-phthalocyanine-beta), and the like, when used, the pigment is 1 to 10% by weight, preferably 1 to 5% by weight, in the photocurable polymer composition for optical fiber coating. It is preferably included in the amount.

The method for preparing the resin composition for optical fiber coating of the present invention is as follows:

A composition comprising a photopolymerizable urethane acrylate oligomer (A), a reactive photopolymerizable monomer (B), a photoinitiator (C) and a pigment (D) is added to the reactor and at a temperature of 15 to 50 ° C. and a humidity of 60% or less. Reaction is carried out using a dispersion impeller at a uniform speed of at least 1000 rpm. If the reaction temperature is less than 15 ° C., the viscosity of the oligomer (A) is increased to cause a problem in the process. If the temperature exceeds 50 ° C., the photoinitiator (C) forms a radical to cause a curing reaction. When the reaction humidity exceeds 60%, the resulting resin composition generates bubbles during the subsequent coating process, and there is a problem in that a side reaction occurs in which an unreacted substance reacts with moisture in the air. In addition, if the stirring speed is less than 1,000 rpm may not be well blended.

The resin composition of the present invention has high viscosity and relatively low curing properties and is therefore particularly advantageous for inline coating of optical fibers.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Preparation Example 1: Preparation of Urethane Acrylate Oligomer (A)

Polytetramethylene glycol (molecular weight 1,000) (manufactured by BASF Corporation) 885.5 g, methylpropylene diol (molecular weight 90) (48.8 g by Aldrich) and isophorone diisocyanate (IPDI) of diol type in a 2 L flask (Manufacturer: Liondell Chemical Company) 634.5 g were mixed, and then 1 g of n-butyltinlaurate (DBTL) (Songwon Industry) was added while increasing the temperature to 40 to 50 ° C. . After the exotherm was completed, the temperature was maintained at 50 to 70 ° C. until the -OH peak disappeared. Hydroquinone monomethyl ether (HQMMA) (eastman) 2.25 g, 2-hydroxypropyl acrylate (2-HPA) (Nippon Shokubai) when the -OH peak disappears completely on IR. ) 427 g were added. When the exotherm was completed, the urethane acrylate oligomer was prepared by adding and reacting 2 g of DBTL until the -NCO peak on the IR disappeared while maintaining the temperature at 60 to 75 ° C.

Examples 1 to 4 and Comparative Example: Preparation of Photocurable Resin Composition for Optical Fiber Inline Coating

Using the oligomer prepared in Preparation Example 1, as shown in Table 1 below, the compositions according to the present invention were combined.

Component, weight (%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Preparation Example 1 Oligomer 85 85 85 84 55 Triethylpropane triacrylate 5 5 5 5 25 Isobonyl Acrylate 3.5 3 3 3 10 Darocure 1173 2 One 2 2 2.5 CGI 1800 2 2 2 2 3 Irgalite Blue GLN 1.2 Daihan Orange D513 2 Heliogen Green L8731 1.5 Daihan Red C410 3 3.3 TiO ₂ 1.3 2 1.5 One 1.2 Viscosity (cps), 25 ℃ 7,200 7,450 7,230 7,860 3,100

Test Example 1 MEK Friction Test of Colored Optical Fiber

Methyl ethyl ketone (MEK) friction experiment of the optical fiber colored with the resin composition for coating the optical fiber ink prepared in Examples 1 to 4 and the resin composition of Comparative Example 1 similar to the ink used in the prior art was performed. The coloring coating conditions were set at 300 m / min and the coating temperature was 35 m / min for the fiber colorizer (OFC 55: Nextrom), and the MEK friction test was performed by rubbing more than 200 times with a 1kg load using a cloth moistened with MEK. This was done by checking the number of frictions when this occurred.

The test results are shown in Table 2 below.

Coating thickness (㎛) MEK Friction Count Example 1 8 > 200 Example 2 8 > 200 Example 3 8 > 200 Example 4 7 > 200 Comparative Example 1 2 to 6 -

As can be seen in Table 2, while the coating composition according to the present invention exhibits a uniform coating thickness and excellent MEK friction strength, in Comparative Example 1, the coating thickness is non-uniform and does not partially color, and a thin coating Over-hardening of the cotton caused the colored coating surface to break during the MEK friction test.

Test Example 2 Colorimetric Experiment of Colored Fiber

After coloring the optical fiber with the optical fiber ink coating resin prepared in Examples 1 to 4, the Munsell index of the colored optical fiber was measured using Minolta CM-3700D.

H (color) V / C (brightness / saturation) Example 1 0.5 PB 4.4 / 11.2 Example 2 10 R 5.3 / 13.4 Example 3 2.5 G 5.5 / 10.4 Example 4 3.4 R 4.3 / 13.8

Test Example 3 Preparation of Optical Fiber Coating Ink Film and MEK Friction Experiment

Films were prepared from the resin compositions for optical fiber ink coatings prepared in Examples 1 to 4 and Comparative Example 1, and subjected to MEK friction experiments. Film manufacturing conditions were 200 m / min of the curing machine flux, and the coating thickness was 20 micrometers.

Coating thickness (㎛) MEK Friction Count Example 1 20 <10 Example 2 20 <10 Example 3 20 <10 Example 4 20 <10 Comparative Example 1 20 > 200

As shown in Examples 1 to 4 and Comparative Example 1 of Table 4, Examples 1 to 4 exhibiting a low degree of curing were easily colored, and Comparative Example 1 exhibited a higher degree of curing.

As can be seen from the above examples and comparative examples, the resin composition for optical fiber coating according to the present invention not only exhibits the high viscosity characteristics required for the horizontal in-line optical fiber colorant, but also exhibits a lower degree of curing than the ink used in the prior art. It exhibited a characteristic of not causing excessive curing even at high light quantity.

Claims (9)

(A) 70-90 wt% of the photopolymerizable urethane acrylate oligomer, (B) 5-20 wt% of the photopolymerizable monomer having at least one acrylate group, methacrylate group or vinyl group, (C) 0.5-10 photoinitiator A photocurable resin composition for optical fiber in-line coating, comprising% by weight and 1-10% by weight of (D) pigment. The method of claim 1, The photopolymerized urethane acrylate oligomer (A) was (i) 23-50 wt% of polyol copolymer, (ii) 20-40 wt% of polyisocyanate, (iii) 20-35 wt% of acrylate alcohol, (iv) urethane reaction A resin composition, characterized in that it is prepared from a composition comprising from 0.01 to 1% by weight of catalyst and from 0.01 to 1% by weight of (v) polymerization initiator. The method of claim 2, The polyol copolymer (i) has a molecular weight of 100 to 10,000 and comprises repeating units of -CH ₂ CH ₂ O- or -CH ₂ CH (CH ₂ CH ₃ ) O-, polyester polyol, polyether polyol, poly Resin composition, characterized in that selected from the group consisting of a carbonate polyol, polycaprolactone polyol and ring-opening tetrahydrofuran propylene oxide copolymer. The method of claim 2, Polyisocyanate (ii) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1, Resin composition, characterized in that selected from the group consisting of 6-hexane diisocyanate, isophorone diisocyanate and mixtures thereof. The method of claim 2, Acrylate alcohol (iii) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, neopentylglycomono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylic Resin, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, and mixtures thereof. The method of claim 2, The urethane reaction catalyst (iv) is selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphate, n-butyltinlaurate, tristilamine, 2-methyltriethylenediamide and mixtures thereof Resin composition. The method of claim 2, Resin composition, characterized in that the polymerization initiator (v) is selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, para-benzoquinone, phenothiazine and mixtures thereof. The method of claim 1, The photopolymerizable monomer (B) is phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate, isobornyl acrylate, isobornyl methacrylate, N-vinyl Pyrrolidone, bisphenol ethoxylate diacrylate, ethoxylate phenol monoacrylate, polyethylene glycol 200 diacrylate, tripropylene glycol diacrylate, trimethylpropane triacrylate, polyethylene glycol diacrylate, ethylene oxide addition type tri Ethyl propane triacrylate, pentaerythritol tetraacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylated pentaerythritol tetraacrylate, 2-phenoxyethyl acrylate Toxylated Bisphenol A Diacrylate And a mixture thereof, characterized in that the resin composition. delete