KR20020074791A - Resin compositions for coating optical fiber ribbon - Google Patents

Abstract

PURPOSE: Provided is a resin composition for coating of optical fiber ribbon, which shows increased tensile and surface-sliding properties, and reduced contraction when cured, and reduced surface friction in lamination of ribbons, as well as minimized optical loss. CONSTITUTION: The resin composition for coating of optical fiber ribbon comprises (A) 50-80 wt% of photopolymerizable urethane acrylate oligomer, (B) 15-50 wt% of photopolymerizable monomer, (C) 3-15 wt% of photoinitiator, and (D) 0.1-5 wt% of at least one of silica type or wax type slipping agent and antifoaming agent. The photopolymerizable urethane acrylate oligomer(A) is produced from composition comprising (i) 5-30 wt% of polyol copolymer, (ii) 20-40 wt% of polyisocyanate, (iii) 20-35 wt% of acrylate alcohol, (iv) 0.01-1 wt% of urethane reactive catalyst, (v) 0.01-1 wt% of polymerization initiator, and (vi) 0.1-5 wt% of at least one additive selected from the group consisting of a slipping agent, an antifoaming agent and an antioxidant.

Description

Resin composition for optical fiber ribbon coating {RESIN COMPOSITIONS FOR COATING OPTICAL FIBER RIBBON}

The present invention relates to a resin composition for optical fiber ribbon coating, and more particularly, includes a photopolymerizable urethane acrylate oligomer, a photopolymerizable monomer, a photoinitiator, and an additive such as a silica type or wax type slip agent, an antifoaming agent, and tensile strength. The present invention relates to a resin composition for coating an optical fiber ribbon capable of increasing sliding properties of a surface and minimizing light loss.

In recent years, the coating method using UV curable resins has a shorter reaction time, higher energy efficiency, does not require high temperature during curing, and can simplify equipment and equipment. There are many advantages, and research on this is being actively conducted.

Meanwhile, as a method of arranging coated optical fibers, a ribbon process has been developed, and various operations can be performed at the same time. In such a ribbon process, when using a conventional alkyl chain type resin for the optical fiber ribbon coating, the surface tension is 30 mN / m or more, which makes it difficult to exhibit its own surface slip, and the coated resin has a large shrinkage rate when cured. Also, a bending phenomenon in which the ribbon is bent in the direction of the force due to the contracting force occurs. This bending causes light loss by disturbing straight light. In addition, the ribbon is laminated in a slot process after coating the ribbon, where bending occurs even when friction occurs on the surface.

In order to solve the problem that bending occurs due to the surface friction, the present inventors have developed a technology for imparting sliding characteristics by adding a silicone additive to the optical fiber ribbon coating resin, and filed in Korean Patent Application No. 99-45335 have.

However, this method adds a large amount of silicone additives because it is difficult to solve the problem with a small amount of additives, thereby adversely affecting the tensile strength, shrinkage rate, curing rate, viscosity, and the like of the optical fiber coating resin. In addition, in the conventional ribbon process, there is a method of imparting sliding characteristics by coating talc on a surface, but this has a disadvantage in that the process is complicated, such as requiring an additional process.

Therefore, an object of the present invention, in order to solve the above problems, by adding a small amount of silica type or wax type additive to the optical fiber ribbon coating resin, the tensile strength and surface sliding characteristics are increased, and also minimize the shrinkage of the resin during curing The present invention provides a resin composition for optical fiber ribbon coating, which can minimize light loss arising from bending of a ribbon by reducing surface friction in a lamination process during ribbon assembly.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the surface frictional force on the resin film for optical fiber ribbon coating manufactured in Example 1 and Comparative Examples 1-5.

Figure 2 is a graph showing the tensile strength of the resin for optical fiber ribbon coating prepared in Example 1 and Comparative Examples 1 to 5.

Figure 3 is a graph showing the shrinkage of the resin for optical fiber ribbon coating prepared in Example 1 and Comparative Examples 1 to 5.

Figure 4 is a graph showing the viscosity of the resin for optical fiber ribbon coating prepared in Example 1 and Comparative Examples 1 to 5.

In order to achieve the above object, the present invention (A) 50 to 80% by weight of the photopolymerized urethane acrylate oligomer, (B) 15 to 50% by weight of the photopolymerizable monomer and (C) 3 to 15% by weight of the photoinitiator and (D) Provided is a resin composition for optical fiber ribbon coating comprising at least one of silica type or wax type slip agent and antifoaming agent at 0.1 to 5% by weight, respectively.

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 has a sliding property on the surface, (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 included in an amount of 50 to 80% by weight of the resin composition for optical fiber ribbon coating. If it is less than 50% by weight, there is a problem in that the curing shrinkage of the resin composition is increased to increase the light loss due to the micro bending, and when it is more than 80% by weight, the work viscosity is increased, resulting in problems 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) are polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, ring-opening tetrahydrofuran propylene Tetrahydrofurane propyleneoxide ring opening copolymer, and the like, of which polyester polyol or ring-opening tetrahydrofuran propylene oxide copolymer is preferable.

The polyol copolymer may be optionally mixed with the diol compound, wherein the diol compound is preferably about 0.1 to 5% by weight based on the content of the polyol copolymer. These diol compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,5-pentanediol, and 1,6-hexane Diol (1,6-hexanediol), neopentyl glycol, 1,4-cyclohexane dimethanol, bisphenol-A, bisphenol-F ) And mixtures thereof.

The polyol copolymer (i) is preferably contained in an amount of 5 to 30% by weight of the photopolymerizable urethane acrylate oligomer (A), more preferably 10 to 15% by weight.

(ii) polyisocyanates

Preferred examples of the polyisocyanate (ii) include 2,4-tolyenediisocyanate, 2,6-tolyenediisocyanate, 1,3-xylenediisocyanate, 1,4-xylenediisocyanate, 1,5-naphthalenediisocyanate, 1,6-hexanediisocyanate, isophoronedi-isocyanate (IPDI) and It is selected from the group consisting of a mixture thereof. 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 at least one acrylate or methacrylate, and a hydroxy group, preferred examples of which are 2-hydroxyethyl (meth) acrylate, 2-hydroxy 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethylacrylate, 2 2-hydroxypropylacrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxybutylacrylate (4 -hydroxybutylacrylate), neopentylglycomono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono ( Meth) acrylate (1,6-hexanediolmono (meth) acrylate), pentaerys Tolyl-penta (meth) acrylate is selected from (pentaery-thritolpenta (meth) acrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritolpenta (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 added in a small amount during the urethane reaction, and examples thereof include copper naphthenate, cobalt naphthenate, zinc naphthate and n-butyltinlaurate. (butyltinlaurate), tristhylamine, 2-methyltriethlenediamide 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, hydroquinonmonomethylether, para-benzoquinone, phenothiazine and mixtures thereof , It is preferable to use in an amount of 0.01 to 1% by weight of the oligomer (A).

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

After the polyol copolymer, optionally a diol compound, and a polymerization initiator are placed in a reactor, the pressure is reduced to 760 mmHg or more for 30 minutes, and water is removed to prevent side reactions between water and isocyanate. The water-free mixture is maintained at a temperature of 40-65 ° C., then polyisocyanate is added and stirred at 200-300 rpm while about one third of the total catalyst used is added. 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 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 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 has at least one acrylate group, methacrylate group or vinyl group in its molecular structure. The monomer (B) is preferably a low molecular weight monomer in order to match the working viscosity with the oligomer (A) having a polymer structure, it is preferable to have a low curing shrinkage while having a high tensile strength on the film. Preferred examples thereof include phenoxyethylacrylate, phenoxydiethylene-glycolacrylate, phenoxytetraethylene-glycolacrylate, and phenoxyhexaethylene-glycolacrylate. Isobornylacrylate (IBOA), isobornylmethacrylate (isobornylmethacrylate), N-vinylpyrrolidone (N-VP), bisphenol ethoxylate diacrylate, Ethoxylate phenol monoacrylate, polyethyleneglycol 200 diacrylate, tripropyleneglycol diacrylate, trimethylpropane triacrylate (TMPTA), polyethyleneglycol diacrylate Acrylate yleneglycol diacrylate, ethyleneoxide-addition triethylolpropanetri acrylate (Eo-TMPTA), pentaerythritol tetraacrylate (PETA), 1,4-butanediol diacrylate (1,4- butanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylated pentaerythritol tetraacrylate, 2-phenoxyethyl acrylate , Ethoxylated bisphenol A diacrylate, and mixtures thereof.

It is preferable that the said photopolymerizable monomer (B) occupies 15-50 weight% of the resin composition for optical fiber ribbon coating. When it is less than 15% by weight, it is difficult to dilute the high viscosity oligomeric compound (A) to a working viscosity of 5,000 to 8,000 cps (25 ° C), and when it exceeds 50% by weight, the curing shrinkage rate of the film during curing increases, bending. There is a problem of light loss by the.

(C) photoinitiator

The photoinitiator (C) used in the present invention is added to maintain the fast curing speed of the resin itself since the optical fiber coating is made while maintaining a fast line speed of 300 m / min or more. 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 (hydroxycyclohexyl-phenylketone), Irgacure # 907 (2-methyl-1 [4- (methylthio) phenyl] -2-morpholino- Propane-1-on (2-methyl-1 [4- (methythio) phenyl] -2-morpholino-propan-1-on)), Irgacure # 500, Irgacure # 651, Darocure # 1173 (2-hydroxy-2 2-methyl-2-phenyl-1-propan-1-one), Darocure # 116, CGI # 1800 and CGI # 1700 . The photoinitiator (C) is preferably used in an amount of 3 to 15% by weight of the resin composition for optical fiber ribbon coating.

(D) slip and / or antifoam

The slip agent and the antifoaming agent used in the present invention are preferably silica type or wax type additives. These are particularly effective for imparting surface sliding characteristics of the resin composition for optical fiber ribbon coating, and are preferably used in the range of 0.1 to 5% by weight of the total resin composition, respectively.

In the case of using a silicone type additive as in the prior art, it is necessary to add a large amount in order to solve the problems caused by the surface friction of the resin composition for optical fiber ribbon coating, which causes the tensile strength, shrinkage, curing rate of the resin composition It has a bad effect on viscosity, viscosity, and the like.

Preferred examples of the slip agent include commercially available PP1362D (polypropylene wax type), CP1481SF (polypropylene wax type), CP1481F (polyethylene wax type), PE1500F (polyethylene wax type), PEW1555 (polyethylene wax type), PE1544F (Polyethylene wax type), TF1778 (polyethylene wax type), TF1780 (polyethylene wax type), TF1830 (polyethylene wax type), TFW1765 (polyethylene wax type), D2S (fatty acid amide wax type), E2S (fatty acid ester amide wax type) Wax types such as A1601 (fatty acid amide wax type) and HM 1666 (polycarboxylic acid amide wax type) (manufactured by Langer &Co); SYLOID63, SYLOID65, SYLOID66, SYLOID72, SYLOID74, SYLOID79, SYLOID404, SYLOID620, SYLOID308, SYLOID978, SYLOID160, SYLOID161, SYLOID162, SYLOID800, SYLOID810, SLOLOID244, SLOLO2 ; And silica or wax types such as HK125, HK400, OK412, OK412LC, OK520, OK607, TS100, TT600 (Degussa).

Preferred examples of the defoamer include BYK-011, BYK-019, BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-026, BYK-027, BYK-028, BYK-045, BYK-055, BYK-057 and BYK-066.

It is preferable that the said slip agent / antifoamer of a silica or wax type is used with a dispersing agent. Preferred examples of such dispersants include commercially available BYK-151, BYK-154, BYK-220S, BYK-P104, BYK-P104S, BYK-P105, Anti-Terra-203, Anti-Terra-204, Anti-Terra -205, Anti-Terra-206, Anti-Terra-U, Anti-Terra-U80, Bykumen, Disperbyk, Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-110, Disperbyk-111, Disperbyk -115, Disperbyk-116, Disperbyk-130, Disperbyk-140, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-169, Disperbyk-170 , Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-181, Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-190, Lactimon, Lactiomon-WS) (above: BYK-Chemie ). It is preferably used in an amount of 0.1 to 5% by weight of the dispersant resin composition.

In addition, the resin composition of the present invention may further include an antioxidant to prevent the formed film is corroded due to oxidation to lower the physical properties. The antioxidant is usually a phenolic additive is mainly used, a preferred example thereof is commercially available Irganox 1010 (tetrakis [methylene (3,5-di-ter-butyl-4-hydroxyhydrocinnamate)] Methane (tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane) Irganox1035 (thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ( thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)), Irganox1076 (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (octadecyl 3,5-di-tert -butyl-4-hydroxyhydrocinnamate)) (above manufactured by Cibageigy) and mixtures thereof The antioxidant is preferably used in an amount of 0.1 to 5% by weight of the resin composition.

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

Additives, such as a dispersing agent and antioxidant, are added to a reactor, including a photopolymerization urethane acrylate oligomer (A), a photopolymerizable monomer (B), a photoinitiator (C), and a slip agent and / or an antifoamer (D), and 15-15 The reaction is carried out at a temperature of 50 ° C. and a humidity of 60% or less using a dispersed 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 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 of Urethane Acrylate Oligomer

Manufacture 1

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

Manufacture 2

To a 2 L flask, 1278.02 g of polytetramethylene glycol (molecular weight 3000) manufactured by BASF Corporation and 189.4 g of isophorone diisocyanate (IPDI) manufactured by Liondel Chemical Company were prepared, followed by n-butyltinlaurate ( DBTL) (manufactured by Songwon Industrial Co., Ltd.) was reacted in the same manner as in Example 1 while adding 0.8 g. Subsequently, 2.20 g of hydroquinone monomethyl ether (HQMMA) and 127.38 g of 2-hydroxypropyl acrylate (2-HPA) were added and reacted in the same manner as in Example 1 to prepare an oligomer, where 1.5 g of DBTL was added.

Manufacture 3

352.32 g of polytetramethylene glycol (molecular weight: 1,000) (BASF Corporation), 285.38 g of polycapralactone polyol (molecular weight: 540) (trade name: TONE-0305) and isophorone diisocyanate (IPDI) in a 2 L flask After mixing 636.34 g of Chemical Company), the reaction was carried out in the same manner as in Example 1 while adding 0.8 g of n-butyltin laurate (DBTL) (Songwon Industry). Subsequently, 2.25 g of hydroquinone monomethyl ether (HQMMA) and 520.98 g of 2-hydroxypropyl acrylate (2-HPA) were added and reacted in the same manner as in Example 1 to prepare an oligomer, and 1.7 g of DBTL was added thereto.

Manufacture 4

Into a 2 L flask was mixed 860.5 g of polytetramethylene glycol (molecular weight 1000) manufactured by BASF Corporation, 57.2 g of methylpropylene diol (molecular weight 90) manufactured by Aldrich, and 674.5 g of 2,4-toylene diisocyanate. The reaction was carried out in the same manner as in Example 1 while adding 1 g of n-butyltin laurate (DBTL) (Songwon Industry). Subsequently, 2.15 g of hydroquinone monomethyl ether (HQMMA) and 450 g of 2-hydroxypropyl acrylate (2-HPA) were added and reacted in the same manner as in Example 1 to prepare an oligomer, where 2 g of DBTL was added.

Manufacture 5

Into a 2 L flask was mixed 855.5 g of polytetramethylene glycol (molecular weight 1000) manufactured by BASF Corporation, 48.8 g of methylpropylene diol (molecular weight 90) and 630.5 g of 1.5-naphthalene diisocyanate manufactured by Aldrich, followed by n The reaction was carried out in the same manner as in Example 1 while adding 1 g of -butyltin laurate (DBTL) (Songwon Industry). Subsequently, 2.25 g of hydroquinone monomethyl ether (HQMMA) and 427 g of 2-hydroxypropyl acrylate (2-HPA) were added and reacted in the same manner as in Example 1 to prepare an oligomer, where 2 g of DBTL was added.

Manufacture 6

In a 2 L flask, 885.5 g of polytetramethylene glycol (molecular weight 1000) manufactured by BASF Corporation, 48.8 g of methyl propylene diol (molecular weight 90) manufactured by Aldrich, and isophorone diisocyanate (IPDI) manufactured by Liondel Chemical Campani) 634.5 g were mixed and reacted in the same manner as in Example 1 while adding 1 g of n-butyltinlaurate (DBTL) (Songwon Industry). Subsequently, 2.25 g of hydroquinone monomethyl ether (HQMMA) and 447.6 g of 2-hydroxybutyl (meth) acrylate were added and reacted in the same manner as in Example 1 to prepare an oligomer, where 2 g of DBTL was added.

Manufacture 7

In the same manner as in Example 5, except that 0.5 g and 1.5 g of 2-methyltriethylene diamide (manufactured by Songwon Industry) were used instead of n-butyltin laurate (DBTL) as the reaction catalyst, respectively. Oligomers were prepared.

Preparation of Resin Composition for Fiber Optic Ribbon Coating

Example 1

73% by weight of oligomer prepared in Preparation 1, 10% by weight of isobornylacrylate, 7% by weight of N-vinylpynolidone, 3.7% by weight of photoinitiator, and 0.5% by weight of PE1500F as an additive, 0.5% by weight of Anti-Terra-206 And Irganox 1010 1% by weight to prepare a resin composition for coating the optical fiber ribbon.

Example 2

A resin composition for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 0.5 wt% of TS100, 0.5 wt% of BYK-220S, and 1 wt% of Irganox 1010 were used.

Example 3

A resin composition for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 0.5 wt% OK607, 0.5 wt% BYK-P104S, and 1 wt% Irganox 1010 were used as the additive.

Example 4

A resin composition for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 0.5 wt% OK607, 0.5 wt% BYK-P104S, 1 wt% BYK-011, and 1 wt% Irganox 1010 were used. .

Example 5

Except for using 0.5% by weight of HK450 (manufactured by Dagussa), 0.5% by weight of Disperbyk-115 and 1% by weight of Irganox 1010 as an additive, the resin composition for optical fiber ribbon coating in the same manner as in Example 1 Prepared.

Example 6

A resin composition for coating an optical fiber ribbon was prepared in the same manner as in Example 1, except that 0.5 wt% of aerosil 200 (manufactured by Dagusa Inc.), 0.5 wt% of BYK-220S, and 1 wt% of Irganox 1010 were used as the additive. .

Example 7

A resin composition for coating an optical fiber ribbon was prepared in the same manner as in Example 1, except that 0.5 wt% of aerosil 300 (manufactured by Dagusa Inc.), 0.5 wt% of BYK-220S, and 1 wt% of Irganox 1010 were used as the additive. .

Examples 8-14

Except for using the oligomer prepared in Preparation 2, each of the resin composition for optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Examples 15-21

Except for using the oligomer prepared in Preparation 3, each of the resin for the optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Examples 22-28

Except for using the oligomer prepared in Preparation 4, each of the resin for the optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Examples 29-35

Except for using the oligomer prepared in Preparation 5, each of the resin for the optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Examples 36 to 42

Except for using the oligomer prepared in Preparation 6, each of the resin for the optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Examples 43-49

Except for using the oligomer prepared in Preparation 7, each of the resin for the optical fiber ribbon coating was prepared in the same manner as in Examples 1 to 7.

Comparative Example 1

Example 1 A silicon type additive was used in place of the silica and wax type, except that Tago 440 1.5 wt%, Rad 2100 1.5 wt%, Rad 2600 3.5 wt%, and Irganox 1010 1 wt% were used as the additive. In the same manner as the resin for the optical fiber ribbon coating was prepared.

Comparative Example 2

A resin for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 1.5 wt% of Tago 440, 1.5 wt% of Rad 2100, 3.0 wt% of Rad 2600, and 1 wt% of Irganox 1010 were used as the additive.

Comparative Example 3

Resin for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 3.0% by weight of Rad 2100, 3.0% by weight of Rad 2600, and 1% by weight of Irganox 1010 were used as the additive.

Comparative Example 4

A resin for optical fiber ribbon coating was prepared in the same manner as in Example 1, except that 0.5 wt% of Tago 440, 0.5 wt% of Rad 2100, 0.5 wt% of Rad 2600, and 1 wt% of Irganox 1010 were used as the additive.

Comparative Example 5

Except not using an additive, a resin for optical fiber ribbon coating was prepared in the same manner as in Example 1.

Experiment 1: Surface Characterization

In order to compare the surface properties of the optical fiber ribbon coating resins prepared in Examples 1, 9, 17, 25, 33, and 41 and the optical fiber ribbon coating resins prepared in Comparative Examples 1 to 5, the surface frictional force on the film was measured. The results of the measurement are shown in Table 1 and Fig. 1. The frictional force was measured by a force generated when a 500 g weight was pulled horizontally using a tensile strength meter (Instron 4443 from Instron).

Example Comparative Example One 9 17 25 33 41 One 2 3 4 5 Surface friction (kgf) 0.058 0.155 0.152 0.133 0.136 0.236 0.152 0.212 0.337 0.987 2.472

As shown in Table 1, when one of the additives, such as the resin composition prepared in Comparative Example 5 is not added, it can be seen that the surface frictional force value is much larger than the resin film containing the additive. When the same amount of additives were used, the resin film of Comparative Example 4 prepared with the silicone type additive was the surface of the resin films of Examples 1, 9, 17, 25, 33 and 41 made with the additive of silica and wax type. It can be seen that the increase significantly compared to the frictional force. In addition, in the case of using a large amount of additives (Comparative Examples 1, 2 and 3) showed a high surface friction force compared to the resin film of the Example. This resulted in superior surface frictional force by using a relatively small amount of silica and wax type additives compared to the silicone type additives used in the prior art, and problems such as lowering of strength strength, curing rate, and viscosity caused by using excessive additives To show that they can be solved.

Experiment 2: Tensile Strength Test

Tensile strength of the optical fiber ribbon coating resins prepared in Examples and Comparative Examples was measured at room temperature using a tensile strength meter (Instron 4443 from Instron) according to ASTM D-638. The results are shown in Table 2 and FIG.

Example Comparative Example One 9 17 25 33 41 One 2 3 4 5 Tensile Strength (kg / mm ² ) 50 20 80 62 63 60 42.2 43.0 43.1 49.5 50

As shown in Table 2, the resin compositions of Comparative Examples 1 to 4 containing the silicone type additives had a tensile strength of up to 20% lower than that of the resins of Comparative Example 5 containing no additives. In the case of using a wax type additive, it can be seen that the tensile strength remains almost unchanged.

Experiment 3: Shrinkage Test

Shrinkage of the optical fiber ribbon coating resin prepared in Examples and Comparative Examples was measured at room temperature in accordance with ASTM D-792, the results are shown in Table 3 and FIG.

Example Comparative Example One 9 17 25 33 41 One 2 3 4 5 Shrinkage (%) 10.5 5.5 14 12 12.2 11.6 10.0 10.2 10.2 10.4 10.5

As shown in Table 3, as the tensile strength increases, the curing shrinkage rate generally increases, and the change according to the content of the additive is fine.

Experiment 4: Viscosity Test

The viscosity of the optical fiber ribbon coating resin prepared in Examples and Comparative Examples was measured at room temperature according to ASTM D-2196, and the results are shown in Table 4 and FIG. 4.

Example Comparative Example One 9 17 25 33 41 One 2 3 4 5 Viscosity (Cps) 11000 16000 12000 11500 12000 10000 12500 12000 12200 11500 11000

As shown in Table 4, the change in viscosity according to the content of the additive is not very large, it can be seen that it has a slight effect.

In the resin composition for optical fiber ribbon coating of the present invention, a small amount of silica type or wax type slip agent / foaming agent is used instead of the silicone type additive, thereby increasing tensile strength and surface sliding characteristics and minimizing shrinkage of the resin during curing. And by reducing the surface friction in the lamination process during ribbon assembly, it is possible to minimize the light loss resulting from the bending phenomenon of the ribbon.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (14)

(A) 50 to 80% by weight of the photopolymerized urethane acrylate oligomer, (B) 15 to 50% by weight of the photopolymerizable monomer and (C) 3 to 15% by weight of the photoinitiator and (D) slip and antifoaming agents of silica type or wax type. The resin composition for optical fiber ribbon coating containing 0.1-5 weight% of each 1 or more types. The method of claim 1, The photopolymerized urethane acrylate oligomer (A) is (i) 5-30 wt% of a polyol copolymer, (ii) 20-40 wt% of polyisocyanate, (iii) 20-35 wt% of acrylate alcohol, (iv) urethane From 0.01 to 1% by weight of a reaction catalyst, from 0.01 to 1% by weight of a polymerization initiator and (vi) from 0.1 to 5% by weight of at least one additive selected from the group consisting of slip agents, antifoaming agents and antioxidants. Resin composition for optical fiber ribbon coating characterized by the above-mentioned. The method of claim 2, The polyol copolymer (i) has a molecular weight of 100 to 10,000, comprises a repeating unit of -CH ₂ CH ₂ O- or -CH ₂ CH (CH ₂ CH ₃ ) O-, polyester polyol, polyether polyol, Resin composition for optical fiber ribbon coating, characterized in that selected from the group consisting of polycarbonate polyol, polycaprolactone polyol and ring-opening tetrahydrofuran propylene oxide copolymer. The method of claim 3, The polyol copolymer (i) is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, bisphenol-A , Bisphenol-F and mixtures thereof, characterized in that mixed with one selected from the group consisting of, the resin composition for optical fiber ribbon coating. The method of claim 2, The said polyisocyanate (ii) is 2, 4- tolyenedi isocyanate, 2, 6- tolyenedi isocyanate, 1, 3- xylene diisocyanate, 1, 4- xylene diisocyanate, 1, 5- naphthalene diisocyanate, 1 Resin composition for optical fiber ribbon coating, characterized in that selected from the group consisting of, 6-hexane diisocyanate, isophorone diisocyanate and mixtures thereof. The method of claim 2, The 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) Optical fiber ribbon, characterized in that selected from the group consisting of acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, and mixtures thereof Resin composition for coating. 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-methyltriethylene diamide and mixtures thereof A resin composition for coating an optical fiber ribbon. The method of claim 2, The polymerization initiator (v) is selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, para- benzoquinone, phenothiazine and mixtures thereof, the resin composition for optical fiber ribbon coating. The method of claim 1, The photopolymerizable monomer (B) has at least one acrylate group, methacrylate group or vinyl group, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylic Latex, isobornyl acrylate, isobornyl methacrylate, N-vinylpyrrolidone, bisphenol ethoxylate diacrylate, ethoxylate phenol monoacrylate, polyethylene glycol 200 diacrylate, tripropylene glycol diacrylate, Trimethylpropane triacrylate, polyethylene glycol diacrylate, ethylene oxide addition type triethyl propane triacrylate, pentaerythritol tetraacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylay Tied pentaerythritol tetraacrylate Bit, 2-phenoxyethyl acrylate, ethoxylated bisphenol A diacrylate, and federated one selected from the group consisting of mixtures thereof, characterized in, the optical fiber ribbon coating resin composition. The method of claim 1, Optical fiber ribbon coating, characterized in that the photoinitiator (C) is selected from the group consisting of Irgacure # 184, Irgacure # 907, Irgacure # 500, Irgacure # 651, Darocure # 1173, Darocure # 116, CGI # 1800 and CGI # 1700 Resin composition. The method of claim 1, The slip agent is PP1362D, CP1481SF, CP1481F, PE1500F, PEW1555, PE1544F, TF1778, TF1780, TF1830, TFW1765, D2S, E2S, A1601, HM 1666, SYLOID63, SYLOID65, SYLOID66, SLOIDID, SLOID74, SLOID74, SLOID7, SLOID7, SLOID, SLOID, Ribbon coating selected from the group consisting of resins for SYLOID978, SYLOID160, SYLOID161, SYLOID162, SYLOID800, SYLOID810, SYLOID150, SYLOID244, SYLOID266, SYLOID255, HK125, HK400, OK412, OK412LC, OK520, OK607, TS100 and TT600 Composition. The method of claim 1, The antifoaming agent is BYK-011, BYK-019, BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-026, BYK-027, BYK-028, BYK-045 , BYK-055, BYK-057 and BYK-066, characterized in that the resin composition for optical fiber ribbon coating. The method of claim 1, Dispersant further comprises 0.1 to 5% by weight, wherein the dispersant is BYK-151, BYK-154, BYK-220S, BYK-P104, BYK-P104S, BYK-P105, Anti-Terra-203, Anti-Terra-204, Anti-Terra-205, Anti-Terra-206, Anti-Terra-U, Anti-Terra-U80, Bykumen, Disperbyk, Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-110, Disperbyk- 111, Disperbyk-115, Disperbyk-116, Disperbyk-130, Disperbyk-140, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-169, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-181, Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-190, Lactimon and Lactiomon-WS Resin composition for optical fiber ribbon coating characterized by the above-mentioned. The method of claim 1, An antioxidant further comprises 0.1 to 5% by weight, wherein the antioxidant is selected from the group consisting of Irganox 1010, Irganox1035, Irganox1076, and mixtures thereof, the resin composition for optical fiber ribbon coating.