JP2008250076A - Optical fiber ribbon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical fiber ribbon which is excellent in releasability between a first ribbon layer and a second ribbon layer. <P>SOLUTION: The optical fiber ribbon has a dual layer structure composed of a first ribbon comprising a plurality of optical fibers bundled together with the first ribbon layer, and the second ribbon layer outside a plurality of first ribbons bundled together. The first ribbon layer is formed by curing a liquid curable resin composition including: a urethane (meth)acrylate having a bisphenol structure (A1); a urethane (meth)acrylate obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group containing (meth)acrylate (A2); a compound having a bisphenol structure and an ethylenically unsaturated group (B); and a compound having an ethylenically unsaturated group except for components (A1), (A2), and (B) (C), and the second ribbon layer is formed by curing a liquid curable resin composition including: 30-90 mass% urethane (meth)acrylate having a structure originating from a polypropylene glycol with 400-1,000 number average molecular weight measured with a gel permeation chromatography method (D); 1-70 mass% of a compound having an ethylenically unsaturated group (E); 0.1-10 mass% polymerization initiator (F); and 1-50 mass% silicone compound with 1,500-35,000 average molecular weight (G), wherein 50-100 mass% of the total amount of the component (E) is a compound having two or more ethylenically unsaturated groups by defining the total amount of the component (E) as 100 mass%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical fiber tape that easily peels the first and second tape layers.

  In the production of an optical fiber, a glass fiber is hot melt-spun and a resin coating is applied for the purpose of protection and reinforcement. This process is called drawing, and as the resin coating, a structure in which a flexible primary coating layer is first provided on the surface of the optical fiber and a highly rigid secondary coating layer is provided on the outside thereof is known. . In addition, in order to put these optical fiber strands coated with resin into practical use, a structure in which a plurality of tapes are arranged on a plane and hardened with a binding material is provided. The resin composition for forming the primary coating layer is a soft material, the resin composition for forming the secondary coating layer is a hard material, and the resin composition for forming a tape-shaped coating layer Is referred to as tape material.

Further, a light having a two-layer structure comprising a first tape in which a plurality of optical fiber strands are bundled with a first tape layer, and an outer second tape layer in which a plurality of the first tapes are bundled. Fiber tapes are also known (Patent Documents 1 to 4). Such multi-fiber optical fiber tapes are required to have excellent peelability and splitting properties when branched.
JP 2007-72195 A JP 2005-321645 A Japanese Patent Laid-Open No. 7-134230 JP-A-6-265737

  The objective of this invention is providing the optical fiber tape which is easy to peel the 1st layer and the 2nd tape layer.

  Therefore, the present inventors have studied the strength, function, and peelability of the cured product as an optical fiber coating layer by blending various components with the liquid curable resin composition containing urethane (meth) acrylate. However, it has been found that the above-described object can be achieved by employing a coating material having a specific configuration for each of the first and second layers.

That is, the present invention comprises a first tape in which a plurality of optical fiber strands are bundled with a first tape layer, and a second tape layer of an outer layer in which a plurality of the first tapes are bundled. A layered optical fiber tape,
The first tape layer has the following components (A1), (A2), (B) and (C):
(A1) Urethane (meth) acrylate having a bisphenol structure,
(A2) urethane (meth) acrylate obtained by reacting aliphatic polyether polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate,
(B) a compound having a bisphenol structure and an ethylenically unsaturated group,
(C) a liquid curable resin composition containing a compound having an ethylenically unsaturated group other than components (A1), (A2) and (B) is cured;
The second tape layer has the following components (D), (E), (F) and (G):
(D) 30 to 90% by mass of urethane (meth) acrylate having a structure derived from polypropylene glycol having a number average molecular weight of 400 to 1000 determined by a gel permeation chromatography method,
(E) 1 to 70% by mass of a compound having an ethylenically unsaturated group,
(F) Polymerization initiator 0.1-10% by mass,
(G) 1-50 mass% of silicone compounds having an average molecular weight of 1,500-35,000
Containing, and
(E) The total amount of the component is 100% by mass, and 50 to 100% by mass of the component is a compound having two or more ethylenically unsaturated groups.
An optical fiber tape is provided which is obtained by curing a liquid curable resin composition.

  The optical fiber tape of the present invention is excellent in the peelability of the first layer and the second layer.

The optical fiber tape of the present invention includes a first tape in which a plurality of optical fiber strands are bundled in a first tape layer, and a second tape layer in an outer layer in which a plurality of the first tapes are bundled. It has a two-layer structure.
The first tape layer comprises the following components (A1), (A2), (B) and (C):
(A1) Urethane (meth) acrylate having a bisphenol structure,
(A2) urethane (meth) acrylate obtained by reacting aliphatic polyether polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate,
(B) a compound having a bisphenol structure and an ethylenically unsaturated group,
(C) It is formed by curing a liquid curable resin composition (composition 1) containing a compound having an ethylenically unsaturated group other than components (A1), (A2) and (B).

  The urethane (meth) acrylate of component (A1) used in composition 1 has a bisphenol structure. For example, it is produced by reacting a polyol having a bisphenol structure with a polyisocyanate and a hydroxyl group-containing (meth) acrylate. That is, it is produced by reacting the isocyanate group of diisocyanate with the hydroxyl group of polyol and the hydroxyl group of hydroxyl group-containing (meth) acrylate, respectively.

  As this reaction, for example, a method in which polyol, diisocyanate and hydroxyl group-containing (meth) acrylate are charged together and reacted; a method in which polyol and diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; A method of reacting acrylate, then reacting polyol; reacting diisocyanate and hydroxyl group-containing (meth) acrylate, then reacting polyol, and finally reacting hydroxyl group-containing (meth) acrylate again.

  Examples of the polyol having a bisphenol structure include an alkylene oxide addition polyol of bisphenol A, an alkylene oxide addition polyol of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, an alkylene oxide addition polyol of hydrogenated bisphenol A, and hydrogenated bisphenol F. An alkylene oxide addition polyol etc. are mentioned. Among these, those having a bisphenol A structure are preferable, and an alkylene oxide addition polyol of bisphenol A is particularly preferable. These polyols can also be obtained as commercial products such as Uniol DA400, DA700, DA1000, DB400 (above, manufactured by NOF Corporation).

Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6-hexane Diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fuma , 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5 (or 2,6)- Bis (isocyanatemethyl) -bicyclo [2.2.1] heptane and the like can be mentioned. In particular, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like are preferable.

  These diisocyanates can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl (meth) acrylate. 1,4-butanepolyol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanepolyol mono (meth) acrylate, neopentyl glycol mono ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) Acrylate, the following formula (1) or (2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and n represents a number of 1 to 15)
(Meth) acrylate represented by the following. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can also be used. Of these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable.

  These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.

  The proportion of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate used is 1.1 to 3 equivalents of the isocyanate group contained in the diisocyanate and 0.1 hydroxyl group of the hydroxyl group-containing (meth) acrylate with respect to 1 equivalent of the hydroxyl group contained in the polyol. It is preferable to be 2 to 1.5 equivalents.

  In the reaction of these compounds, for example, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1 It is preferable to use 0.01 to 1 part by mass of a urethane catalyst such as 1,4-diazabicyclo [2.2.2] octane with respect to 100 parts by mass of the total amount of reactants. The reaction temperature is usually 10 to 90 ° C, particularly preferably 30 to 80 ° C.

  A part of the hydroxyl group-containing (meth) acrylate may be replaced with a compound having a functional group that can be added to an isocyanate group. Examples thereof include γ-mercaptotrimethoxysilane and γ-aminotrimethoxysilane. By using these compounds, adhesion to a substrate such as glass can be enhanced.

  The urethane (meth) acrylate having a bisphenol structure as the component (A1) is blended in the total composition of the composition 1 in an amount of 5 to 40% by mass, further 10 to 30% by mass, and particularly 15 to 20% by mass. It is preferable in view of mechanical properties such as Young's modulus, breaking strength, and breaking elongation.

  Urethane (meth) acrylate obtained by reacting (A2) component aliphatic polyether polyol, polyisocyanate, and hydroxyl group-containing (meth) acrylate contains diisocyanate isocyanate group, aliphatic polyether polyol hydroxyl group and hydroxyl group-containing It is produced by reacting with a hydroxyl group of (meth) acrylate.

  The urethane (meth) acrylate of (A2) can be produced by using an aliphatic polyether polyol in place of the polyol having the bisphenol A structure in the synthesis method of the urethane (meth) acrylate of (A1). .

  Examples of the aliphatic polyether polyol include ring-opening copolymerization of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more ion-polymerizable cyclic compounds. Aliphatic polyether polyols obtained in this way. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, and tetraoxane. , Cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, glycidyl benzoate And cyclic ethers such as Further, a polyether polyol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with a cyclic imine such as ethyleneimine, a cyclic lactone acid such as β-propiolactone or glycolic acid lactide, or dimethylcyclopolysiloxane. Can also be used. Specific combinations of the two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 And terpolymers of -oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, ethylene oxide, and the like. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form.

  These aliphatic polyether polyols are, for example, PTMG650, PTMG1000, PTMG2000 (Mitsubishi Chemical), PPG-400, PPG1000, PPG2000, PPG3000, EXCENOL720, 1020, 2020 (above, Asahi Glass Urethane), PEG1000, Unisafe DC1100. , DC1800 (above, manufactured by NOF Corporation), PPTG2000, PPTG1000, PTG400, PTGL2000 (above, manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000A, PBG2000B (above, manufactured by Daiichi Kogyo Seiyaku) It can also be obtained as a commercial product. Diols that are copolymers of butene-1-oxide and ethylene oxide are commercially available such as EO / BO500, EO / BO1000, EO / BO2000, EO / BO3000, and EO / BO4000 (above, manufactured by Daiichi Kogyo Seiyaku). Available as a product.

  (A2) The urethane (meth) acrylate obtained by reacting the aliphatic polyether polyol, polyisocyanate, and hydroxyl group-containing (meth) acrylate is 10 to 50% by mass, and further 20 to 50% by mass in the total composition of composition 1. %, Particularly 20 to 40% by mass is preferable in view of mechanical properties such as Young's modulus, breaking strength and breaking elongation of the cured product.

  If necessary, urethane (meth) acrylate (A3) other than (A1) and (A2) can be blended with Composition 1 as long as the characteristics of the present invention are not impaired. (A3) The urethane (meth) acrylate is not particularly limited, and examples thereof include urethane (meth) acrylate that does not have a polyol component and is obtained by a reaction between diisocyanate and a hydroxyl group-containing (meth) acrylate. Specific examples of the component (A3) include urethane (meth) acrylate in which hydroxyethyl (meth) acrylate is bonded to both ends of 2,4-tolylene diisocyanate and 2,4-tolylene diisocyanate and hydroxyethyl (meth) acrylate. And an equimolar reaction product with hydroxypropyl (meth) acrylate.

  The urethane (meth) acrylate other than (A3) and (A2), which are the components (A3), is preferably blended in the total composition of the composition 1 in an amount of 0 to 20% by mass, particularly 0 to 10% by mass.

  The component (B) is a compound having a bisphenol structure and an ethylenically unsaturated group. Such compounds include, for example, both end (meth) acrylic acid adducts of bisphenol A diglycidyl ether, di (meth) acrylates of polyols of bisphenol A ethylene oxide or propylene oxide adducts, hydrogenated bisphenol A ethylene oxide. Or the propylene oxide adduct polyol di (meth) acrylate, the epoxy (meth) acrylate which added (meth) acrylate to the diglycidyl ether of bisphenol A, etc. are mentioned. Among these, those having a bisphenol A structure are preferable, and di (meth) acrylate of bisphenol A to which ethylene oxide is added is particularly preferable.

  The compound of component (B) is preferably contained in the total composition of composition 1 in an amount of 5 to 50% by mass, further 10 to 40% by mass, particularly 10 to 35% by mass.

  The compound having an ethylenically unsaturated group as component (C) is a component other than components (A1), (A2) and (B). When component (A3) is blended, component (A1) , (A2), (A3), and (B), and a polymerizable monofunctional compound or a polymerizable polyfunctional compound can be used. Here, the polymerizable monofunctional compound is a compound having one ethylenically unsaturated group, and the polymerizable polyfunctional compound is a compound having two or more ethylenically unsaturated groups. Examples of such monofunctional compounds include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, di- Examples include alicyclic structure-containing (meth) acrylates such as cyclopentanyl (meth) acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, and vinylpyridine. Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodec (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7- Amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, The compound represented by following formula (3)-(6) can be mentioned.

Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, and r represents a number of 0-12, preferably 1-8)

Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R ⁷ represents a hydrogen atom or a methyl group, and p is preferably The number of 1-4 is shown.)

(In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independent of each other and are H or CH ₃ , and q is an integer of 1 to 5)

  Among these polymerizable monofunctional compounds, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, and lauryl acrylate are preferable.

  As commercially available products of these polymerizable monofunctional compounds, IBXA (manufactured by Osaka Organic Chemical Industry), Aronix M-111, M-113, M114, M-117, TO-1210 (above, manufactured by Toagosei Co., Ltd.) should be used. Can do.

  Examples of the polymerizable polyfunctional compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) ) Acrylate, tricyclodecane dimethylol diacrylate, 1,4-butane polyol di (meth) acrylate, 1,6-hexane polyol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethylol diacrylate, triethylene glycol divinyl ether and the following formula (7)

(Wherein R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group and n is a number from 1 to 100)
The compound etc. which are represented by these are mentioned.

  Among these polymerizable polyfunctional compounds, compounds represented by the above formula (7) such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tricyclodecane dimethylol diacrylate, tris (2-hydroxyethyl) Iaoocyanurate tri (meth) acrylate and tripropylene glycol di (meth) acrylate are preferred, and tripropylene glycol di (meth) acrylate is particularly preferred.

  As commercial products of these polymerizable polyfunctional compounds, for example, Iupimer UV, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Aronix M-215, M-315, M-325 (above, manufactured by Toagosei Co., Ltd.) can be used. . Moreover, Arrowix TO-1210 (product made from Toagosei) can be used.

  These (C) compounds having an ethylenically unsaturated group are preferably contained in the total composition of Composition 1 in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 40% by mass.

The second tape layer has the following components (D), (E), (F) and (G):
(D) 30 to 90% by mass of urethane (meth) acrylate having a structure derived from polypropylene glycol having a number average molecular weight of 400 to 1000 determined by gel permeation chromatography method,
(E) 1 to 70% by mass of a compound having an ethylenically unsaturated group,
(F) Polymerization initiator 0.1 to 10% by mass,
(G) 1-50 mass% of silicone compounds having an average molecular weight of 1,500-35,000
Containing, and
(E) The total amount of the component is 100% by mass, and 50 to 100% by mass of the component is a compound having two or more ethylenically unsaturated groups.
It is formed by curing a liquid curable resin composition (Composition 2).

  The urethane (meth) acrylate of the component (D) used in the composition 2 is produced, for example, by reacting polypropylene glycol (polyol) having a number average molecular weight of 400 to 1000, diisocyanate, and hydroxyl group-containing (meth) acrylate. Is done. That is, it is produced by reacting the isocyanate group of diisocyanate with the hydroxyl group of polyol and the hydroxyl group of hydroxyl group-containing (meth) acrylate, respectively.

  As this reaction, for example, a method in which polyol, diisocyanate and hydroxyl group-containing (meth) acrylate are charged together and reacted; a method in which polyol and diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; A method of reacting acrylate, then reacting polyol; reacting diisocyanate and hydroxyl group-containing (meth) acrylate, then reacting polyol, and finally reacting hydroxyl group-containing (meth) acrylate again.

The polyol used here is polypropylene glycol having a number average molecular weight of 500 to 4000. The number average molecular weight is determined by a gel permeation chromatography method (GPC method) using polystyrene as a molecular weight standard.
Polypropylene glycol is available as a commercial product such as PPG-400, PPG1000, PPG2000, PPG3000, EXCENOL720, 1020, and 2020 (above, manufactured by Asahi Glass Urethane Co., Ltd.).

  As diisocyanate and hydroxyl group-containing (meth) acrylate, those similar to those used in the component (A) can be used. In addition, the proportions of polyol, diisocyanate and hydroxyl group-containing (meth) acrylate used, and these reactions can be carried out in the same manner as described above.

  The urethane (meth) acrylate as the component (D) is contained in the entire composition 2 in an amount of 30 to 75% by mass, preferably 35 to 70% by mass, and more preferably 45 to 65% by mass.

  Although it does not specifically limit as a compound which has an ethylenically unsaturated group which is (E) component, The thing similar to the components (B) and (C) of the said composition 1 can be used.

(E) The compound which has an ethylenically unsaturated group of a component is 20-65 mass% in the whole composition of the composition 2, Preferably it is 25-60 mass%, More preferably, 30-50 mass% is contained.
Furthermore, when the total amount of component (E) is 100% by mass, 50 to 100% by mass is preferably a compound having two or more ethylenically unsaturated groups, more preferably 70 to 100% by mass, Preferably it is 90-100 mass%, Most preferably, it is 100 mass%. Although it does not specifically limit as a compound which has 2 or more of ethylenically unsaturated groups used as (E) component, Tripropylene glycol di (meth) acrylate etc. are preferable.

  As the polymerization initiator of the component (F) used in the composition 2, a thermal polymerization initiator or a photoinitiator can be used.

  When the liquid curable resin composition of the composition 2 is thermosetting, a thermal polymerization initiator such as a peroxide or an azo compound is usually used. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like.

  Moreover, when the liquid curable resin composition of the composition 2 is photocurable, it is preferable to use a photopolymerization initiator and further use a photosensitizer if necessary. Here, as the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2- Lorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide; IRGACURE 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61; Examples include Lucirin TPO (manufactured by BASF); Ubekrill P36 (manufactured by UCB) and the like. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. Isoamyl acid; Ubekryl P102, 103, 104, 105 (above, manufactured by UCB) and the like.

  When the liquid curable resin composition of the present invention is cured using both heat and ultraviolet rays, the thermal polymerization initiator and the photopolymerization initiator can be used in combination. (F) The polymerization initiator is contained in the entire composition 2 in an amount of 0.1 to 10% by mass, preferably 0.3 to 7% by mass.

Furthermore, the composition 2 contains a silicone compound having an average molecular weight of 1,500 to 35,000 as the component (G). The said (G) component is important when obtaining the peelability improvement effect from the layer which the film formed using the resin composition of this invention adjoins. When the average molecular weight of the component (G) is less than 1,500, a sufficient peelability improvement effect cannot be obtained, and when the average molecular weight exceeds 35,000, the peelability improvement effect becomes insufficient. A more preferable average molecular weight is 1,500 to 20,000, further preferably 1,500 to 20,000, and particularly preferably 3,000 to 15,000.
Moreover, it is preferable that (G) component does not have polymerizable groups, such as an ethylenically unsaturated group. Since the component (G) does not have a polymerizable group such as an ethylenically unsaturated group, good peelability can be maintained even when a thermal history is applied.

Examples of the silicone compound include polyether-modified silicone, alkyl-modified silicone, urethane acrylate-modified silicone, urethane-modified silicone, methylstyryl-modified silicone, epoxy polyether-modified silicone, and alkylaralkyl polyether-modified silicone. Ether-modified silicone is particularly preferred. The polyether-modified silicone, at least one group to the silicon atom ^{R 14 - (R 15 O)} s -R 16 - ( wherein, R ¹⁴ represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, R ¹⁵ Represents an alkylene group having 2 to 4 carbon atoms (R ¹⁵ may be a mixture of two or more alkylene groups), R ¹⁶ represents an alkylene group having 2 to 12 carbon atoms, and s represents 1 to 20 carbon atoms. A polydimethylsiloxane compound having a number attached thereto is preferred. Among these, R ¹⁵ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. Among the commercially available products of the silicone compound, those having no polymerizable group such as an ethylenically unsaturated group include, for example, SH28PA; dimethylpolysiloxane polyoxyalkylene copolymer, Toray Dow Corning Co., Paintad 19, 54; Polysiloxane polyoxyalkylene copolymer, Toray Dow Corning, FM0411; Silaplane, Chisso, SF8428; Dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH), Toray Dow Corning, BYK UV3510 (BIC Chemie Japan) Dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 (Toray Dow Corning Silicone Co., dimethylpolysiloxane-polyoxyalkylene copolymer), and the like. Moreover, as a commercial item of the said silicone compound which has an ethylenically unsaturated group, Tego Rad 2300, 2200N, Tego Chemie, etc. can be mentioned, for example.

  (G) A component is 0.1-50 mass% in the whole composition of the composition 2, Preferably it is 0.5-40 mass%, More preferably, 1-20 mass% is contained.

  In composition 1 and composition 2, as necessary, various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, as long as the properties of the present invention are not impaired. Thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, coating surface improvers and the like can be blended.

  The composition 1 can further contain a silicone compound having an average molecular weight of 1,500 to 35,000 and a polymerization initiator as in the case of the composition 2. These may be the same as those used in the composition 2.

  The composition 1 and the composition 2 are cured by heat and / or radiation. Here, the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like. Say.

  The optical fiber tape of the present invention bundles a plurality of optical fiber strands and coats with a first tape layer using the composition 1 to form a first tape, and a plurality of the first tapes are collected. An optical fiber tape having a two-layer structure can be obtained by coating with the second tape layer using the composition 2.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

[Production Example 1: (A1) Synthesis of urethane (meth) acrylate 1]
While adding 0.120 g of 2,6-di-t-butyl-p-cresol, 354.86 g of 2,4-tolylene diisocyanate and 0.240 g of dibutyltin dilaurate to a reaction vessel equipped with a stirrer, Cooled to ° C. 236.60 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was then heated to 40 ° C. and stirred for 1 hour. Thereafter, the liquid temperature was cooled to 20 ° C., and 407.51 g of bisphenol A ethylene oxide addition diol (manufactured by NOF Corporation, DA400) was added. After confirming the exotherm, the mixture was stirred at 65 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate was 0.1% by mass or less. Let the obtained (A) urethane (meth) acrylate be UA-1.
The obtained urethane (meth) acrylate has a structure in which 2-hydroxyethyl acrylate is bonded to both ends of a diol having a bisphenol A structure via 2,4-tolylene diisocyanate.

[Production Example 2: (A2) Synthesis of urethane (meth) acrylate 1]
Into a reaction vessel equipped with a stirrer, 0.240 g of 2,6-di-t-butyl-p-cresol, 271.72 g of 2,4-tolylene diisocyanate, and 546.07 g of polypropylene glycol having a number average molecular weight of 700 were added. It cooled until the liquid temperature became 15 degreeC. After adding 0.799 g of dibutyltin dilaurate, the mixture was stirred for 1 hour so that the liquid temperature did not exceed 40 ° C. These were cooled with ice until the liquid temperature became 15 ° C. or lower while stirring. Thereafter, 181.17 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted by stirring for 1 hour. Stirring was continued for 3 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate became 0.1% by mass or less. Let the obtained (A) urethane (meth) acrylate be UA-2.
The obtained urethane (meth) acrylate has a structure in which 2-hydroxyethyl acrylate is bonded to both ends of propylene glycol via 2,4-tolylene diisocyanate.

[Production Example 3: (A2) Synthesis of urethane (meth) acrylate 2]
To a reaction vessel equipped with a stirrer, 0.240 g of 2,6-di-t-butyl-p-cresol, 42.10 g of 2,4-tolylene diisocyanate and 0.799 g of dibutyltin dilaurate were added, Cooled to ° C. 570.86 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was then placed in a hot water bath at 40 ° C. and stirred for 1 hour. Then, after confirming that the temperature rise was not seen, it was made to stir at 65 degreeC for 3 hours, and it was set as reaction completion when the residual isocyanate became 0.1 mass% or less. Let the obtained (A) urethane (meth) acrylate be UA-3.
The obtained urethane (meth) acrylate has a structure in which 2-hydroxyethyl acrylate is bonded to both ends of 2,4-tolylene diisocyanate.

[Production Example 4]
Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer, and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a liquid curable resin composition (Composition 1).

In Table 1,
Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals).
Lucillin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Specialty Chemicals).
Irganox 245: ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by Ciba Specialty Chemicals).
SH28PA: dimethylpolysiloxane polyoxyalkylene copolymer (manufactured by Dow Corning Toray)

[Production Example 5: (D) Synthesis of urethane (meth) acrylate:]
In a reaction vessel equipped with a stirrer, 209.27 g of tripropylene glycol diacrylate, 0.31 g of 2,6-di-t-butyl-p-cresol, 35.32 g of 2,4-tolylene diisocyanate, a number average molecular weight of 700 Then, 71.11 g of polypropylene glycol was added and cooled until the liquid temperature reached 15 ° C. After adding 0.104 g of dibutyltin dilaurate, the mixture was stirred for 1 hour so that the liquid temperature did not exceed 40 ° C. While stirring these, the solution was ice-cooled until the liquid temperature became 10 ° C. or lower. Thereafter, 23.55 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted by stirring for 1 hour. Stirring was continued for 3 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate became 0.1% by mass or less. Let the obtained (D) urethane (meth) acrylate be UA-4.

[Production Example 6: Synthesis of urethane (meth) acrylate]
A reaction vessel equipped with a stirrer was charged with 1.484 g of 2,4-tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol and 0.080 g of dibutyltin dilaurate, and these were stirred. However, the solution was cooled on ice until the liquid temperature became 15 ° C. or lower. 77.422 g of a ring-opened polymer of propylene oxide having a number average molecular weight of 2000 was added, and the mixture was reacted by stirring for 2 hours while controlling the liquid temperature to be 35 ° C. or lower. Next, 8.990 g of 2-hydroxypropyl acrylate was added dropwise, and further, 24.740 g of hydroxyethyl acrylate was added dropwise, and stirring was continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when it became less than%. Let the obtained urethane (meth) acrylate be UA-5.

[Production Example 7]
Each component having the composition shown in Table 2 was charged into a reaction vessel equipped with a stirrer and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a liquid curable resin composition (Composition 2).

In Table 2,
SH28PA; dimethylpolysiloxane polyoxyalkylene copolymer (manufactured by Dow Corning Toray).
UA-3; the same as (A) urethane (meth) acrylate obtained in Production Example 3.

Example 1, Comparative Examples 1-3
An optical fiber tape was manufactured using the composition 1 (a or b) shown in Table 1 and the composition 2 (a or b) shown in Table 2 in the combinations shown in Table 3. About the obtained optical fiber tape, peeling stress and splitting property were evaluated. The results are also shown in Table 3.

(Method for producing sample for evaluation)
Composition 1 was coated on glass with an applicator to a thickness of 130 μm and cured under 500 mJ / cm ² and 1% oxygen. Further, the resin liquid of the composition 2 was applied from above with a 381 μm applicator and cured under nitrogen at 500 mJ / cm ² to form a bilayer film having a total thickness of 200 μm.

(Evaluation methods)
1. Peel stress:
A strip-shaped sample was prepared from the two-layer cured film obtained above so that the stretched portion had a width of 10 mm. The stress at the time of peeling off the two layers was measured in accordance with JIS Z0237 (adhesion test) using a tensile tester. From the tensile strength at a tensile speed of 50 mm / min, the sticking force of the two-layer film was determined.

2. Divisibility:
A strip-shaped sample was prepared from the two-layer cured film obtained above so that the stretched portion had a width of 10 mm. The composition 2 of the two-layer film was scratched with a cutter, and it was confirmed that the composition 1 was not scratched when being bent and only the composition 2 was cracked. The test was performed 40 times, and the number of cracks without being scratched was counted.

Claims (1)

An optical fiber tape having a two-layer structure comprising a first tape in which a plurality of optical fiber strands are bundled with a first tape layer and an outer second tape layer in which a plurality of the first tapes are bundled. Because
The first tape layer has the following components (A1), (A2), (B) and (C):
(A1) Urethane (meth) acrylate having a bisphenol structure,
(A2) urethane (meth) acrylate obtained by reacting aliphatic polyether polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate,
(B) a compound having a bisphenol structure and an ethylenically unsaturated group,
(C) a liquid curable resin composition containing a compound having an ethylenically unsaturated group other than components (A1), (A2) and (B) is cured;
The second tape layer has the following components (D), (E), (F) and (G):
(D) 30 to 90% by mass of urethane (meth) acrylate having a structure derived from polypropylene glycol having a number average molecular weight of 400 to 1000 determined by a gel permeation chromatography method,
(E) 1 to 70% by mass of a compound having an ethylenically unsaturated group,
(F) Polymerization initiator 0.1 to 10% by mass,
(G) 1-50 mass% of silicone compounds having an average molecular weight of 1,500-35,000
Containing, and
(E) The total amount of the component is 100% by mass, and 50 to 100% by mass of the component is a compound having two or more ethylenically unsaturated groups.
An optical fiber tape obtained by curing a liquid curable resin composition.