KAMO SATOSHI (JP)
KUROSAWA TAKAHIKO (JP)
JSR CORP (JP)
YAMAGUCHI HIROSHI (JP)
KAMO SATOSHI (JP)
KUROSAWA TAKAHIKO (JP)
| WO2006049488A1 | 2006-05-11 | |||
| WO2006025734A1 | 2006-03-09 | |||
| WO2005026228A1 | 2005-03-24 |
| US20030119934A1 | 2003-06-26 |
Claims
1. An optical fiber ribbon with a double layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, wherein the first ribbon layer is produced by curing a curable liquid resin composition, Composition 1, comprising:
(Al) a urethane (meth) aery late having a bisphenol structure;
(A2) a urethane (meth) aery late obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group -containing (meth)acrylate; (B) a compound having a bisphenol structure and an ethylenically unsaturated group; and
(C) a compound having an ethylenically unsaturated group other than the components (Al), (A2), and (B): and the second ribbon layer is produced by curing a curable liquid resin composition, Composition 2, comprising:
(D) from about 30 to about 90 mass% of a urethane (meth)acrylate having a structure derived from polypropylene glycol with a number average molecular weight determined by gel permeation chromatography of from about 400 to about 1,000; (E) from about 1 to about 70 mass% of a compound having an ethylenically unsaturated group;
(F) from about 0.1 to about 10 mass% of a polymerization initiator; and
(G) from about 1 to about 50 mass% of a silicone compound with an average molecular weight of from about 1,500 to about 35,000; wherein from about 50 to about 100 mass% of the component (E) is a compound having two or more ethylenically unsaturated groups.
2. A process to create an optical fiber ribbon with a double layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, comprising the steps of a) providing an optical fiber; b) coating said optical fiber with a radiation curable coating, which is a primary coating, and optionally applying radiation to cure said primary coating; c) coating said optical fiber with a second radiation curable coating, which is a Secondary coating, applied over the Primary coating; and d) applying radiation to cure said Secondary coating; and e) arranging more than one optical fibers from step d) in a desired ribbon configuration; f) applying the first ribbon layer radiation curable liquid resin composition of claim 1 to the one or more optical fibers in the desired configuration of step e) to create a first ribbon layer and applying radiation to cure said first ribbon layer radiation curable liquid resin composition of claim l; g) arranging more than one first ribbon layers from step f) into a desired second ribbon layer configuration; h) applying the second ribbon layer radiation curable liquid resin composition of Claim 1 to the second ribbon layer configuration and applying radiation to cure said second ribbon layer radiation curable liquid resin composition of Claim 1. |
Title: Liquid curable resin composition for optical fiber tapes
FIELD OF THE INVENTION
The present invention relates to an optical fiber ribbon in which a first ribbon layer and a second ribbon layer are easily separated.
BACKGROUND OF THE INVENTION
In the manufacture of optical fibers, a glass fiber is produced by spinning molten glass, and a resin coating is provided over the glass fiber for protection and reinforcement. This step is referred to as fiber drawing. As the resin coating, a structure is known in which a flexible primary coating layer is formed on the surface of an optical fiber and a rigid secondary coating layer is applied over the primary coating layer.
A structure is also known in which the resin-coated optical fibers are placed side by side in a plane and bundled with a bundling material to produce a ribbon-shaped coating layer for practical use. A resin composition for forming the primary coating layer is called a primary material, a resin composition for forming the secondary coating layer is called a secondary material, and a resin composition for forming the ribbon-shaped coating layer is called a ribbon matrix material.
An optical fiber ribbon with a double -layer structure is also known, which comprises a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon having the first ribbons as an outer layer. See JP-A-2007-72195 and JP-A-2005-321645 and JP-A-7-134230 and JP-A-6- 265737.
Such a multicore optical fiber ribbon is required to have an excellent peelability and splitability when branching.
SUMMARY OF THE INVENTION
The first aspect of the instant claimed invention is an optical fiber ribbon with a double layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, wherein the first ribbon layer is produced by curing a curable liquid resin composition, Composition 1, comprising:
(Al) a urethane (meth)acrylate having a bisphenol structure;
(A2) a urethane (me th) aery late obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group -containing (meth)acrylate;
(B) a compound having a bisphenol structure and an ethylenically unsaturated group; and
(C) a compound having an ethylenically unsaturated group other than the components (Al), (A2), and (B): and wherein the second ribbon layer is produced by curing a curable liquid resin composition, Composition 2, comprising:
(D) from about 30 to about 90 mass% of a urethane (me th) aery late having a structure derived from polypropylene glycol with a number average molecular weight determined by gel permeation chromatography of from about 400 to about 1,000;
(E) from about 1 to about 70 mass% of a compound having an ethylenically unsaturated group;
(F) from about 0.1 to about 10 mass% of a polymerization initiator; and (G) from about 1 to about 50 mass% of a silicone compound with an average molecular weight of from about 1,500 to about 35,000; wherein from about 50 to about 100 mass% of the component (E) is a compound having two or more ethylenically unsaturated groups.
The second aspect of the instant claimed invention is a process to create an optical fiber ribbon with a double layer structure comprising a first ribbon
formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, comprising the steps of a) providing an optical fiber; b) coating said optical fiber with a radiation curable coating, which is a primary coating, and optionally applying radiation to cure said primary coating; c) coating said optical fiber with a second radiation curable coating, which is a Secondary coating, applied over the Primary coating; and d) applying radiation to cure said Secondary coating; and e) arranging more than one optical fibers from step d) in a desired ribbon configuration; f) applying the first ribbon layer radiation curable liquid resin composition, Composition 1, to the one or more optical fibers in the desired configuration of step e) to create a first ribbon layer and applying radiation to cure said first ribbon layer radiation curable liquid resin composition of the first aspect of the instant claimed invention; g) arranging more than one first ribbon layers from step f) into a desired second ribbon layer configuration; and h) applying the second ribbon layer radiation curable liquid resin composition, Composition 2, to the second ribbon layer configuration and applying radiation to cure said second ribbon layer radiation curable liquid resin composition of the instant claimed invention.
An object of the present invention is to provide an optical fiber ribbon in which a first ribbon layer and a second ribbon layer are easily separated.
The inventors of the present invention have prepared curable liquid resin compositions containing urethane (meth) aery late to evaluate the strength, functions, and peelability as the optical-fiber coating layers. As a result, the inventors have found that the above object can be achieved by using covering materials with specific compositions for the first ribbon layer and the
second ribbon layer. The first ribbon layer can be easily peeled off from the second ribbon layer in the optical fiber ribbon of the present invention.
DETAILED DESCRIPTION OF THE INVENTION The first aspect of the instant claimed invention is an optical fiber ribbon with a double layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, wherein the first ribbon layer is produced by curing a curable liquid resin composition, Composition 1, comprising:
(Al) a urethane (me th) aery late having a bisphenol structure; (A2) a urethane (meth)acrylate obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group -containing (meth)acrylate; (B) a compound having a bisphenol structure and an ethylenically unsaturated group; and
(C) a compound having an ethylenically unsaturated group other than the components (Al), (A2), and (B): and the second ribbon layer is produced by curing a curable liquid resin composition, Composition 2, comprising:
(D) from about 30 to about 90 mass% of a urethane (meth)acrylate having a structure derived from polypropylene glycol with a number average molecular weight determined by gel permeation chromatography of from about 400 to about 1,000; (E) from about 1 to about 70 mass% of a compound having an ethylenically unsaturated group;
(F) from about 0.1 to about 10 mass% of a polymerization initiator; and
(G) from about 1 to about 50 mass% of a silicone compound with an average molecular weight of from about 1,500 to about 35,000;
wherein from about 50 to about 100 mass% of the component (E) is a compound having two or more ethylenically unsaturated groups.
The optical fiber ribbon of the present invention has a double-layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon which bundles and covers a number of the first ribbons as an outer layer.
The first ribbon layer is produced by curing a curable liquid resin composition (Composition 1) comprising
(Al) a urethane (me th) aery late having a bisphenol structure, (A2) a urethane (me th) aery late obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group -containing (meth) aery late,
(B) a compound having a bisphenol structure and an ethylenically unsaturated group, and (C) a compound having an ethylenically unsaturated group other than the components (Al), (A2), and (B).
The urethane (meth)acrylate of the component (Al) used in Composition 1 has a bisphenol structure and is produced by, for example, reacting a polyol having a bisphenol structure, a polyisocyanate, and a (meth)acrylate containing a hydroxyl group. Specifically, the urethane (meth)acrylate is produced by reacting isocyanate groups of a diisocyanate with hydroxyl groups of the polyol and the hydroxyl group -containing (meth)acrylate.
As the method for reacting these compounds, a method of reacting the polyol, the diisocyanate, and the hydroxyl group-containing (meth) aery late all together; a method of reacting the polyol with the diisocyanate, and reacting the resulting product with the hydroxyl group -containing (meth)acrylate; a method of reacting the diisocyanate with the hydroxyl group -containing (meth)acrylate, and reacting the resulting product with the polyol; a method of reacting the diisocyanate with the hydroxyl group -containing (meth) aery late, reacting the resulting product with the polyol, and further reacting the
resulting product with the hydroxyl group -containing (meth) aery late; and the like can be given.
As examples of the polyol having a bisphenol structure, 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, alkylene oxide addition polyol of hydrogenated bisphenol F, and the like can be given. Of these, a polyol having a bisphenol A structure, particularly an alkylene oxide addition polyol of bisphenol A is preferable. These polyols are commercially available as "Uniol DA400", "Uniol DA700", "Uniol DAlOOO", and "Uniol DB400" (manufactured by Nippon Oil and Fats Co., Ltd.), and the like.
As examples of the diisocyanate, 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, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanateethyl)fumarate, 6-isopropyl-l,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 given. Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are preferable.
These diisocyanates may be used either individually or in combination of two or more.
Examples of (meth)acrylates containing a hydroxyl group include 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth) aery late, 1,4-butanepolyol
mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4- hydroxycyclohexyl (meth) aery late, 1,6-hexanepolyol mono (me th) aery late, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylates shown by the following formulas (1) and (2):
CH 2
=C(R 1
)—COOCH 2
CH 2
— (OCOCH 2
CH 2
CH 2
CH 2
CH 2
)JT-OH (1)
wherein R 1 represents a hydrogen atom or a methyl group and n is an integer from 1 to 15.
A compound obtained by the addition reaction of (meth)acrylic acid and a glycidyl group-containing compound such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth) aery late may also be used. Of these hydroxyl group-containing (meth)acrylates, 2-hydroxyethyl (meth)acrylate and 2- hydroxypropyl (meth)acrylate are preferable.
These hydroxyl group -containing (meth) aery late compounds may be used either individually or in combination of two or more.
The polyol, the diisocyanate, and the hydroxyl group-containing (meth)acrylate are preferably used so that the isocyanate groups included in the diisocyanate and the hydroxyl groups included in the hydroxyl group - containing (meth) aery late are respectively 1.1 to 3 equivalents and 0.2 to 1.5 equivalents for one equivalent of the hydroxyl groups included in the polyol.
When reacting these compounds, it is preferable to use a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, l,4-diazabicyclo[2.2.2]octane, or 2,6,7- trimethyl-l,4-diazabicyclo[2.2.2]octane in an amount of 0.01 to 1 part by mass
for 100 parts by mass of the reactants. The reaction temperature is preferably
10 to 9O 0 C, and particularly preferably 30 to 8O 0 C.
The hydroxyl group -containing (meth)acrylate may be partially replaced with a compound having a functional group which can be added to an isocyanate group. As examples of such compound, γ- mercaptotrimethoxysilane, γ-aminotrimethoxysilane, or the like can be given.
Use of these compounds improves adhesion to a substrate such as glass.
The content of the urethane (meth)acrylate having a bisphenol structure of the component (Al) in the composition is preferably 5 to 40 mass%, more preferably 10 to 30 mass%, and particularly preferably 15 to 20 mass%, in order to maintain high Young's modulus of elasticity and ensure bending resistance of the cured product.
The urethane (meth) aery late obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate, which is the component (A2), can be produced by reacting the isocyanate group of the isocyanate with the hydroxyl groups in the aliphatic polyether polyol and the hydroxyl group -containing (meth)acrylate.
The urethane (meth) aery late of the component (A2) can be prepared by the method of synthesizing urethane (meth)acrylate (Al) mentioned above by using an aliphatic polyether polyol instead of the polyol having a bisphenol A structure used in the synthesis of the urethane (meth) aery late (Al).
As examples of the polyether polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and aliphatic polyether polyols obtained by ring-opening copolymerization of two or more ion- polymerizable cyclic compounds can be given. As examples of the ion- polymerizable cyclic compound, cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin,
glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyloxetane, vinyltetrahydrofuran, vinylcyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate can be given. A polyether polyol obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compound and a cyclic imine such as ethyleneimine, a cyclic lactonic acid such as 6-propyolactone or lactide glycolic acid, or a dimethylcyclopolysiloxane may also be used. As specific combinations of two or more ion-polymerizable cyclic compounds, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2- methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide, a ternary polymer of tetrahydrofuran, butene-1-oxide, and ethylene oxide, and the like can be given. The ring- opening copolymer of these ion-polymerizable cyclic compounds may be either a random copolymer or a block copolymer.
The aliphatic polyether polyol is commercially available as "PTMG650", "PTMGlOOO", and PTMG2000 (manufactured by Mitsubishi Chemical Corp.), "PPG-400", "PPGlOOO", "PPG2000", "PPG3000", "EXCENOL 720", "EXCENOL 1020", and "EXCENOL 2020" (manufactured by Asahi Glass Urethane Co., Ltd.), "PEGlOOO", "Unisafe DCIlOO", and "Unisafe DC1800" (manufactured by Nippon Oil and Fats Co., Ltd.), "PPTG2000", "PPTGlOOO", "PTG400", and "PTGL2000" (manufactured by Hodogaya Chemical Co., Ltd.), "Z-3001-4", "Z- 3001-5", "PBG2000A", and "PBG2000B" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like. The copolymer diol of butene-1-oxide and ethylene oxide is commercially available as "EO/BO500", "EO/BO1000", "EO/BO2000", "EO/BO3000", and "EO/BO4000" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.
The content of the urethane (meth) aery late (A2) obtained by reacting an aliphatic polyether polyol, a polyisocyanate, and a hydroxyl group -containing (meth)acrylate in Composition 1 is preferably 10 to 50 mass%, more preferably
20 to 50 mass%, and particularly preferably 20 to 40 mass% from the viewpoint of mechanical characteristic of the cured product such as Young's modulus of elasticity, breaking strength, and breaking elongation.
In addition to the urethane (meth)acrylate (Al) and urethane (meth)acrylate (A2), other urethane (meth)acrylates (urethane (meth)acrylate (A3) may optionally be added to Composition 1 to the extent that the effects of the present invention are not impaired. Although not specifically limited, a urethane (meth) aery late which does not contain a polyol component and is obtained by reacting a diisocyanate compound and a hydroxyl group- containing (meth) aery late compound can be given as an example of the urethane (meth) aery late (A3). As more specific examples of the urethane (meth)acrylate (A3), a urethane (meth) aery late having a structure in which hydroxyethyl (meth)acrylates are bonded to both ends of 2,4-tolylene diisocyanate, an equimolar reaction product of 2,4-tolylene diisocyanate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth) aery late, and the like can be given.
The amount of the component (A3), that is, urethane (meth)acrylates other the component (Al) and the component (A2), added to the curable liquid resin composition is preferably of 0 to 20 mss%, and more preferably 0 to 10 mss%.
The component (B) is a compound having a bisphenol structure and an ethylenically unsaturated group. As examples of such a compound, a (meth)acrylic acid adduct to both ends of bisphenol A diglycidyl ether, a di(meth) aery late of polyol of an ethylene oxide or propylene oxide adduct to bisphenol A, a di(meth) aery late of polyol of an ethylene oxide or propylene oxide adduct to hydrogenated bisphenol A, an epoxy (meth) aery late obtained by adding (meth) aery late to bisphenol A diglycidyl ether, and the like can be given. Of these, a compound having a bisphenol A structure, particularly a di(meth) aery late of ethylene oxide addition bisphenol A is preferable.
The amount of the component (B) in Composition 1 is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 10 to 35 mass%.
As the compound having an ethylenically unsaturated group of component (C), compounds other than the components (Al), (A2), and (B), and when the component (A3) is used, a polymerizable monofunctional compound or a polymerizable polyfunctional compound other than the components (Al), (A2), (A3), and (B) can be used. The polymerizable monofunctional compound refers to a compound having one ethylenically unsaturated group, and the polymerizable polyfunctional compound refers to a compound having two or more ethylenically unsaturated groups. As examples of the monofunctional compound, vinyl group -containing lactams such as N-vinylpyrrolidone and N- vinylcaprolactam, alicyclic structure -containing (meth)acrylates such as isobornyl (meth)acrylate, bornyl (me th) aery late, tricyclodecanyl (meth)acrylate, and dicyclopentanyl (meth) aery late, benzyl (meth)acrylate, 4- butylcyclohexyl (meth) aery late, acryloylmorpholine, vinylimidazole, vinylpyridine, and the like can be given. Further examples include 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) aery late, 2-hydroxybutyl (meth) aery late, methyl (meth)acrylate, ethyl (meth) aery late, propyl (meth)acrylate, isopropyl (meth) aery late, butyl (meth) aery late, amyl (meth) aery late, isobutyl (meth) aery late, t-butyl (meth) aery late, pentyl (meth)acrylate, isoamyl (meth) aery late, hexyl (meth) aery late, heptyl (meth)acrylate, octyl (meth) aery late, isooctyl (meth)acrylate, 2-ethylhexyl (meth) aery late, nonyl (meth) aery late, decyl (meth) aery late, isodecyl (meth) aery late, undecyl (meth) aery late, dodecyl (meth) aery late, lauryl (meth)acrylate, stearyl (meth) aery late, isostearyl (meth) aery late, tetrahydrofurfuryl (meth) aery late, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth) aery late, benzyl (meth) aery late, phenoxyethyl (meth) aery late, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono (meth) aery late, methoxyethylene glycol (meth)acrylate, ethoxyethyl
(meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (me th) aery late, 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) aery late, N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth) aery lamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and compounds shown by the following formulas (3) to (6).
CH 2 =C(R 2 )- CO- -(R 3 O) 1 — R* (3) o
wherein R 2 represents a hydrogen atom or a methyl group, R 3 represents an alkylene group having 2 to 6, and preferably 2 to 4 carbon atoms, R 4 represents a hydrogen atom or an alkyl group having 1 to 12, and preferably 1 to 9 carbon atoms, and r represents an integer from 0 to 12, and preferably from 1 to 8.
wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkylene group having 2 to 8, and preferably 2 to 5 carbon atoms, R 7 represents a hydrogen atom or a methyl group, and p represents an integer preferably from 1 to 4.
wherein R 8 , R 9 , R 10 , and R 11 individually represent H or CH3, and q represents an integer from 1 to 5. Of these polymerizable monofunctional compounds, N-vinylpyrrolidone, vinyl group-containing lactam such as N-vinylcaprolactam, isobornyl (meth)acrylate, and lauryl acrylate are preferable.
As the commercially available products of these polymerizable monofunctional compounds, "IBXA" (manufactured by Osaka Organic Chemical Industry Co., Ltd.), "Aronix M-Hl", "Aronix M-113", "Aronix M-114", "Aronix M-117", and "Aronix TO-1210" (manufactured by Toagosei Co., Ltd.) may be used.
Examples of the polymerizable polyfunctional compounds, trimethylolpropane tri(meth) acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, pentaerythritol tri(meth) acrylate, triethylene glycol diacrylate, tetra-ethylene glycol di(meth)acrylate, tricyclodecanedimethylol diacrylate, 1,4-butanepolyol di(meth)acrylate, 1,6-hexanepoly 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 di(meth) acrylate, tris(2- hydroxyethyl)isocyanurate tri(meth) acrylate, tris(2-hydroxyethyl) isocyanulate di(meth)acrylate, tricyclodecanedimethylol diacrylate, triethylene glycol divinyl ether, and compounds shown by the following formula (7):
CH 2 =C(R 12 )-COO— (CH 2 - CH(R 13 )-O) n ~CO-C(R 12 )=CH 2 (7)
wherein R 12 and R 13 individually represent a hydrogen atom or a methyl group, and n represents an integer from 1 to 100.
Of these polymerizable polyfunctional compounds, the compounds shown by the formula (7) such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tricyclodecanedimethylol diacrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and tripropylene glycol di(meth)acrylate are preferable, with tripropylene glycol di(meth) aery late being particularly preferable.
As the commercially available products of these polymerizable polyfunctional compounds, "Yupimer UV" and "SA1002" (manufactured by Mitsubishi Chemical Corp.), "Aronix M-215", "Aronix M-315", and "Aronix M- 325" (manufactured by Toagosei Co., Ltd.), and the like can be given. "Aronix TO-1210" (manufactured by Toagosei Co., Ltd.) may also be used.
The amount of the compound having an ethylenically unsaturated group in Composition 1 is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 40 mass%.
The second ribbon layer is formed by curing a curable liquid resin composition (Composition 2) comprising: (D) 30 to 90 mass% of a urethane (me th) aery late having a structure derived from polypropylene glycol with a number average molecular weight determined by gel permeation chromatography of 400 to 1,000; (E) 1 to 70 mass% of a compound having an ethylenically unsaturated group; (F) 0.1 to 10 mass% of a polymerization initiator; and (G) 1 to 50 mass% of a silicone compound with an average molecular weight of 1,500 to 35,000; wherein 50 to 100 mass% of the component (E) is a compound having two or more ethylenically unsaturated groups.
The urethane (meth)acrylate used as the component (D) of Composition 2 is produced by reacting a polypropylene glycol (polyol) having a number average molecular weight of 400 to 1,000, a diisocyanate, and a hydroxyl group-containing (meth) aery late, for example. Specifically, the urethane
(metli)acrylate is produced by reacting isocyanate groups of a diisocyanate with hydroxyl groups of the polyol and the hydroxyl group -containing (meth)acrylate.
As the method for reacting these compounds, a method of reacting the polyol, the diisocyanate, and the hydroxyl group -containing (meth) aery late all together; a method of reacting the polyol with the diisocyanate, and reacting the resulting product with the hydroxyl group -containing (meth) aery late; a method of reacting the diisocyanate with the hydroxyl group -containing (meth)acrylate, and reacting the resulting product with the polyol; a method of reacting the diisocyanate with the hydroxyl group-containing (meth)acrylate, reacting the resulting product with the polyol, and further reacting the resulting product with the hydroxyl group -containing (meth)acrylate; and the like can be given.
The polyol used is a polypropylene glycol having a number average molecular weight of 500 to 4,000. The number average molecular weight is determined by gel permeation chromatography (GPC method) as a polystyrene-reduced molecular weight.
The polypropylene glycol is commercially available as "PPG400", "PPGlOOO", "PPG2000", "PPG3000", "EXCENOL 720", "EXCENOL 1020", and "EXCENOL 2020" (manufactured by Asahi Glass Urethane Co., Ltd.), and the like.
The Diisocyanates and the hydroxyl group -containing (meth) aery late s previously mentioned in connection with the component (A) can be used. The ratio of the polyol, diisocyanate, and (meth) aery late containing a hydroxyl group used in the reaction and the method of the reaction of these compounds are the same as mentioned above.
The urethane (meth) aery late of the component (D) is added to Composition 2 in an amount of 30 to 75 mass%, preferably 35 to 70 mass%, and more preferably from 45 to 65 mass%.
Although not particularly limited, the same compounds as mentioned in connection with the component (B) and component (C) of Composition 1 may be used as the compound having an ethylenically unsaturated group of the component (E). The compound having an ethylenically unsaturated group of the component (E) is added to Composition 2 in an amount of 20 to 65 mass%, preferably 25 to 60 mass%, and more preferably from 30 to 50 mass%.
The component (E) preferably comprises the compound having two or more ethylenically unsaturated groups in an amount of 50 to 100 mass%, more preferably 70 to 100 mass%, particularly preferably 90 to 100 mass%, and most preferably 100 mass% in the total 100 mass%. Although not particularly limited, tripropylene glycol di(meth)acrylate and the like are preferable as the compound having two ore more ethylenically unsaturated groups used as the component (E). As the polymerization initiator used as the component (F) in
Composition 2, a heat polymerization initiator or a photo polymerization initiator may be used.
In the case of curing the curable liquid resin composition of Composition 2 with heat, a heat polymerization initiator such as a peroxide or an azo compound is usually used. As specific examples of the heat polymerization initiator, benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like can be given.
A photo polymerization initiator is used when the curable liquid resin composition of the component 2 is photo-curable. It is preferable to use a photosensitizer in combination, if required. As examples of the photoinitiator, 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, benzyl dimethyl ketal, l-(4-isopropylphenyl)-
2-hydroxy-2-methylpropane-l-one, 2-hydroxy-2-methyl-l-phenylpropane-l-one, thioxanethone, diethylthioxanthone, 2-isopropylthioxanthone, 2- chlorothioxanthone, 2-methyl- 1- [4-(methylthio)phenyl] -2-morpholino-propane- 1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6- dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; "IRGACURE 184", "IRGACURE 369", "IRGACURE 651", "IRGACURE 500", "IRGACURE 907", "CGI 1700", "CGI 1750", "CGI 1850", "CG24-61", "Darocur 1116", and "Darocure 1173" (manufactured by Ciba Specialty Chemicals Co.); "Lucirin TPO" (manufactured by BASF); "Ubecryl P36" (manufactured by UCB); and the like can be given. As examples of the photosensitizer, trie thy lamine, diethylamine, N-methyldiethanoleamine, ethanolamine, 4- dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4- dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; "Ubecryl P102", "Ubecryl 103", "Ubecryl 104", and "Ubecryl 105" (manufactured by UCB); and the like can be given.
When curing the curable liquid resin composition of the present invention using heat and ultraviolet rays, the heat polymerization initiator and the photoinitiator can be used in combination. The content of the polymerization initiator (F) in Composition 2 is 0.1 to 10 mass%, and preferably 0.3 to 7 mass%.
Composition 2 comprises a silicone compound having an average molecular weight of 1,500 to 35,000 as a component (G). The component (G) plays an important role in obtaining effects of improving peelability for removing a coating layer formed of the resin composition of the present invention from the adjacent layer thereof. If the average molecular weight of the component (G) is less than 1,500, sufficient effects of improving peelability may not be obtained. If the average molecular weight of the component (G) exceeds 35,000, the effects of improving peelability may be insufficient. The average molecular weight is more preferably 1,500 to 20,000, still more preferably 1,500 to 20,000, and particularly preferably 3,000 to 15,000.
It is preferable that the component (G) does not have a polymerizable group such as an ethylenically unsaturated group. If the component (G) does not have a polymerizable group, excellent peelability can be maintained even after subjecting the product to a heat history. As examples of the silicone compound, polyether-modified silicone, alkyl- modified silicone, urethane acrylate-modified silicone, urethane-modified silicone, methylstyryl-modified silicone, epoxy polyether-modified silicone, alkylaralkyl polyether-modified silicone, and the like can be given. Of these, polyether-modified silicone is particularly preferable. As the polyether- modified silicone, a polydimethylsiloxane compound in which at least one silicon atom is bonded to the group R 14 -(R 15 O) S -R 16 - (wherein R 14 indicates a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, R 15 indicates an alkylene group having 2 to 4 carbon atoms (R 15 may have two or more different alkylene groups), R 16 indicates an alkylene group having 2 to 12 carbon atoms, and s is an integer of 1 to 20) is preferably used. As R 15 in the above, an ethylene group and a propylene group are preferable, with an ethylene group being particularly preferable. As the commercially available products of the silicone compound which does not include a polymerizable group such as an ethylenically unsaturated group, "SH28PA" (manufactured by Dow Corning Toray Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), "Paintad 19" and "Panitad 54" (manufactured by Dow Corning Toray Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), "Silaplane FM0411" (manufactured by Chisso Corp.), "SF8428" (manufactured by Dow Corning Toray Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer (including side chain OH)), "BYKUV3510" (manufactured by BYK-Chemie Japan., dimethylpolysiloxane-polyoxyalkylene copolymer), "DC57" (manufactured by Dow Corning Toray Co., Ltd., dimethylpolysiloxane- polyoxyalkylene copolymer), and the like can be given. As the commercially available products of the silicone compound which includes a polymerizable group such as an ethylenically unsaturated group, "TegoRad 2300" and
"2200N" (manufactured by Tego Chemie Service (Degussa Japan Co., Ltd.)) can be given.
The component (G) is added to Composition 2 in an amount of 0.1 to 50 mass%, preferably 0.5 to 40 mass%, and more preferably 1 to 20 mass%. Various additives such as antioxidants, coloring agents, UV absorbers, light stabilizers, silane coupling agents, heat polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging preventives, wettability improvers, and coating surface improvers may be optionally added to Composition 1 and Composition 2 insofar as the characteristics of the present invention are not adversely affected.
Like Composition 2, Composition 1 may further comprise a silicone compound having an average molecular weight of 1,500 to 35,000 and a polymerization initiator. These compounds may be the same as those used for Composition 2. The second aspect of the instant claimed invention is a process to create an optical fiber ribbon with a double layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer and a second ribbon formed by bundling the first ribbons using a second ribbon layer, comprising the steps of a) providing an optical fiber; b) coating said optical fiber with a radiation curable coating, which is a primary coating, and optionally applying radiation to cure said primary coating; c) coating said optical fiber with a second radiation curable coating, which is a Secondary coating, applied over the Primary coating; and d) applying radiation to cure said Secondary coating; and e) arranging more than one optical fibers from step d) in a desired ribbon configuration; f) applying the first ribbon layer radiation curable liquid resin composition, Composition 1, to the one or more optical fibers in the desired
configuration of step e) to create a first ribbon layer and applying radiation to cure said Composition 1; g) arranging more than one first ribbon layers from step f) into a desired second ribbon layer configuration; and h) applying the second ribbon layer radiation curable liquid resin composition, Composition 2, to the second ribbon layer configuration and applying radiation to cure said Composition 2.
It is known in the art how to manufacture optical fibers and coat them with one or more radiation curable liquid resin compositions. The one or more radiation curable liquid resin compositions may include a Primary Coating, a
Secondary Coating and an Ink Coating. Primary Coatings, Secondary
Coatings (not of this invention) and Ink Coatings for optical fiber are commercially available from JSR Corporation in Japan, http://www.isr.co.ip/isr e/ and are also commercially available from DSM Desotech in the United States, http://www.dsm.com/en US/html/dsmd/desotech home.htm and other countries.
The arrangement of optical fibers into a first ribbon configuration and a second ribbon configuration is standardized based on either industry standard or government standard or both depending upon where the optical fiber is manufactured and used. People of ordinary skill in the art of optical fibers know what type of first ribbon configurations and what type of second ribbon configurations are acceptable in what jurisdiction.
Composition 1 and Composition 2 are cured by heat or radiation. It is preferable under most circumstances to cure both of these compositions by applying radiation. Radiation used herein refers to infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, and the like. The optical fiber ribbon of the present invention has a double-layer structure comprising a first ribbon formed by bundling optical fibers using a first ribbon layer which is produced from Composition 1, and a second ribbon
which bundles and covers a number of the first ribbons as an outer layer produced from Composition 2.
It has been found that the second ribbon layer, covered in Composition 2, may be easily peeled off from the first ribbon layers covered in Composition 1.
EXAMPLES
The present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.
Preparation Example 1: synthesis 1 of urethane (meth)acrylate (Al) A reaction vessel equipped with a stirrer was charged with 0.120 g of 2,6-di-t-butyl-p-cresol, 354.86 g of 2,4-tolylene diisocyanate, and 0.240 g of dibutyl tin dilaurate. The mixture was cooled to 15 0 C while stirring. After the addition of 236.60 g of hydroxyethyl acrylate dropwise while controlling the temperature at 2O 0 C or less, the mixture was stirred at 4O 0 C in a water bath for one hour. Then, after cooling to 2O 0 C, 407.51 g of ethylene oxide addition diol of bisphenol A ("DA400" manufactured by NOF Corp.) was added. After confirming generation of heat, the mixture was stirred at 65 0 C for three hours and the reaction was terminated when remaining isocyanate was reduced to 0.1 mass% or less. The resulting urethane (meth)acrylate (A) is referred to as "UA-I".
The resulting urethane (meth)acrylate has a structure having 2- hydroxyethyl acrylate bonded to both ends of a diol having a bisphenol A structure via 2,4-tolylene diisocyanate.
Preparation Example 2: synthesis 1 of urethane (meth)acrylate (A2)
A reaction vessel equipped with a stirrer was charged with 0.240 g of 2,6-di-t-butyl-p-cresol, 271.72 g of tolylene diisocyanate, and 546.07 g of polypropylene glycol with a number average molecular weight of 700. The
mixture was cooled to 15 0 C. After the addition of 0.799 g of dibutyltin dilaurate, the mixture was stirred for one hour while controlling the liquid temperature at less than 4O 0 C. The mixture was cooled with ice to 15 0 C or less with stirring. After the dropwise addition of 181.17 g of hydroxyethyl acrylate, the mixture was allowed to react for one hour with stirring while controlling the liquid temperature at 2O 0 C or less. The mixture was then stirred at 70 to 75 0 C for three hours. The reaction was terminated when the residual isocyanate content became 0.1 mass% or less. The resulting urethane (meth)acrylate (A) is referred to as "UA-2". The resulting urethane (meth)acrylate has a structure having 2- hydroxyethyl acrylate bonded to both ends of propylene glycol via 2,4-tolylene diisocyanate.
Preparation Example 3: synthesis 2 of urethane (meth)acrylate (A2) A reaction vessel equipped with a stirrer was charged with 0.240 g of
2,6-di-t-butyl-p-cresol, 428.10 g of 2,4-tolylene diisocyanate, and 0.799 g of dibutylin dilaurate. The mixture was cooled to 15 0 C while stirring. After the addition of 570.86 g of hydroxyethyl acrylate dropwise while controlling the temperature at 2O 0 C or less, the mixture was stirred at 40 0 C in a water bath for one hour. After confirming that the temperature does not increase, the mixture was stirred at 65 0 C for three hours and the reaction was terminated when remaining isocyanate was reduced to 0.1 mass% or less. The resulting urethane (me th) acrylate (A) is referred to as "UA-3".
The resulting urethane (me th) acrylate has a structure having 2- hydroxyethyl acrylate bonded to both ends of 2,4-tolylene diisocyanate.
Preparation Example 4
A reaction vessel equipped with a stirrer was charged with the components listed in Table 1. The mixture was then stirred for one hour while controlling the liquid temperature at 50 0 C to obtain a curable liquid resin composition (Composition 1).
Table 1
In Table 1: "Irgacure 184": 1-hydroxy-cyclohexyl phenyl ketone (manufactured by Ciba
Specialty Chemicals Co., Ltd.)
"Lucirin TPO": 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Speciality Chemicals Co., Ltd.)
"Irganox 245": ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m- tolyl)propionate] (manufactured by Ciba Specialty Chemicals Co., Ltd.)
"SH28PA": dimethylpolysiloxane polyoxyalkylene copolymer (manufactured by
Dow Corning Toray Co., Ltd.)
Preparation Example 5: synthesis of urethane (meth)acrylate (D)
A reaction vessel equipped with a stirrer was charged with 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, and 71.11 g of polypropylene glycol with a number average molecular weight of 700. The mixture was cooled to 15 0 C. After the addition of 0.104 g of dibutyltin dilaurate, the mixture was stirred for one hour while controlling the liquid temperature at less than 4O 0 C. The mixture was
cooled with ice to 10 0 C or less while stirring. After the dropwise addition of 23.55 g of hydroxyethyl acrylate while controlling the liquid temperature at 2O 0 C or less, the mixture was allowed to react for one hour with stirring. The mixture was then stirred at 70 to 75 0 C for three hours. The reaction was terminated when the residual isocyanate content became 0.1 mass% or less. The resulting urethane (meth)acrylate (D) is referred to as "UA-4".
Preparation Example 6: synthesis of urethane (meth)acrylate
A reaction vessel equipped with a stirrer was charged with 13.484 g of 2,4-tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, and 0.080 g of dibutyltin dilaurate. The mixture was cooled with ice to 15 0 C or less with stirring. After the addition of 77.422 g of a ring-opening polymer of propylene oxide having a number average molecular weight of 2,000, the mixture was allowed to react for two hours with stirring while controlling the liquid temperature at 35 0 C or less. After the dropwise addition of 8.990 g of 2- hydroxypropyl acrylate and further dropwise addition of 24.740 g of hydroxyethyl acrylate, the mixture was continuously stirred at 70 to 75 0 C for three hours. The reaction was terminated when the residual isocyanate content was 0.1 wt% or less. The resulting urethane (me th) acrylate is referred to as "UA-5".
Preparation Example 7
A reaction vessel equipped with a stirrer was charged with the components listed in Table 2. The mixture was then stirred for one hour while controlling the liquid temperature at 50 0 C to obtain a curable liquid resin composition (Composition 2). Table 2
In Table 2:
"SH28PA": dimethylpolysiloxane-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)
UA-3: the same urethane (meth)acrylate (A) obtained in Preparation Example 3
Example 1 and Comparative Examples 1 to 3 The optical fiber ribbons shown in Table 3 were prepared from combinations of Composition 1 (a or b) shown in Table 1 and Composition 2 (a or b) shown in Table 2. Peelability (delamination stress) and splitability of the resulting optical fiber ribbons were evaluated. The results are shown in Table 3. (Preparation method of samples for evaluation)
Composition 1 was applied to a glass plate to using a 130 μm applicator. The coating was cured with light rays at a dose of 500 mJ/cm 2 in a 1% oxygen atmosphere. A resin liquid of Composition 2 was applied over the coating of Composition 1 using a 381 μm applicator. The film was cured with light rays
at a dose of 500 J/cm 2 in a nitrogen atmosphere to obtain a two-layer ribbon with a total thickness of 200 μm. 1. Peelability
A sample in the shape of a strip having a pulling portion with a width of 10 mm was prepared from the two-layer ribbon. An adhesion test to determine the stress required for delaminating the two layers was carried out using a tensile tester according to JIS Z0237. The adhesion force of the two-layer ribbon was determined from the tensile strength at a tensile rate of 50 mm/min. 2. Splitability
A sample in the shape of a strip having a pulling portion with a width of 10 mm was prepared from the two-layer ribbon. A blemish was produced with a cutter on Composition 2 side of the two-layer ribbon to confirm if only the layer of Composition 2 cracks without damaging Composition 1 side when the ribbon was folded. The test was repeated 40 times to count the number of times when the layer of Composition 2 cracked without damaging Composition 1 layer.
Table 3
It has been found that the second ribbon layer, covered in Composition 2, may be easily peeled off from the first ribbon layers covered in Composition 1.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein. The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non- claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-
described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.