Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

• the present invention relates to a curable liquid resin composition.
• the present invention relates to a curable liquid resin composition suitable as a coating material such as a secondary material or a ribbon matrix material for optical fibers, particularly as a secondary material.
• a resin coating is applied for protection and reinforcement immediately after spinning molten glass fibers.
• the resin coating a structure in which a flexible primary coating layer is provided on the surface of a glass fiber and a rigid secondary coating layer is provided on the outside of the primary coating layer has been known.
• four or eight optical fibers are arranged side by side on a plane and secured using a bundling material, thereby forming a ribbon structure with a rectangular cross-section.
• a resin composition for forming the first coating layer is called a primary material
• a resin composition for forming the second coating layer is called a secondary material
• a material for binding several optical fibers is called a ribbon matrix material.
• One of the functions of the secondary material and the ribbon matrix material is to act as strong protective films which do not cause an external load to be applied to the primary material in the lower layer and quartz glass fibers. Therefore, these materials are designed so as to have a glass transition temperature of more than room temperature and a high modulus of rigidity.
• a radiation-curable liquid resin composition comprising a polyurethane (meth)acrylate oligomer which has one branch point per molecule, has (meth)acrylic groups at two of the three molecular ends extending from this branch point, and does not have a (meth) acrylic group at the remaining end is disclosed in Japanese Patent Application Laid-open No. 2000-351818.
• an object of the present invention is to provide a curable liquid resin composition which after curing can be used as a protective film, particularly as a secondary material, and which is capable of forming a cured layer producing only a slight residual stress therein and easily absorbing external loads.
• a curable liquid resin composition comprising the following components (A), (B), and (C): (A) 0.5-50 wt% of a urethane (meth)acrylate oligomer obtained from a polyol (a) having a branched structure comprising at least one branch point and at least three molecular chains extending from that branch point, said molecular chains having a molecular weight of 200 g/mol or more, including a hydroxyl group at the terminal of at least two molecular chains extending from the branch point, a polyisocyanate (b), and a hydroxyl group- containing (meth)acrylate (c); (B) 5-90 wt% of a polymerizable organic compound; and (C) 0.1-10 wt% of a polymerization initiator, wherein the cured product has a Young's modulus of 350 MPa or more at 23°C.
• the curable liquid resin composition of the present invention is useful as a secondary material and a ribbon matrix material for optical fibers, particularly as a secondary material.
• the urethane (meth)acrylate oligomer (A) is obtained by reacting (a) the polyol with the branched structure (branched polyol), (b) the polyisocyanate, and (c) the hydroxyl group-containing (meth)acrylate by adjusting the raw material molar ratio so that hydroxyl groups originating from the polyol (a) may remain in the resulting oligomer. Preferably, almost all to all hydroxyl groups originating from the polyol (a) react.
• a method of reacting these compounds a method of reacting (a) the branched polyol, (b) the polyisocyanate, and (c) the hydroxyl group-containing (meth)acrylate all together; a method of reacting (a) the branched polyol with (b) the polyisocyanate, and reacting the resulting product with (c) the hydroxyl group- containing (meth)acrylate ; a method of reacting (b) the polyisocyanate with (c) the hydroxyl group-containing (meth)acrylate, and reacting the resulting product with (a) the branched polyol; a method of reacting (b) polyisocyanate with (c) the hydroxyl group-containing (meth)acrylate, reacting the resulting product with (c) the polyol, and further reacting the resulting product with (c) the hydroxyl group-containing (meth)acrylate; and the like can be given.
• a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, 1,4-diazabicyclo[2.2.2]octane, or 2,6,7-trimethyl-1 ,4-diazabicyclo[2.2.2]octane in an amount of 0.01-1 part by weight for 100 parts by weight of the total reactant.
• the reaction is carried out at a temperature of preferably 10-90°C, and particularly preferably 30-80°C.
• the branched polyol (a) is obtained by ring-opening polymerization of glycerol or sorbitol with at least one of ethylene oxide, propylene oxide, or butylene oxide.
• the branched polyol (a) is made in situ by reacting a polyol (a'), which comprises at least three hydroxyl groups and which is preferably a triol or a tetraol with a relatively low molecular weight, for example a triol such as Polyol TP30LW (ethoxylated trimethylolpropane) or a tetraol such as Polyol PP50 (ethoxylated pentaerythritol), both from Neste Oxo, with a polyisocyanate (b), at least one other polyol (a"), preferably a diol, and a hydroxyl group containing (meth)acrylate (c).
• a polyol (a') which comprises at least three hydroxy
• branched polyols (a) are formed by reaction of the polyol (a') with the polyisocyanate, and subsequently with the at least one other polyol (a"), preferably a diol, which forms the molecular chain extending from the branch point.
• the at least one other polyol (a") can for example be chosen from the group of polyols described below as "(a2)" ("polyols other than (a) or mixtures of polyols").
• the branched polyol (a) of this embodiment thus exists of a branch point (core), being formed by the polyol (a'), molecular chains extending from the branch point, being formed by the at least one other polyol (a"), preferably a diol, and reactive end groups from the hydroxyl containing (meth)acrylate.
• the polyisocyanate connects the branch point (core), the molecular chain extending from the branch point and the (meth)acrylate reactive group.
• the reaction mixture may also still contain free diols (a"), which may react with the hydroxyl containing (meth)acrylate to form a difunctional oligomer.
• low molecular polyols can be used which are usually liquid at room temperature and thus easy to handle during synthesis. Reactions with said polyols can usually be carried out without a solvent. Also, said polyols relatively cheap and easily available polyols can be used.
• a large variety of branched oligomers, or mixtures of branched oligomers and linear oligomers can be made in one pot by varying the type of polyol (a') (e.g. number of hydroxyl groups, molecular weight), the type of the at least one other polyol (a"), preferably a diol (e.g. molecular weight), and the ratios between the reactants.
• the molecular weight of at least three molecular chains extending from the branch point of the branched polyol (a) is preferably 500 g/mol or more, more preferably 700 g/mol or more. In one embodiment of the invention the molecular weight of at least three molecular chains extending from the branch point of the branched polyol (a) is preferably 1000 g/mol or more. The molecular weight of at least three molecular chains extending from the branch point of the branched polyol (a) is preferably 10,000 g/mol or less, more preferably 5,000 g/mol or less, most preferably 3000 g/mol or less.
• the molecular weight of at least three molecular chains extending from the branch point of the branched polyol (a) is preferably 2,000 g/mol or less.
• the number average molecular weight of the polyol (a) is preferably from 1 ,500 to 20,000 g/mol, more preferably from 1,500 to 12,000 g/mol, most preferably from 2,000 to 10,000 g/mol, and particularly preferably from 2,500 to 8,000 g/mol.
• the number average molecular weight per one side chain of the polyol (a) is preferably from 500 to 2,000 g/mol, and more preferably from 1,000 to 1 ,500 g/mol.
• the branched polyol (a) has 3-6 molecular chains extending form the branch point, more preferably 3 or 4 molecular chains extending form the branch point. At least two, preferably at least three, more preferably all molecular chains extending from the branch point include a terminal hydroxyl group.
• branched polyols which can be reacted with the polyisocyanate (b) and the hydroxyl group containing (meth)acrylate (c), products manufactured by Daiichi Kogyo Seiyaku Co., Ltd., such as G3000; Asahi Glass Urethane Co., Ltd.; or Sanyo Chemical Industries, Ltd.
• branched polyol (a) wherein apart from a polyol (a') at least one other polyol (a"), preferably a diol, is used to form the branched polyol (a), relatively small branched polyols, such as Polyol TP30LW (ethoxylated trimethylolpropane) or a tetraol such as Polyol PP50 (ethoxylated pentaerythritol), both from Neste Oxo, Sannix TP-400, Sannix GP-250, Sannix GP-400, may be used as the polyol (a') with a relatively low molecular weight.
• branched polyols such as Polyol TP30LW (ethoxylated trimethylolpropane) or a tetraol such as Polyol PP50 (ethoxylated pentaerythritol), both from Neste Oxo, Sannix TP-
• Polyols other than (a) or mixtures of polyols may be added to (a). These other polyols or mixtures of polyols are defined as (a2). Examples of (a2) include aliphatic or cyclic polyether diols, polyester diols, polycarbonate diols, and polycaprolactone diols. There are no specific limitations to the manner of polymerization of the structural units of these polyols. These polyols may be any of a random polymer, block polymer, or a graft polymer.
• polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, polyether polyols obtained by the ring-opening copolymerization of two or more ion- polymerizable cyclic compounds, and the like can be given.
• cyclic ethers such as ethylene oxide, propylene oxide, 1,2-butylene 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, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and g
• polyether polyols obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compounds with monomers for example, cyclic imines such as ethyleneimine, cyclic lactone acids such as ⁇ - propyolactone and glycolic acid lactide, and dimethylcyclopolysiloxanes can be used.
• cyclic imines such as ethyleneimine
• cyclic lactone acids such as ⁇ - propyolactone and glycolic acid lactide
• dimethylcyclopolysiloxanes can be used.
• combinations of 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 copolymer 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.
• These polyether polyols are commercially available as PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), PEG1000, Unisafe DC1100, DC1800 (manufactured by Nippon Oil and Fats Co., Ltd.), PPTG2000, PPTG 000, PTG400, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000A, PBG2000B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim polypropylene glycols, such as Acclaim 4200 and Acclaim 200, Desmophen 2061 BD (all manufactured by Bayer), and the like.
• alkylene oxide addition diol of bisphenol A alkylene oxide addition diol of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide addition diol of anthrahydroquinone, 1 ,4-cyclohexanediol and alkylene oxide addition diol thereof, tricyclodecanediol, tricyclodecanedimethanol, pentacyclopentadecanediol, pentacyclopentadecanedimethanol, and the like can be given.
• alkylene oxide addition diol of bisphenol A alkylene oxide addition diol of hydrogenated bisphenol A, and tricyclodecanedimethanol are preferable.
• These polyols are commercially available as Uniol DA400, DA700, DA1000, DB400 (manufactured by Nippon Oil and Fats Co., Ltd.), N1162 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), tricyclodecanedimethanol (manufactured by Mitsubishi Chemical Corp.), and the like.
• polyester polyol polyester polyols obtained by reacting a polyol with a diacidic base and the like can be given.
• polyol examples include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2- methyl-1,8-octanediol.
• dibasic acids examples include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid can be given.
• polyester diols are commercially available as Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.), and the like.
• polycarbonate polyols polycarbonate of polytetrahydrofuran, polycarbonate of 1,6-hexanediol, and the like can be given.
• products of polycarbonate polyols DN-980, 981, 982, 983 (manufactured by Nippon Polyurethane Industry Co., Ltd. ), PC-8000 (manufactured by PPG), PC-THF-CD (manufactured by BASF), and the like can be given.
• polycaprolactone diols obtained by reacting ⁇ -caprolactone and diols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1 ,4-butanediol can be given.
• diols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1 ,4-butanediol
• diols are commercially available as PLACCEL 205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel Chemical Industries, Ltd.), and the like.
• a number of polyols (a2) other than those illustrated above may be used.
• diamines can be used in combination with polyols.
• diamines ethylenediamine, tetramethylenediamine, hexamethylenediamine, p-phenylenediamine, 4,4'- diaminodiphenylmethane, diamines containing a hetero atom, polyether diamines, and the like can be given.
• polyols (a2) polyether diols, alkylene oxide addition diol of bisphenol A, and alkylene oxide addition diol of hydrogenated bisphenol A are preferable.
• diols are commercially available as PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), Uniol DA400, DA700, DA1000, DB400 (manufactured by Nippon Oil and Fats Co., Ltd.), and N1162 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
• the number average molecular weight of the other polyol component (a2) is 300-5,000, preferably 300-2,000, and more preferably 300-1 ,000.
• diisocyanates are preferable.
• 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-isocyanate ethyl)fumarate, 6-isopropyl-1,3
• 2,4-tolylene diisocyanate isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4- cyclohexylisocyanate) are particularly preferable.
• These polyisocyanates (b) may be used either individually or in combinations of two or more.
• the molar ratio of the raw materials is adjusted during preparation of the urethane (meth)acrylate oligomer (A) so that almost all to preferably all hydroxyl groups originating from the polyol (a) are reacted with the diisocyanate (b) and the hydroxyl group containing (meth)acrylate (c). In said embodiment only small amounts of hydroxyl groups may remain.
• the raw material molar ratio it is preferable to adjust the raw material molar ratio so that patrt of the hydroxyl groups originating form the polyol (a) does not react with the diisocyanate (b) and the hydroxyl group containing (meth)acrylate (c) but is still present as a hydroxyl group in the oligomer (A).
• the urethane (meth)acrylate of component (A) is added to the curable liquid resin composition of the present invention in an amount of 0.5-50 wt%, preferably 3-45 wt%, and more preferably 5-40 wt%. If the content is less than 0.5 wt%, coatability may be impaired.
• the urethane (meth)acrylate oligomer (A) is added as the main component of the total amount of urethane (meth)acrylate oligomer in the curable liquid resin composition.
• the urethane (meth)acrylate oligomer (A) is added as a modifier, for example a rheology modifier, of the main component of the urethane (meth)acrylate oligomer. This embodiment is aimed at providing a curable liquid resin composition, in particular a secondary resin composition, with improved processability.
• the preparation of coated optical fibers today involves passing the fibers through a coating die mounted within a device known as a draw tower, followed by curing the applied resin compositions.
• secondary resin compositions are applied to an optical glass fiber simultaneously with a primary resin composition, after which both resin compositions are simultaneously cured.
• the rheological properties of primary resin compositions and secondary resin compositions are different, i.e. said compositions feature a limited rheological compatibility. This may cause certain problems.
• the drag flow induced by the moving fiber at high drawing speeds gives rise to high shear rates, typically being between 10 5 and 10 6 s '1 at the location near the exit of the coating cup.
• Optical fiber resin compositions usually show complicated non-Newtonian behavior as shear rate increases. Due to this, processability instabilities often occur during fiber production, in particular in wet-on-wet applications where primary resin compositions and secondary resin compositions with different rheological properties are applied. Another significant problem concerns the degree of uniformity in the coating after curing. More specifically, in high quality coated fibers, the thickness of the coating layer possesses a high degree of uniformity along the length of the fiber.
• Optical fibers with low levels of coating uniformity can present problems when one desires to splice two optical fibers together. Non-uniformity may also translate into data transmissions problems after installation into a data network, e.g., signal attenuation.
• One means of addressing processing instability is to control, in some manner, the rheological properties of the curable liquid secondary resin composition.
• the main component of the urethane (meth)acrylate oligomer is preferably a urethane
• the steady state compliance J e which is a measure of the elasticity of the resin, is preferably 2 MPa "1 or more, more preferably 3 MPa "1 or more, most preferably 4 MPa '1 or more, particularly preferably 5 MPa "1 or more.
• a urethane (meth)acrylate obtained by reacting 1 mol of diisocyanate with 2 mols of (meth)acrylate containing a hydroxyl group may be added to the curable liquid resin composition of the present invention.
• a urethane (meth)acrylate is the reaction product of hydroxyethyl (meth)acrylate and 2,4-tolylene diisocyanate, reaction product of hydroxyethyl (meth)acrylate and 2,5 (or 6)-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, reaction product of hydroxyethyl (meth)acrylate and isophorone diisocyanate, reaction product of hydroxypropyl (meth)acrylate and 2,4-tolylene diisocyanate, and reaction product of hydroxypropyl (meth)acrylate and isophorone diisocyanate.
• a polymerizable monofunctional compound is blended with the liquid curable resin composition of the present invention as component (B).
• the monofunctional compound N-vinylpyrrolidone, lactams containing a vinyl group such as N-vinylcaprolactam, (meth)acrylates containing an alicyclic structure such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, vinyl imidazole, vinyl pyridine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (
• R 5 represents a hydrogen atom or a methyl group
• R 6 represents an alkylene group having 2-8, and preferably 2-5 carbon atoms
• R 7 represents a hydrogen atom or a methyl group
• p is preferably an integer from 1 to 4.
• R 8 , R 9 , R 10 , and R 11 individually represent a hydrogen atom or a methyl group, and q is an integer from 1 to 5.
• monofunctional compounds (B) N-vinylpyrrolidone, lactams containing a vinyl group such as N-vinylcaprolactam, isobornyl (meth)acrylate, lauryl acrylate, and a compound of the above formula (6) are preferable.
• These monofunctional compounds (B) are commercially available as
• the amount of the polymerizable monofunctional compound (B) in the curable liquid resin composition of the present invention is preferably 5-90 wt%, and more preferably 10-80 wt%.
• the curable liquid resin composition of the present invention comprises a polymerization initiator as component (C).
• a polymerization initiator a heat polymerization initiator or a photoinitiator can be used.
• a heat polymerization initiator such as a peroxide or azo compound is used.
• a heat polymerization initiator benzoyl peroxide, t-butyloxybenzoate, and azobisisobutyronitrile can be given.
• a photoinitiator is used.
• a photosensitizer is preferably added as required.
• photoinitiators 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, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2- hydroxy-2-methyl-1-phenylpropan-1-one, thioxanethone, diethylthioxanthone, 2- isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1 -[
• photosensitizers triethylamine, diethylamine, N- methyldiethanoleamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4- dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4- dimethylaminobenzoate; Ubecryl P102, 103, 104, 105 (manufactured by UCB); and the like can be given.
• the heat polymerization initiator and the photoinitiator may be used in combination.
• the polymerization initiator (C) is used in the curable liquid resin composition of the present invention in an amount of preferably 0.1-10 wt%, and particularly preferably 0.5-7 wt%.
• a polymerizable polyfunctional compound may further be incorporated in the curable liquid resin composition of the present invention as component (D).
• polyfunctional compound (D) trimethylolpropane tri(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecanediyldimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid addition compound of bisphenol A diglycidyl ether, pentaerythritol tri(meth)acrylate, pen
• tricyclodecanediyldimethanol di(meth)acrylate di(meth)acrylate of ethylene oxide addition diol of bisphenol A
• tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate are preferable.
• polymerizable polyfunctional compounds (D) Yupimer UV, SA-1002 (manufactured by Mitsubishi Chemical Corp.), Aronix M-215, M-315, M-325, TO-1210 (manufactured by Toagosei Co., Ltd.), GX-8345 (manufactured by a Daiichi Kogyo Seiyaku Co., Ltd.), and the like can be given.
• These polymerizable polyfunctional compounds (D) are added to the curable liquid resin composition of the present invention in an amount of preferably 5- 90 wt%, and particularly preferably 10-80 wt%.
• the amount is less than 5 wt% or exceeds 90 wt%, application may become uneven due to changes in the application form.
• 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 the curable liquid resin composition of the present invention, insofar as the characteristics of the composition are not adversely affected.
• the curable liquid resin composition of the present invention is cured by heat or radiation.
• Radiation used herein refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
• the cured product of the curable liquid resin composition prepared according to the above-described method has a stress relaxation time of less than 4 minutes, preferably 3 minutes or less, and more preferably 2 minutes or less. If the stress relaxation time is 4 minutes or more, a coating stress may remain during manufacturing of fibers or during handling, resulting in problems, particularly, such as formation of voids in the primary layer and peeling of the primary layer from quartz glass.
• the cured products have a Young's modulus of elasticity of 350 MPa or more, preferably 400 MPa or more, more preferably 500 MPa or more at 23°C.
• part(s) refers to “part(s) by weight”.
• a reaction vessel equipped with a stirrer was charged with 6.651 g of isophorone diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.080 g of dibutyltin dilaurate, and 0.008 g of phenothiazine.
• the mixture was cooled with ice to 10°C or below while stirring.
• oligomer (A-1) After the addition of 89.763 g of polypropylenetriol with a number average molecular weight of 6,000 (G3000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), the mixture was stirred at 70-75°C for three hours. The reaction was terminated when the residual isocyanate concentration was 0.1 wt% or less. This liquid resin is called "oligomer (A-1)".
• A-2 A reaction vessel equipped with a stirrer was charged with 16.489 g of isophorone diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.080 g of dibutyltin dilaurate, and 0.008 g of phenothiazine. The mixture was cooled with ice to 10°C or below while stirring. After the dropwise addition of 8.666 g of hydroxyethyl acrylate, while controlling the temperature at 20°C or less, the mixture was allowed to react for one hour while stirring.
• oligomer (U-1) After the addition of 20.099 g of ethylene oxide addition diol of bisphenol A with a number average molecular weight of 400 (manufactured by NOF Corporation), the mixture was stirred at 70-75°C for three hours. The reaction was terminated when the residual isocyanate content was 0.1 wt% or less. This liquid resin is called "oligomer (U-1)".
• Synthesis (B-1 ) A reaction vessel equipped with a stirrer was charged with 5.287 g of 2,4-totylene diisocyanate, 0.024 g of 2,6-di- t-butyl-p-cresol, 0.080 g of dibutyltin dilaurate, and 0.008 g of phenothiazine. The mixture was cooled with ice to 10°C or below while stirring. After the dropwise addition of 3.525 g of hydroxyethyl acrylate, while controlling the temperature at 20°C or less, the mixture was allowed to react for one hour while stirring.
• oligomer (B-1) The liquid resin obtained in this manner is called "oligomer (B-1)".
• Test Example Preparation of test film The curable liquid resin composition was applied to a glass plate using an applicator bar for a thickness of 250 ⁇ m. The curable liquid resin composition was cured by irradiation of ultraviolet rays at a dose of 1 J/cm 2 in air to obtain a test film. 1. Measurement of Young's modulus of elasticity: The test film was cut into a sample in the shape of a strip with a width of 6 mm and a length of 25 mm. The sample was subjected to a tensile test at a temperature of 23°C and a humidity of 50%. The Young's modulus was calculated from the tensile strength at a strain of 2.5% and a tensile rate of 1 mm/min. 2.
• Measurement of stress relaxation time The above test film was cut into a sample in the shape of a strip with a width of 6 mm and a length of 25 mm. A strain of 5% was applied to the sample at a rate of 1 ,000 mm/minute at a temperature of 23°C and a humidity of 50%. Changes in the stress were monitored by suspending the cross head of a tensile tester (Autograph AGS- 50G manufactured by Shimazu Corp.). A period of time in which the stress was reduced to 37% of the initial stress was determined as the stress relaxation time. 3. Observation of void occurrence in primary material:
• compositions of the Examples and Comparative Examples were applied to the cured primary material.
• the optical fiber drawing conditions were as follows.
• the diameter of the glass fiber was 125 ⁇ m.
• the primary coating material was applied to the metal line and cured so that the diameter of the optical fiber was 200 ⁇ m after curing.
• the composition of the Example or Comparative Example was applied to the primary material thus formed so that the diameter was 250 ⁇ m after curing.
• As UV irradiation equipment a UV lamp "SMX 3.5 kw" manufactured by ORC Corp. was used.
• Applicability was evaluated at an optical fiber drawing rate of 1,000 m/min.
• the resin compositions of the Examples exhibited a high stress relaxation rate and satisfactory Young's modulus of elasticity as a secondary material, showing that the compositions are free from defects such as void formation in the primary material and peeling of the primary material from quartz glass.
• triol Polyol TP30 LW an ethoxylated trimethylolpropane with OH number 629 from Neste Oxo
• tetraol Polyol PP50 an ethoxylated pentaerythritol with OH number 638 from Neste Oxo
• 2-Hydroxyethyl acrylate (HEA) was then added through a dropping funnel at 10 °C. After approximately 1 hour the midpoint was reached, after which the reactor was heated to 20 °C.
• the reaction was allowed to proceed until the NCO content was below 0.05 %.
• the polyols and diols, IPDI and HEA were added in stoichiometric amounts.
• Table 3 the oligomers prepared using the above method are listed.
• the experiment was run by performing isothermal frequency sweeps with angular frequencies between 100 and 0.1 rad/s (3 frequencies per decade, measured in decreasing order) at 5°C temperature intervals, starting with 20 °C and lowering the temperature in 5 °C steps until the sample becomes to stiff for the instrument to measure (for the cited examples this limit is typically passed between about -20 °C and about -30 °C). Care had to be taken that the applied strains are well within the linear viscoelastic range. A typical value for the strain amplitude at room temperature is about 20-40 %, decreasing to values as low as 0.01-0.02 % at the lowest temperatures.
• the data of Table 4 show that the M w of the oligomer (or mixture of oligomers) is dependent on the number of molecular chains extending from the branch point in the polyol and the ratio difunctional/trifunctional or difunctiona tetrafunctional.
• the results of Table 4 indicate that the steady state compliance J e , which is a measure of the elasticity of the liquid composition, increases with an increasing amount of tri/tetrafunctional oligomer in the composition (J e increases going from 100:0 via 85:15 to 50:50 difunctionaktri/tetrafunctional) and with the number of molecular chains extending from the branch point (J e is higher for mixtures with tetrafunctional oligomers) .
• the elasticity is an important parameter, in particular for secondary resin compositions: a higher J e often results in an improved wet-on-wet processability.

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