[go: up one dir, main page]

WO2000022022A1 - Photo curable resin composition for tension members - Google Patents

Photo curable resin composition for tension members Download PDF

Info

Publication number
WO2000022022A1
WO2000022022A1 PCT/NL1999/000629 NL9900629W WO0022022A1 WO 2000022022 A1 WO2000022022 A1 WO 2000022022A1 NL 9900629 W NL9900629 W NL 9900629W WO 0022022 A1 WO0022022 A1 WO 0022022A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
group
compound
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL1999/000629
Other languages
French (fr)
Inventor
Masahito Mase
Zen Komiya
Takashi Ukachi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Koninklijke DSM NV
Original Assignee
JSR Corp
DSM NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp, DSM NV filed Critical JSR Corp
Publication of WO2000022022A1 publication Critical patent/WO2000022022A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to a photo curable resin composition useful as an overcoat material for tension members in an optical fiber unit.
  • Optical fibers generally are bundled in certain units before being cabled.
  • One type of optical fiber unit which is used for submarine cable and the like, generally has a structure as shown in Figure 1.
  • a steel wire (1) coated with copper which is called a tension member is provided in the center of such an optical fiber unit.
  • the steel wire (1) has an overcoat layer (2) to prevent braking of an optical fiber by a tension strength during manufacturing. Outside of the overcoat layer (2) several optical fibers (3) coated with a photo curable resin are twisted with a certain space between them.
  • an internal coating layer (4) made from a photo curable resin with a low Young's modulus of elasticity and an outside coating layer (5) made from a photo curable resin with a high Young's modulus of elasticity.
  • the tension member has been coated with either a photo curable resin with a low Young's modulus of elasticity (10 kg/mm or less) used for internal layer coating or a photo curable resin with a high Young's modulus of elasticity (50 kg/mm or more) used for outside layer coating.
  • the problem to be solved by the present invention is therefore to provide a photo curable resin composition capable of forming coatings exhibiting high adhesion to steel wires coated with copper which are used as a tension member for optical fiber unit.
  • an object of the present invention is to provide a photo curable resin composition for coating a tension member comprising,
  • the composition when cured preferably has a Young's modulus of 10 kg/mm 2 or higher, and preferably has a 90° peel strength of 20 g/cm or higher.
  • the number average molecular weight means a polystyrene-reduced number average molecular weight measured by gel permeation chromatography.
  • the urethane (meth) acrylate which is used as the component (A) (hereinafter referred to as “urethane (meth) acrylate (A)") is generally obtained by reacting (a) a polyol compound, (b) a polyisocyanate compound, and
  • polyether polyols for example, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, aliphatic hydrocarbons having two or more hydroxyl groups in the molecule, alicyclic hydrocarbons having two or more hydroxyl groups in the molecule, and unsaturated hydrocarbons having two or more hydroxyl groups in the molecule can be used.
  • These polyol compounds may be used either individually or in combination of two or more.
  • the manner of bonding of the structural units in these polyols is not specifically limited, and may be random bond, block bond, or graft bond.
  • Suitable examples of the above-mentioned polyether polyols include aliphatic polyether polyols, alicyclic polyether polyols, aromatic polyether polyols .
  • aliphatic polyether polyols examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds.
  • Suitable examples of the above-mentioned ion-polymerizable cyclic compounds include cyclic ethers such as ethylene oxide, propylene oxide, butene- 1-oxide, isobutene oxide, 3 , 3-bis (chloromethyl) oxetane, tetrahydrofuran, 2 -methyl tetrahydrofuran, 3- ethyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl ether, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl gly
  • Suitable examples of specific combinations of two or more ion-polymerizable cyclic compounds include binary copolymers such as tetrahydrofuran and ethylene oxide, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2- methyltetrahydrofuran, tetrahydrofuran and 3- methyltetrahydrofuran, ethylene oxide and propylene oxide, and ethylene oxide and butene-1-oxide; and ternary copolymers such as tetrahydrofuran, butene-1- oxide , and ethylene oxide .
  • polyether polyols obtained by the ring-opening copolymerization of the above- mentioned ion-polymerizable cyclic compound and a cyclic imine such as ethylenimine, a cyclic lactone acid such as b-propyolactone or glycollic acid lactide, or a dimethylcyclopolysiloxane can be used.
  • the ring- opening copolymer of these ion-polymerizable cyclic compounds may be bonded randomly or the copolymer may be block-bonded.
  • Suitable examples of the alicyclic polyether polyols include alkylene oxide addition diols of hydrogenated bisphenol A, alkylene oxide addition diols of hydrogenated bisphenol F, and alkylene oxide addition diols of 1, 4-cyclohexane diol .
  • Suitable examples of the alicyclic polyether polyols include alkylene oxide addition diols of bisphenol A, alkylene oxide addition diols of bisphenol F, and alkylene oxide addition diols of hydroquinone .
  • polyether polyols examples include PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), EXCENOL1020, EXCENOL2020, EXCENOL3020 (manufactured by Asahi Glass Co., Ltd.), Unisafe DC1100, Unisafe DC1800, Unisafe DCB1100, Unisafe DCB1800 (manufactured by Nippon Oil and Fats Co., Ltd.), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG2000, PTG3000, PTGL1000, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000, PBG2000B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like; and commercially available
  • the polyester polyols can be obtained by the reaction of a polyhydric alcohol and a polybasic acid.
  • suitable examples of the polyhydric alcohol include ethylene glycol , polyethylene glycol , propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1, 4-butanediol, 1,5-pentane diol, 1, 6-hexanediol, 1,7-heptane diol, 1,8 -octane diol, neopentyl glycol, 1, 4-cyclohexane diol, 1,4- cyclohexanedimethanol, 3 -methyl -1, 5-pentane diol, 1,9- nonane diol, 2 -methyl-1, 8-octane diol, and the like.
  • the polybasic acid phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid,
  • Suitable commercially available polyester polyols include Kurapol P-1010, P-2010, F-1010, F-2010, PMIPA-2000, PKA-A, PKA-A2 and PNA-2000 (manufactured by Kuraray Co., Ltd.) .
  • polycarbonate polyols include polycarbonate of polytetrahydrofuran, poly (hexanediolcarbonate) , poly (nonanediolcarbonate) , and poly (3 -methyl- 1, 5-pentamethylene carbonate).
  • Suitable commercially available polycarbonate polyols include DN-980, DN-981, DN-982, DN-983 (manufactured by Nippon Polyurethane Industry, Co., Ltd.), PC-8000 (manufactured by PPG Co.), PNOC- 1000, PNOC-2000, PMC-100, PMC-2000 (manufactured by Kuraray Co., Ltd.), PLACCEL CD205 , CD210, CD220, CD205PL, CD210PL, CD220PL, CD205HL, CD210HL, CD220HL, CD210T and CD220T (manufactured by Daicel Chemical Industries, Ltd.) .
  • Polycaprolactone diols obtained by the reaction of ⁇ -caprolactone and a diol can be given as examples of the polycaprolactone polyols.
  • diols include 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 .
  • Suitable commercially available polycaprolactone polyols include PLACCEL 205, 210, 212, 220, 210N and 220AL
  • Suitable examples of the aliphatic hydrocarbons having two or more hydroxyl groups in the molecule include ethylene glycol, propylene glycol, tetramethylene glycol, 1, 4-butanediol , 1,5-pentane diol, 1, 6-hexanediol, 1,7-heptane diol, 1,8 -octane diol, 1,9-nonane diol, neopentyl glycol, 2,2- diethyl- 1, 3-propanediol, 3 -methyl-1 , 5-pentane diol, 2- methyl- 1,8-octane diol, hydroxy terminal hydrogenated polybutadiene, glycerol, trimethylolpropane, pentaerythritol , sorbitol, and the like.
  • Suitable examples of the alicyclic hydrocarbons having two or more hydroxyl groups in the molecule include 1, 4-cyclohexane diol, 1,4- cyclohexanedimethanol, 1,2- bis (hydroxyethyl) cyclohexane, dimethylol compounds of dicyclopentadiene and tricyclodecanedimethanol .
  • Suitable examples of unsaturated hydrocarbons having two or more hydroxyl groups in the molecule include hydroxy terminal polybutadiene and hydroxy terminal polyisoprene .
  • polyols examples include diol compounds such as ⁇ - methyl- ⁇ -valerolactone diol, castor oil modified diol, polydimethylsiloxane with terminal diol, polydimethylsiloxane with terminal carbitol modified diol .
  • the number average molecular weight of these polyol compounds (a) is in the range from 50 to 15,000, and preferably from 100 to 8,000.
  • polyisocyanate (b) which is used for the synthesis of urethane (meth) acrylate (A) 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, 2 , 2 , 4-trimethylhexamethylene diisocyanate, bis (2
  • 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, are preferred.
  • These polyisocyanate compounds (b) can be used either individually or in combinations of two or more.
  • Suitable examples of the hydroxyl group containing (meth) acrylate compound (c) which is a third reaction component to synthesize the urethane (meth) acrylate (A) include 2-hydroxyethyl (meth) crylate, 2-hydroxypropyl (meth) acrylate, 4- hydroxybutyl (meth) acrylate, 2-hydroxy-3- phenyloxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6- hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaeryth
  • H 2 C C(R 1 )COOCH 2 CH 2 (OCOCH 2 CH 2 CH 2 CH 2 CH 2 ) n OH (1)
  • R 1 indicates a hydrogen atom or methyl group and n is an integer from 1-15, and preferably 1-4.
  • compounds obtained by the addition reaction of a glycidyl group containing compound such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth) acrylate) and (meth) acrylic acid can also be used.
  • 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate and 4- hydroxybutyl (meth) acrylate
  • These hydroxyl group containing (meth) acrylate may be used either individually or in combinations of two or more.
  • urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin di-laurylate, triethylamine, 4- diazabicyclo [2.2.2] octane, 1,1, 4-diaza-2- methylbicyclo [2.2.2] octane usually in an amount of 0.01-1 part by weight per 100 parts by weight of the total of polyol (a) , polyisocyanate (b) , and hydroxyl group containing (meth) acrylate (c) .
  • the reaction temperature in this reaction is usually in the range of 0-90, and preferably 10-80.
  • the number average molecular weight of the urethane (meth) acrylate which is used in the present invention is from 100 to 20,000, and preferably from 500 to 15,000.
  • a compound having at least one mercapto group and at least one group shown by the formula -SiR a R b R c (wherein R a , R b , and R c independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom) in the molecule (hereinafter called organosilyl group containing mercaptan (B) ) .
  • Suitable examples the alkyl group represented by R a , R , or R c include a methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.
  • Suitable examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, and butoxy group.
  • a phenyl group can be used.
  • a phenyloxy group for example, a phenyloxy group can be used.
  • a halogen atom for example, fluorine, chlorine, and bromine can be used.
  • Suitable examples of the organosilyl group containing mecaptan (B) include ⁇ -mercaptopropylmethylmonomethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropylmonoethoxy silane , ⁇ -mercaptopropyldiethoxysilane , ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptoethylmonoethoxysilane , ⁇ -mercaptoethyltriethoxysilane , ⁇ -mercaptoethyltriethoxysilane, and the like.
  • ⁇ -mercaptopropyltrimethoxysilane ⁇ -mercaptopropylmethyldimethoxysilane
  • ⁇ -mercaptoethyltriethoxysilane are especially preferred.
  • organosilyl group containing mercaptans may be used either individually or in combination of two or more.
  • Suitable commercially available organosilyl group containing mecaptan (B) include SH6062 and
  • photopolymerization initiators used for photo curable resin compositions can be used as the component (C) of the present invention without any specific restrictions.
  • Suitable examples of such photopolymerization initiators include 1- hydroxycyclohexyl phenyl ketone, 3-methylacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, • .
  • triphenylamine carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'- dimethoxybenzophenone, 4 , 4 ' -diaminobenzophenone, benzoin ethyl ether, benzoin propyl ether, Michiler's ketone, benzyl methyl ketal, 1- (4-isopropylphenyl) -2- hydroxy-2-methylpropan-l-one, 2-hydroxy-2- methyl-1- phenylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- methylpropan-1-one, 4- (2 -hydroxyethoxy) phenyl- (2- hydroxy-2-propyl) ketone, 2-methyl-l- [4- (methylthio) henyl] -2-morpholino-propan-l-one, 2,4,6- trimethylbenzoyl phenylphosphinate, 2,
  • preferable photopolymerization initiators are 1-hydroxycyclohexylketone, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-l- one, bis (2 , 6-dimethoxybenzoyl-2 , 4 , 4- trimethylpentylphosphine oxide , 2,4,6- trimethylbenzoyldiphenylphosphine oxide, and 2,4,6- trimethylbenzoylphenylphosphinate.
  • Examples of commercially available photopolymerization initiators include, IRGACURE 184, 261, 369, 500, 651, 907, 819, 1700, 1800, 1850, CGI- 403, Darocur 953, 1116, 1173, 1664, 2273, 2959, ZL13331 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, LR8893 (manufactured by BASF) , Ubecryl P36 (manufactured by UCB) , VICURE55 (manuf ctured by Akzo) , ESACURE KIP 100F, KIP 150 (manufactured by Lamberti) , KAYACURE ITX, QTX, DETX and BMS (manufactured by Nippon Kayaku Co., Ltd.). Of these photo-initiators, IRGACURE 184, 369, 651, 907, 1700, 1800, 1850, Lucirin TPO, LR88
  • photo-initiators can be used either individually or in combinations of two or more.
  • composition of the present invention Besides the components (A) , (B) and (C) , various components may be added to the composition of the present invention to the extent that the effect of the present invention is not impaired.
  • composition of the present invention also (D) an ethylenically unsaturated monomer having at least one amino or amide group in the molecule and (E) a (meth) acrylate compound other than the component (A) or component (D) which has at least one a (meth) acryloyl group in the molecule.
  • Suitable examples of the ethylenically unsaturated monomer having at least one amino or amide group in the molecule (hereinafter called "amino group containing compound (D)") used as the component (D) in the present invention include N-vinylpyrrolidone, N- vinylcaprolactam, (meth) acryloylmorpholine, (meth) acrylamide, N,N-dimethyl (meth) acrylamide, N,N- dimethylaminopropyl (meth) acrylamide, octyl (meth) acrylamide, N,N-diethylaminoethyl- (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7- dimethyloctyl (meth) acrylate and the like can be given.
  • This amino group containing compound (D) can be used either individually or in
  • the addition of the component (D) not only increases the adhesion, but also extends the adhesion stability over time.
  • the (meth) acrylate compound other than the component (A) or component (D) which has at least one (meth) acryloyl group in the molecule (hereinafter called " (meth) acrylate compound (E)") used as component (E) in the present invention includes monofunctional compounds having one (meth) acryloyl group in the molecule and polyfunctional compounds which have two or more (meth) acryloyl groups in the molecule. They may be used jointly in a suitable proportion.
  • Suitable examples of the monofunctional compounds include 2 -hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, 4-hydroxy butyl (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, iso-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth)
  • (meth) acrylate ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxy ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl
  • (meth) acrylate tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7- dimethyloctyl (meth) acrylate, phenoxyethyl
  • (meth) acrylate polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7
  • (meth) acryloyloxyethylsuccinic acid trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and acrylate monomers shown by the following formulas (3) to (5) .
  • R represents a hydrogen atom or methyl group
  • R represents an alkylene group having 2-6, preferably 2-4 carbon atoms
  • R 4 is a hydrogen atom, an organic group having 1-12 carbon atoms, or an organic group having an aromatic ring
  • m is an integer from 0 to 12, and preferably from 1 to 8 ,
  • R 5 is an alkylene group having 2-8, and preferably 2-5 carbon atoms
  • p is an integer from 1 to 8, and preferably from 1 to 4 ,
  • R , R 5 , and p are the same as defined above, and R is a hydrogen atom or methyl group.
  • Suitable examples of commercially available monofunctional (meth) acrylate compounds (E) include Aronix M-101, M-102, M-110, M-lll, M-113, M-114, M-117, M-120, M-152, M-154, M-5300, M-5400, M-5500, M-5600 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, R-128H, R629, R644 (manufactured by Nippon Kayaku Co., Ltd.), IPAA, AIB, SBAA, T BA, IAAA, HEXA, CHA, NOAA, IOAA, INAA, LA, TDA, MSAA, CAA, HDAA, LTA, STA, ISAA-1, ODAA, NDAA, IBXA, ADAA, TCDA, 2-MTA, DMA, Viscoat #150, #150D, #155, #158, #160, #190, #190D, #192,
  • Suitable examples of polyfunctional (meth) acrylate compounds (E) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,9-nonane diol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylolpropane tri (
  • Suitable commercially available polyfunctional (meth) acrylate compounds (E) are SA- 1002, SA-2006, SA-2007, SA-4100, SA-5001, SA-6000, SA- 7600, SA-8000, SA-9000 (manufactured by Mitsubishi Chemical Corp.), Viscoat #195, #195D, #214HP, #215, #215D, #230, #230D, #260, #295, #295D, #300, #310HP, #310HG, #312, #335HP, #335D, #360, GPT, #400, V#540, #700, GPT (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD MANDA, R-526, NPGDA,
  • PEG400DA R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET- 30, RP-1040, T-1420, DPHA, D-310, D-330, DPCA-20, DPCA- 30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-208, M-215, M-220, M-225,
  • the amount the urethane (meth) acrylate (A) in the composition of the present invention is 30-80 parts by weight, preferably 40-70 parts by weight, for 100 parts by weight of the total of the component (A) , and component (D) , component (E) .
  • the proportion of the component (A) is less than 30 parts by weight, the tenacity of resulting cured products tends to decrease; if more than 80 parts by weight, on the other hand, the viscosity of the composition may be too high to handle the composition with ease.
  • the organosilyl group containing mercaptan (B) is incorporated in an amount of 0.01 parts by weight or more, preferably from 0.05 to 5 parts by weight, and more preferably from 0.1 to 2 part by weight, for 100 parts by weight of the component (A) or, if the component (D) and/or component (E) are used, for 100 parts by weight of total of the component (A) , component (D) , and component (E) .
  • the amount of the component (B) incorporated is too small, the adhesive properties with the adhered substrate such as a metal substrate becomes insufficient; if too large, the Young's modulus of elasticity of cured products may decrease markedly and the storage stability of the composition over time may be impaired.
  • the amount of the component (C) incorporated in the composition of the component (C) is usually from 0.1 to 10 parts by weight, and preferably from 0.5 to 7 parts by weight, for 100 parts by weight of the component (A) or, if the component (D) and/or component (E) are used, for 100 parts by weight of total of the component (A) , component (D) , and component (E) .
  • the proportion of the component (D) be in the range from 2 to 20 parts by weight, preferably from 3 to 15 parts by weight, per 100 parts by weight of total of the component (A) , component (D) , and component (E) . If the proportion of the component (D) is less than 2 parts by weight, adhesion properties of the resulting cured products to copper decreases; if more than 20 parts by weight, on the other hand, water absorption of the cured products becomes high.
  • the amount of the (meth) acrylate compound (E) incorporated in the composition of the present invention is usually from 10 to 68 parts by weight, preferably from 15 to 50 parts by weight, for 100 parts by weight of total of the component (A) , component (D) , and component (E) .
  • composition of the present invention may include the following optional components in addition to the component (D) and component (E) .
  • curable oligomers or polymers can be used, such as for example, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane polymers having a (meth) acryloyloxy group, reactive polymers obtained by reacting a copolymer, made from glycidyl methacrylate and another polymerizable monomer, and (meth) acrylic acid.
  • An a ine can be used to suppress generation of hydrogen gas which causes a transmission loss in optical fibers.
  • an amine for example, diallylamine, diisopropylamine, diethylamine, diethylhexylamine, and the like can be given.
  • paint additives such as antioxidants, UV absorbers, light stabilizers, aging preventives, other silane coupling agents than those defined under (b) above, coating surface improvers, antistatic agents, preservatives, and thermal polymerization inhibitors, for example, may be used as required.
  • Suitable antioxidants include phenol type antioxidants, bisphenol-type antioxidants, macromolecule phenol type antioxidants, sulfur-type antioxidants, and phosphorus-type antioxidants.
  • Suitable commercially available antioxidants include, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and Sumilizer GA-80S (manufactured by Sumitomo Chemical Industries Co., Ltd.) .
  • UV absorbers benzotriazole type UV absorbers, triazine type UV absorbers, and the like can be used.
  • Suitable commercially available UV absorbers include products available under the trade names Tinuvin P, 213, 234, 320, 326, 327, 328, 329 (manufactured by Ciba Specialty Chemicals Co., Ltd.),
  • Suitable light stabilizers include, Tinuvin 144, 292, 622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.) Sanol LS440, LS770 (manufactured by Sankyo Co., Ltd.) and Sumisorb T M-061 (manufactured by Sumitomo Chemical Industries Co., Ltd.).
  • the light stabilizers may be added in an amount of 5 parts by weight or less for 100 parts by weight of total weight of the component (A) , component (B) , and component (C) .
  • Suitable commercially available aging preventives include Antigene W, P, 3C, 6C, RD-G, FR and AW (manufactured by Sumitomo Chemical Industries Co., Ltd.) .
  • Suitable silane coupling agents other than component (B) include N- (2-aminoethyl) -3- aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane , ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxylpropyltrimethoxysilane, ⁇ -glycidoxylpropylmethyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxysilane, ⁇ -chloropropylmethyl dimethoxysilane, ⁇ -chloropropyl trimethoxysilane and ⁇ -methacryloyloxypropyl trimethoxysilane.
  • Suitable commercially available silane coupling agents include Saila Ace S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710, S810 (manufactured by Chisso Corp.), SH6020, SZ6023, SZ6030, SH6040, SH6076, SZ6083 (manufactured by Toray- Dow Corning Silicone Co., Ltd.), KBM403, KBM503, KBM602, KBM603, KBM803, KBE903 (manufactured by Shin- Etsu Chemical Co., Ltd.).
  • Coating surface improvers include silicone additives such as, for example, dimethyl siloxane polyethers .
  • Suitable commercially available coating surface improvers include DC-57, DC-190 (manufactured by Dow Corning) , SH-28PA, SH-29PA, SH-30PA, SH-190 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), KF351, KF352, KF353, KF354 (manufactured by Shin-Etsu Chemical Co., Ltd.), and L-700, L-7002, L-7500, FK-024- 90 (manufactured by Nippon Unicar Co., Ltd.) .
  • the composition of the present invention has a viscosity usually from 200 to 20,000 mPa*s, preferably from 2,000 to 15,000 mPa-s at 25.
  • the composition of the present invention is applied on a tension merge and cured with radiation, preferably UV and/or UV/Vis radiation.
  • the cured product should adhere well to the tension member.
  • the adhesion as tested in a 90° peel strength test should be 20 g/cm or higher, preferably between 30-500 g/cm and more preferably between 30-200 g/cm.
  • the cured product of the photo curable resin composition of the present invention has a Young's modulus of elasticity at 23 °C of 10 kg/mm 2 or higher, preferably 15 kg/mm or higher, and a Young's modulus generally of about 100 kg/mm 2 or lower.
  • a vessel equipped with a stirrer and a thermometer was charged with 20.9 g of tolylene diisocyanate, 0.02 g of 2 , 6-di-t-butyl-p-cresol , 0.01 g of phenothiazine, and 0.08 g of di-n-butyltin dilaurate.
  • the mixture was stirred and cooled over an iced-water bath at 10 under dry air atmosphere, following which 21.2 g 2 -hydroxyethyl acrylate was added dropwise while maintaining the temperature at 10 to 25°C. After the addition, the mixture was reacted for one hour at 30°C. Then, 57.9 g of polytetramethylene glycol with a number average molecular weight of 2,000 was added, followed by a continued reaction for a further 3 hours at 50-70°C.
  • a vessel equipped with a stirrer and a thermometer was charged with 26.5 g of tolylene diisocyanate, 0.02 g of 2 , 6-di-t-butyl-p-cresol , 0.01 g of phenothiazine, and 0.08 g of di-n-butyl tin dilaurate.
  • the mixture was stirred and cooled over an iced-water bath at 10°C under dry air atmosphere, following which 23.8 g of 2-hydroxyethyl acrylate was added dropwise while maintaining the temperature at 10 to 25°C. After the addition, the mixture was reacted for one hour at 30°C.
  • urethane acrylate (A2) .
  • a reaction vessel equipped with a stirrer was charged with the components with formulation respectively shown in Table 1. The components were blended by stirring to prepare the Example compositions respectively.
  • the Comparative Examples were prepared from the formulations shown in Table 1.
  • Al and A2 are respectively the urethane acrylates Al and A2 synthesized in the Synthesis Examples 1 and 2.
  • the other components are as follows.
  • E2 Bisphenol A, EO additioned diacrylate (trade name: Viscoat 700, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • E3 Tricyclodecanedimethanol diacrylate (Trade name: SA 1002, manufactured by Mitsubishi Chemical Co., Ltd.)
  • Component (F)
  • the component (F) was used instead of the component (B) in Comparative Examples.
  • the photo curable resin compositions were applied onto glass plates using an applicator bar for producing coatings with a thickness of 381 ⁇ m.
  • the coatings were cured at a UV dose of 1 J/cm under ambient atmosphere.
  • the cured coatings were conditioned for at least 12 hours at room temperature (23 °C) and relative humidity of 50% to prepare test specimens.
  • the Young's moduli of elasticity were measured at 23 °C conforming to the method of JIS K7113 at a drawing rate of 1 mm/min.
  • the Young's moduli of elasticity were calculated from the tensile stress at 2.5% distortions.
  • the photo curable resin compositions were applied onto copper plates which were previously subjected to an etching treatment process using an applicator bar for producing coatings with a thickness of 70 ⁇ m.
  • the coatings were cured at a UV dose of 0.3 J/cm 2 under nitrogen atmosphere.
  • the cured coatings were conditioned for at least 12 hours at room temperature (23 °C) and relative humidity of 50% to prepare test specimens.
  • the cured coating of the test specimens was cut at 1 cm intervals.
  • the adhesion strength between the coating and the copper substrate was evaluated by measuring the 90° peel strength at 23 °C at a drawing speed of 50 mm/min. The strength per 1 cm width (g/cm) was calculated.
  • the photo curable resin composition of the present invention exhibits high adhesion to copper and has a high Young's modulus and therefore is useful as an overcoat material for the tension member formed from steel wires coated with copper for optical fiber unit.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a photo curable resin composition exhibiting high adhesion to steel wires coated with copper used as a tension member for optical fiber unit. A photo curable resin composition comprising (A) a urethane (meth)acrylate obtained by reacting a polyol compound, polyisocyanate compound, and hydroxyl group containing (meth)acrylate compound, (B) a compound having at least one mercapto group and at least one group shown by the formula -SiRaRbRc (wherein R?a, Rb, and Rc¿ independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom) in the molecule, and (C) a photopolymerization initiator. The composition when cured generally has a Young's modulus of 10 kg/mm2 or higher, and a 90° peel strength of 20 g/cm or higher.

Description

PHOTO CURABLE RESIN COMPOSITION FOR TENSION MEMBERS
The present invention relates to a photo curable resin composition useful as an overcoat material for tension members in an optical fiber unit.
Description of related art
Optical fibers generally are bundled in certain units before being cabled. One type of optical fiber unit, which is used for submarine cable and the like, generally has a structure as shown in Figure 1. Specifically, a steel wire (1) coated with copper which is called a tension member is provided in the center of such an optical fiber unit. The steel wire (1) has an overcoat layer (2) to prevent braking of an optical fiber by a tension strength during manufacturing. Outside of the overcoat layer (2) several optical fibers (3) coated with a photo curable resin are twisted with a certain space between them. Further provided are an internal coating layer (4) made from a photo curable resin with a low Young's modulus of elasticity and an outside coating layer (5) made from a photo curable resin with a high Young's modulus of elasticity.
The tension member has been coated with either a photo curable resin with a low Young's modulus of elasticity (10 kg/mm or less) used for internal layer coating or a photo curable resin with a high Young's modulus of elasticity (50 kg/mm or more) used for outside layer coating.
However, these resins exhibit only poor adhesion to tension members and cause delamination after the unit has been fabricated. This may increase the attenuation loss.
The problem to be solved by the present invention is therefore to provide a photo curable resin composition capable of forming coatings exhibiting high adhesion to steel wires coated with copper which are used as a tension member for optical fiber unit.
As a result of extensive studies, the present inventors have found that a specific photo curable resin composition can solve the above problem.
Summary of the invention
Accordingly an object of the present invention is to provide a photo curable resin composition for coating a tension member comprising,
(A) a urethane (meth) acrylate obtained by reacting a polyol compound, polyisocyanate compound, and hydroxyl group containing (meth) acrylate compound,
(B) a compound having at least one mercapto group and at least one group shown by the formula -SiRaR Rc (wherein Ra, Rb, and Rc independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom) in the molecule, and
(C) a photopolymerization initiator.
The composition when cured preferably has a Young's modulus of 10 kg/mm2 or higher, and preferably has a 90° peel strength of 20 g/cm or higher.
Detailed description of the invention
The photo curable resin composition of the present invention will now be described in detail .
In the description of the present invention, the number average molecular weight means a polystyrene-reduced number average molecular weight measured by gel permeation chromatography. The urethane (meth) acrylate which is used as the component (A) (hereinafter referred to as "urethane (meth) acrylate (A)") is generally obtained by reacting (a) a polyol compound, (b) a polyisocyanate compound, and
(c) a hydroxyl group containing (meth) acrylate compound, as mentioned above.
As polyol compounds, for example, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, aliphatic hydrocarbons having two or more hydroxyl groups in the molecule, alicyclic hydrocarbons having two or more hydroxyl groups in the molecule, and unsaturated hydrocarbons having two or more hydroxyl groups in the molecule can be used. These polyol compounds may be used either individually or in combination of two or more. The manner of bonding of the structural units in these polyols is not specifically limited, and may be random bond, block bond, or graft bond. Suitable examples of the above-mentioned polyether polyols include aliphatic polyether polyols, alicyclic polyether polyols, aromatic polyether polyols .
Suitable examples of the aliphatic polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds.
Suitable examples of the above-mentioned ion-polymerizable cyclic compounds include cyclic ethers such as ethylene oxide, propylene oxide, butene- 1-oxide, isobutene oxide, 3 , 3-bis (chloromethyl) oxetane, tetrahydrofuran, 2 -methyl tetrahydrofuran, 3- ethyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl ether, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate . Suitable examples of specific combinations of two or more ion-polymerizable cyclic compounds include binary copolymers such as tetrahydrofuran and ethylene oxide, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2- methyltetrahydrofuran, tetrahydrofuran and 3- methyltetrahydrofuran, ethylene oxide and propylene oxide, and ethylene oxide and butene-1-oxide; and ternary copolymers such as tetrahydrofuran, butene-1- oxide , and ethylene oxide .
In addition, polyether polyols obtained by the ring-opening copolymerization of the above- mentioned ion-polymerizable cyclic compound and a cyclic imine such as ethylenimine, a cyclic lactone acid such as b-propyolactone or glycollic acid lactide, or a dimethylcyclopolysiloxane can be used. The ring- opening copolymer of these ion-polymerizable cyclic compounds may be bonded randomly or the copolymer may be block-bonded.
Suitable examples of the alicyclic polyether polyols include alkylene oxide addition diols of hydrogenated bisphenol A, alkylene oxide addition diols of hydrogenated bisphenol F, and alkylene oxide addition diols of 1, 4-cyclohexane diol .
Suitable examples of the alicyclic polyether polyols include alkylene oxide addition diols of bisphenol A, alkylene oxide addition diols of bisphenol F, and alkylene oxide addition diols of hydroquinone .
Among the above-mentioned polyether polyols, commercially available products of aliphatic polyether polyols include PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), EXCENOL1020, EXCENOL2020, EXCENOL3020 (manufactured by Asahi Glass Co., Ltd.), Unisafe DC1100, Unisafe DC1800, Unisafe DCB1100, Unisafe DCB1800 (manufactured by Nippon Oil and Fats Co., Ltd.), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG2000, PTG3000, PTGL1000, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000, PBG2000B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like; and commercially available products of aromatic polyether polyols include Uniol DA-400, DA-700, DB-400 (manufactured by Nippon Oil and Fats Co., Ltd.) .
The polyester polyols can be obtained by the reaction of a polyhydric alcohol and a polybasic acid. Suitable examples of the polyhydric alcohol include ethylene glycol , polyethylene glycol , propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1, 4-butanediol, 1,5-pentane diol, 1, 6-hexanediol, 1,7-heptane diol, 1,8 -octane diol, neopentyl glycol, 1, 4-cyclohexane diol, 1,4- cyclohexanedimethanol, 3 -methyl -1, 5-pentane diol, 1,9- nonane diol, 2 -methyl-1, 8-octane diol, and the like. As example of the polybasic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid.
Suitable commercially available polyester polyols include Kurapol P-1010, P-2010, F-1010, F-2010, PMIPA-2000, PKA-A, PKA-A2 and PNA-2000 (manufactured by Kuraray Co., Ltd.) .
Suitable examples of the polycarbonate polyols include polycarbonate of polytetrahydrofuran, poly (hexanediolcarbonate) , poly (nonanediolcarbonate) , and poly (3 -methyl- 1, 5-pentamethylene carbonate).
Suitable commercially available polycarbonate polyols include DN-980, DN-981, DN-982, DN-983 (manufactured by Nippon Polyurethane Industry, Co., Ltd.), PC-8000 (manufactured by PPG Co.), PNOC- 1000, PNOC-2000, PMC-100, PMC-2000 (manufactured by Kuraray Co., Ltd.), PLACCEL CD205 , CD210, CD220, CD205PL, CD210PL, CD220PL, CD205HL, CD210HL, CD220HL, CD210T and CD220T (manufactured by Daicel Chemical Industries, Ltd.) .
Polycaprolactone diols obtained by the reaction of ε-caprolactone and a diol can be given as examples of the polycaprolactone polyols. Suitable examples of diols include 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 . Suitable commercially available polycaprolactone polyols include PLACCEL 205, 210, 212, 220, 210N and 220AL
(manufactured by Daicel Chemical Industries, Ltd.).
Suitable examples of the aliphatic hydrocarbons having two or more hydroxyl groups in the molecule include ethylene glycol, propylene glycol, tetramethylene glycol, 1, 4-butanediol , 1,5-pentane diol, 1, 6-hexanediol, 1,7-heptane diol, 1,8 -octane diol, 1,9-nonane diol, neopentyl glycol, 2,2- diethyl- 1, 3-propanediol, 3 -methyl-1 , 5-pentane diol, 2- methyl- 1,8-octane diol, hydroxy terminal hydrogenated polybutadiene, glycerol, trimethylolpropane, pentaerythritol , sorbitol, and the like.
Suitable examples of the alicyclic hydrocarbons having two or more hydroxyl groups in the molecule include 1, 4-cyclohexane diol, 1,4- cyclohexanedimethanol, 1,2- bis (hydroxyethyl) cyclohexane, dimethylol compounds of dicyclopentadiene and tricyclodecanedimethanol .
Suitable examples of unsaturated hydrocarbons having two or more hydroxyl groups in the molecule include hydroxy terminal polybutadiene and hydroxy terminal polyisoprene .
Other examples of polyols than those mentioned above, include diol compounds such as β- methyl-δ-valerolactone diol, castor oil modified diol, polydimethylsiloxane with terminal diol, polydimethylsiloxane with terminal carbitol modified diol . The number average molecular weight of these polyol compounds (a) is in the range from 50 to 15,000, and preferably from 100 to 8,000. Suitable examples of polyisocyanate (b) which is used for the synthesis of urethane (meth) acrylate (A) 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, 2 , 2 , 4-trimethylhexamethylene diisocyanate, bis (2-isocyanatethyl) fumarate, 6- isopropy1-1, 3 -phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and tetramethyl xylylene diisocyanate. Of these, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, are preferred.. These polyisocyanate compounds (b) can be used either individually or in combinations of two or more.
Suitable examples of the hydroxyl group containing (meth) acrylate compound (c) which is a third reaction component to synthesize the urethane (meth) acrylate (A) include 2-hydroxyethyl (meth) crylate, 2-hydroxypropyl (meth) acrylate, 4- hydroxybutyl (meth) acrylate, 2-hydroxy-3- phenyloxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6- hexanediol mono (meth) acrylate, 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 structural formula (1) or (2) :
H2C=C(R1)COOCH2CH2(OCOCH2CH2CH2CH2CH2)nOH (1)
H2C=C(R1)COOCH2CH(OH)CH2OC6H5 (2)
wherein R1 indicates a hydrogen atom or methyl group and n is an integer from 1-15, and preferably 1-4. In addition, compounds obtained by the addition reaction of a glycidyl group containing compound (such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth) acrylate) and (meth) acrylic acid can also be used.
Of these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4- hydroxybutyl (meth) acrylate, are preferred. These hydroxyl group containing (meth) acrylate may be used either individually or in combinations of two or more.
There are no specific restrictions to the method of preparing the urethane (meth) acrylate (A) . The following methods (i) to (iii) can be given as typical examples. (i) A method of reacting a polyisocyanate compound (b) and a hydroxyl group containing (meth) acrylate compound (c) , and reacting the resulting product with a polyol compound (a) . (ii) A method of reacting the polyol compound (a) , olyisocyanate compound (b) , hydroxyl group containing (meth) acrylate compound (c) altogether, (iii) A method of reacting a polyol compound (a) and a polyisocyanate compound (b) and reacting the resulting product with a hydroxyl group containing (meth) acrylate compound (c) . In the preparation of the urethane (meth) acrylate (A) used in the present invention, it is desirable to use a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin di-laurylate, triethylamine, 4- diazabicyclo [2.2.2] octane, 1,1, 4-diaza-2- methylbicyclo [2.2.2] octane usually in an amount of 0.01-1 part by weight per 100 parts by weight of the total of polyol (a) , polyisocyanate (b) , and hydroxyl group containing (meth) acrylate (c) . The reaction temperature in this reaction is usually in the range of 0-90, and preferably 10-80.
The number average molecular weight of the urethane (meth) acrylate which is used in the present invention is from 100 to 20,000, and preferably from 500 to 15,000.
When the number average molecular weight of the urethane (meth) acrylate is less than 100, Young's modulus of elasticity of the resulting cured products tends to increase; if more than 20,000, on the other hand, the viscosity of the composition increases, making the composition difficult to handle.
As the component (B) in the composition of the present invention, a compound is used having at least one mercapto group and at least one group shown by the formula -SiRaRbRc (wherein Ra, Rb, and Rc independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom) in the molecule (hereinafter called organosilyl group containing mercaptan (B) ) .
Suitable examples the alkyl group represented by Ra, R , or Rc include a methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. Suitable examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, and butoxy group. As the aryl group, for example, a phenyl group can be used. As the aryloxy group, for example, a phenyloxy group can be used. As a halogen atom, for example, fluorine, chlorine, and bromine can be used.
Suitable examples of the organosilyl group containing mecaptan (B) include γ-mercaptopropylmethylmonomethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmonoethoxy silane , γ-mercaptopropyldiethoxysilane , γ-mercaptopropyltriethoxysilane, β-mercaptoethylmonoethoxysilane , β-mercaptoethyltriethoxysilane , β-mercaptoethyltriethoxysilane, and the like. Of these compounds, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, β-mercaptoethyltriethoxysilane are especially preferred. These organosilyl group containing mercaptans may be used either individually or in combination of two or more.
Suitable commercially available organosilyl group containing mecaptan (B) include SH6062 and
AY43-062 (manufactured by Toray-Dow Corning Silicone
Co. , Ltd.) .
Any conventionally known photopolymerization initiators used for photo curable resin compositions can be used as the component (C) of the present invention without any specific restrictions. Suitable examples of such photopolymerization initiators include 1- hydroxycyclohexyl phenyl ketone, 3-methylacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone,• . ■ triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'- dimethoxybenzophenone, 4 , 4 ' -diaminobenzophenone, benzoin ethyl ether, benzoin propyl ether, Michiler's ketone, benzyl methyl ketal, 1- (4-isopropylphenyl) -2- hydroxy-2-methylpropan-l-one, 2-hydroxy-2- methyl-1- phenylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- methylpropan-1-one, 4- (2 -hydroxyethoxy) phenyl- (2- hydroxy-2-propyl) ketone, 2-methyl-l- [4- (methylthio) henyl] -2-morpholino-propan-l-one, 2,4,6- trimethylbenzoyl phenylphosphinate, 2,4,6- trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2 , 6-dimethoxybenzoyl-2 , 4 , 4-trimethylpentylphosphine oxide, methyl benzoyl formate, thioxanethone, diethylthioxanthone, 2- isopropylthioxanthone, 2- chlorothioxanthone and oligo [2-hydroxy-2-methyl-l- [4- (1-methylvinyl) ] phenyl] propanone .
Among these, preferable photopolymerization initiators are 1-hydroxycyclohexylketone, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-l- one, bis (2 , 6-dimethoxybenzoyl-2 , 4 , 4- trimethylpentylphosphine oxide , 2,4,6- trimethylbenzoyldiphenylphosphine oxide, and 2,4,6- trimethylbenzoylphenylphosphinate.
Examples of commercially available photopolymerization initiators include, IRGACURE 184, 261, 369, 500, 651, 907, 819, 1700, 1800, 1850, CGI- 403, Darocur 953, 1116, 1173, 1664, 2273, 2959, ZL13331 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, LR8893 (manufactured by BASF) , Ubecryl P36 (manufactured by UCB) , VICURE55 (manuf ctured by Akzo) , ESACURE KIP 100F, KIP 150 (manufactured by Lamberti) , KAYACURE ITX, QTX, DETX and BMS (manufactured by Nippon Kayaku Co., Ltd.). Of these photo-initiators, IRGACURE 184, 369, 651, 907, 1700, 1800, 1850, Lucirin TPO, LR8893 are preferred.
These photo-initiators can be used either individually or in combinations of two or more.
Besides the components (A) , (B) and (C) , various components may be added to the composition of the present invention to the extent that the effect of the present invention is not impaired.
It is preferred to use in the composition of the present invention also (D) an ethylenically unsaturated monomer having at least one amino or amide group in the molecule and (E) a (meth) acrylate compound other than the component (A) or component (D) which has at least one a (meth) acryloyl group in the molecule.
Suitable examples of the ethylenically unsaturated monomer having at least one amino or amide group in the molecule (hereinafter called "amino group containing compound (D)") used as the component (D) in the present invention include N-vinylpyrrolidone, N- vinylcaprolactam, (meth) acryloylmorpholine, (meth) acrylamide, N,N-dimethyl (meth) acrylamide, N,N- dimethylaminopropyl (meth) acrylamide, octyl (meth) acrylamide, N,N-diethylaminoethyl- (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7- dimethyloctyl (meth) acrylate and the like can be given. This amino group containing compound (D) can be used either individually or in combinations of two or more .
The addition of the component (D) not only increases the adhesion, but also extends the adhesion stability over time.
The (meth) acrylate compound other than the component (A) or component (D) which has at least one (meth) acryloyl group in the molecule (hereinafter called " (meth) acrylate compound (E)") used as component (E) in the present invention includes monofunctional compounds having one (meth) acryloyl group in the molecule and polyfunctional compounds which have two or more (meth) acryloyl groups in the molecule. They may be used jointly in a suitable proportion. Suitable examples of the monofunctional compounds include 2 -hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, 4-hydroxy butyl (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, iso-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, iso-decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl
(meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxy ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl
(meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7- dimethyloctyl (meth) acrylate, phenoxyethyl
(meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3 , 7-dimethyloctyl (meth) acrylate, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2-
(meth) acryloyloxyethylsuccinic acid, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and acrylate monomers shown by the following formulas (3) to (5) .
CH2=C (R ■COO(R30)m-R4 (3)
wherein R represents a hydrogen atom or methyl group, R represents an alkylene group having 2-6, preferably 2-4 carbon atoms, R4 is a hydrogen atom, an organic group having 1-12 carbon atoms, or an organic group having an aromatic ring, and m is an integer from 0 to 12, and preferably from 1 to 8 ,
Figure imgf000019_0001
wherein R is the same as defined above, R5 is an alkylene group having 2-8, and preferably 2-5 carbon atoms, and p is an integer from 1 to 8, and preferably from 1 to 4 ,
Figure imgf000020_0001
wherein R , R5, and p are the same as defined above, and R is a hydrogen atom or methyl group.
Suitable examples of commercially available monofunctional (meth) acrylate compounds (E) include Aronix M-101, M-102, M-110, M-lll, M-113, M-114, M-117, M-120, M-152, M-154, M-5300, M-5400, M-5500, M-5600 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, R-128H, R629, R644 (manufactured by Nippon Kayaku Co., Ltd.), IPAA, AIB, SBAA, T BA, IAAA, HEXA, CHA, NOAA, IOAA, INAA, LA, TDA, MSAA, CAA, HDAA, LTA, STA, ISAA-1, ODAA, NDAA, IBXA, ADAA, TCDA, 2-MTA, DMA, Viscoat #150, #150D, #155, #158, #160, #190, #190D, #192, #193, #220, #320, #2311HP, #2000, #2100, #2150, #2180, MTG (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-1 0G, AMP-2 0G, AMP-60G, AMP-90G, A-SA, LA (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate IA-A, L-A, S-A, BO-A, EC-A, MTG-A, DPM- A, PO-A, P-200A, THF-A, IB-XA, HOA-MS, HOA-MPL, HOA- MPE, HOA-HH, IO-A, BZ-A, NP-EA, NP-1 OEA, HOB-A, FA-1 08, Epoxy Ester M-600A (manufactured by Kyoeisha Chemical Co., Ltd.), and FA-511, FA-512A, FA-513A (manufactured by Hitachi Chemical Co., Ltd.) .
Suitable examples of polyfunctional (meth) acrylate compounds (E) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,9-nonane diol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , dipentaerythritol penta (meth) acrylate , dipentaerythritol hexa (meth) acrylate , trimethylolpropanetrioxyethyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, tris(2- hydroxyethyl) isocyanurate di (meth) acrylate, tris (2- hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol F di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, and bisphenol A diepoxy di (meth) acrylate, bisphenol F diepoxy di (meth) acrylate .
Suitable commercially available polyfunctional (meth) acrylate compounds (E) are SA- 1002, SA-2006, SA-2007, SA-4100, SA-5001, SA-6000, SA- 7600, SA-8000, SA-9000 (manufactured by Mitsubishi Chemical Corp.), Viscoat #195, #195D, #214HP, #215, #215D, #230, #230D, #260, #295, #295D, #300, #310HP, #310HG, #312, #335HP, #335D, #360, GPT, #400, V#540, #700, GPT (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD MANDA, R-526, NPGDA,
PEG400DA, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET- 30, RP-1040, T-1420, DPHA, D-310, D-330, DPCA-20, DPCA- 30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-208, M-215, M-220, M-225,
M-233, M-240, M-245, M-260, M-270, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-400, M-408, M-450 (manufactured by Toagosei Co., Ltd.), SR-212, SR-213, SR-355 (manufactured by Sartomer Co., Ltd.), SP-1506, SP-1507, SP-1509, SP-1519-1, SP-1563, SP-2500, VR60, VR77, VR90 (manufactured by Showa Highpolymer Co., Ltd.), and the like.
In the case where the component (D) and/or component (E) are used, the amount the urethane (meth) acrylate (A) in the composition of the present invention is 30-80 parts by weight, preferably 40-70 parts by weight, for 100 parts by weight of the total of the component (A) , and component (D) , component (E) . When the proportion of the component (A) is less than 30 parts by weight, the tenacity of resulting cured products tends to decrease; if more than 80 parts by weight, on the other hand, the viscosity of the composition may be too high to handle the composition with ease. In the composition of the present invention, the organosilyl group containing mercaptan (B) is incorporated in an amount of 0.01 parts by weight or more, preferably from 0.05 to 5 parts by weight, and more preferably from 0.1 to 2 part by weight, for 100 parts by weight of the component (A) or, if the component (D) and/or component (E) are used, for 100 parts by weight of total of the component (A) , component (D) , and component (E) . When the amount of the component (B) incorporated is too small, the adhesive properties with the adhered substrate such as a metal substrate becomes insufficient; if too large, the Young's modulus of elasticity of cured products may decrease markedly and the storage stability of the composition over time may be impaired. The amount of the component (C) incorporated in the composition of the component (C) is usually from 0.1 to 10 parts by weight, and preferably from 0.5 to 7 parts by weight, for 100 parts by weight of the component (A) or, if the component (D) and/or component (E) are used, for 100 parts by weight of total of the component (A) , component (D) , and component (E) .
When the component (D) and component (E) are used, it is desirable the proportion of the component (D) be in the range from 2 to 20 parts by weight, preferably from 3 to 15 parts by weight, per 100 parts by weight of total of the component (A) , component (D) , and component (E) . If the proportion of the component (D) is less than 2 parts by weight, adhesion properties of the resulting cured products to copper decreases; if more than 20 parts by weight, on the other hand, water absorption of the cured products becomes high. In addition, the amount of the (meth) acrylate compound (E) incorporated in the composition of the present invention is usually from 10 to 68 parts by weight, preferably from 15 to 50 parts by weight, for 100 parts by weight of total of the component (A) , component (D) , and component (E) .
The composition of the present invention may include the following optional components in addition to the component (D) and component (E) .
Other curable oligomers or polymers can be used, such as for example, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane polymers having a (meth) acryloyloxy group, reactive polymers obtained by reacting a copolymer, made from glycidyl methacrylate and another polymerizable monomer, and (meth) acrylic acid.
An a ine can be used to suppress generation of hydrogen gas which causes a transmission loss in optical fibers. As such an amine, for example, diallylamine, diisopropylamine, diethylamine, diethylhexylamine, and the like can be given.
In addition to the above components, various paint additives such as antioxidants, UV absorbers, light stabilizers, aging preventives, other silane coupling agents than those defined under (b) above, coating surface improvers, antistatic agents, preservatives, and thermal polymerization inhibitors, for example, may be used as required.
Suitable antioxidants, for example, include phenol type antioxidants, bisphenol-type antioxidants, macromolecule phenol type antioxidants, sulfur-type antioxidants, and phosphorus-type antioxidants. Suitable commercially available antioxidants include, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and Sumilizer GA-80S (manufactured by Sumitomo Chemical Industries Co., Ltd.) . As UV absorbers, benzotriazole type UV absorbers, triazine type UV absorbers, and the like can be used. Suitable commercially available UV absorbers include products available under the trade names Tinuvin P, 213, 234, 320, 326, 327, 328, 329 (manufactured by Ciba Specialty Chemicals Co., Ltd.),
Seesorb 102, 103, 110, 202, 501, 704, 712 (manufactured by Sypro Chemical Co., Ltd.) and Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Industries Co., Ltd.). Suitable light stabilizers include, Tinuvin 144, 292, 622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.) Sanol LS440, LS770 (manufactured by Sankyo Co., Ltd.) and Sumisorb T M-061 (manufactured by Sumitomo Chemical Industries Co., Ltd.). The light stabilizers may be added in an amount of 5 parts by weight or less for 100 parts by weight of total weight of the component (A) , component (B) , and component (C) .
As aging preventives, phenol type aging preventives, allylamine type aging preventives, ketoneamine type aging preventives, and the like can be used. Suitable commercially available aging preventives include Antigene W, P, 3C, 6C, RD-G, FR and AW (manufactured by Sumitomo Chemical Industries Co., Ltd.) . Suitable silane coupling agents other than component (B) include N- (2-aminoethyl) -3- aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane , γ-aminopropyltriethoxysilane, γ-glycidoxylpropyltrimethoxysilane, γ-glycidoxylpropylmethyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxysilane, γ-chloropropylmethyl dimethoxysilane, γ-chloropropyl trimethoxysilane and γ-methacryloyloxypropyl trimethoxysilane. Suitable commercially available silane coupling agents include Saila Ace S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710, S810 (manufactured by Chisso Corp.), SH6020, SZ6023, SZ6030, SH6040, SH6076, SZ6083 (manufactured by Toray- Dow Corning Silicone Co., Ltd.), KBM403, KBM503, KBM602, KBM603, KBM803, KBE903 (manufactured by Shin- Etsu Chemical Co., Ltd.).
Coating surface improvers include silicone additives such as, for example, dimethyl siloxane polyethers . Suitable commercially available coating surface improvers include DC-57, DC-190 (manufactured by Dow Corning) , SH-28PA, SH-29PA, SH-30PA, SH-190 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), KF351, KF352, KF353, KF354 (manufactured by Shin-Etsu Chemical Co., Ltd.), and L-700, L-7002, L-7500, FK-024- 90 (manufactured by Nippon Unicar Co., Ltd.) .
The composition of the present invention has a viscosity usually from 200 to 20,000 mPa*s, preferably from 2,000 to 15,000 mPa-s at 25. The composition of the present invention is applied on a tension membre and cured with radiation, preferably UV and/or UV/Vis radiation. The cured product should adhere well to the tension member. The adhesion as tested in a 90° peel strength test should be 20 g/cm or higher, preferably between 30-500 g/cm and more preferably between 30-200 g/cm.
Moreover, the cured product of the photo curable resin composition of the present invention has a Young's modulus of elasticity at 23 °C of 10 kg/mm2 or higher, preferably 15 kg/mm or higher, and a Young's modulus generally of about 100 kg/mm2 or lower.
EXAMP ES
The present invention will now described by way examples which are not intended to be limiting of the invention.
Synthesis Example i
Urethane (meth) acrylate of component (A)
A vessel equipped with a stirrer and a thermometer was charged with 20.9 g of tolylene diisocyanate, 0.02 g of 2 , 6-di-t-butyl-p-cresol , 0.01 g of phenothiazine, and 0.08 g of di-n-butyltin dilaurate. The mixture was stirred and cooled over an iced-water bath at 10 under dry air atmosphere, following which 21.2 g 2 -hydroxyethyl acrylate was added dropwise while maintaining the temperature at 10 to 25°C. After the addition, the mixture was reacted for one hour at 30°C. Then, 57.9 g of polytetramethylene glycol with a number average molecular weight of 2,000 was added, followed by a continued reaction for a further 3 hours at 50-70°C.
The reaction was terminated when the amount of residual isocyanate was reduced to 0.1 g. The resulting urethane acrylate is designated as urethane acrylate (Al) .
Synthesis Example 2
Urethane (meth) acrylate of component (A)
A vessel equipped with a stirrer and a thermometer was charged with 26.5 g of tolylene diisocyanate, 0.02 g of 2 , 6-di-t-butyl-p-cresol , 0.01 g of phenothiazine, and 0.08 g of di-n-butyl tin dilaurate. The mixture was stirred and cooled over an iced-water bath at 10°C under dry air atmosphere, following which 23.8 g of 2-hydroxyethyl acrylate was added dropwise while maintaining the temperature at 10 to 25°C. After the addition, the mixture was reacted for one hour at 30°C. Then, 49.7 g of polytetramethylene glycol with a number average molecular weight of 1,000 was added, followed by a continued reaction for a further 3 hours at 50-70°C. The reaction was terminated when the amount of residual isocyanate was reduced to 0.1 g. The resulting urethane acrylate is designated as urethane acrylate (A2) .
Examples and Comparative Examples Preparation of photo curable coating compositions
A reaction vessel equipped with a stirrer was charged with the components with formulation respectively shown in Table 1. The components were blended by stirring to prepare the Example compositions respectively. The Comparative Examples were prepared from the formulations shown in Table 1. In Table 1, Al and A2 are respectively the urethane acrylates Al and A2 synthesized in the Synthesis Examples 1 and 2. The other components are as follows.
Component (B)
Bl : γ-mercaptopropyltrimethoxysilane (trade name: SH6062, manufactured by Toray-Dow Corning Silicone Co., Ltd.) Component (C)
Cl : 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) Component (D) DI : Acryloylmorpholine (trade name: ACMO, manufactured by Kojin Co., Ltd.) D2 : N-vinyl-2-pyrrolidone Component (E)
El: Isobornyl acrylate (trade name: IBXA, manufactured by Osaka Organic Chemical Industry
Co., Ltd.) E2 : Bisphenol A, EO additioned diacrylate (trade name: Viscoat 700, manufactured by Osaka Organic Chemical Industry Co., Ltd.) E3 : Tricyclodecanedimethanol diacrylate (Trade name: SA 1002, manufactured by Mitsubishi Chemical Co., Ltd.) Component (F)
Fl : n-dodecylmercaptan (manufactured by Tokyo Kasei Co., Ltd.)
F2 : Hexyltrimethoxysilane (Trade name: LS-3130, manufactured by Shin-Etsu Chemical Co., Ltd.)
The component (F) was used instead of the component (B) in Comparative Examples.
Next, on each composition of Examples and Comparative Examples, Young's modulus of elasticity and adhesion to copper were measured as follows.
1. Measurement of Young's modulus of elasticity
The photo curable resin compositions were applied onto glass plates using an applicator bar for producing coatings with a thickness of 381 μm. The coatings were cured at a UV dose of 1 J/cm under ambient atmosphere. The cured coatings were conditioned for at least 12 hours at room temperature (23 °C) and relative humidity of 50% to prepare test specimens. The Young's moduli of elasticity were measured at 23 °C conforming to the method of JIS K7113 at a drawing rate of 1 mm/min. The Young's moduli of elasticity were calculated from the tensile stress at 2.5% distortions.
2. Measurement of adhesion to copper (90° peel strength) The photo curable resin compositions were applied onto copper plates which were previously subjected to an etching treatment process using an applicator bar for producing coatings with a thickness of 70 μm. The coatings were cured at a UV dose of 0.3 J/cm2 under nitrogen atmosphere. The cured coatings were conditioned for at least 12 hours at room temperature (23 °C) and relative humidity of 50% to prepare test specimens. The cured coating of the test specimens was cut at 1 cm intervals. The adhesion strength between the coating and the copper substrate was evaluated by measuring the 90° peel strength at 23 °C at a drawing speed of 50 mm/min. The strength per 1 cm width (g/cm) was calculated.
The results were shown in Table 1. TABLE 1
(parts by weight)
Figure imgf000033_0001
Effect of the Invention
As described above, the photo curable resin composition of the present invention exhibits high adhesion to copper and has a high Young's modulus and therefore is useful as an overcoat material for the tension member formed from steel wires coated with copper for optical fiber unit.

Claims

1. A photo curable resin composition for coating a tension member for use in an optical glass fiber cable, comprising,
(A) a urethane (meth) acrylate obtained by reacting a polyol compound, polyisocyanate compound, and hydroxyl group containing (meth) acrylate compound, (B) a compound having at least one mercapto group and at least one group shown by the formula - SiRaRbRc (wherein Ra, Rb, and Rc independently represent an alkyl group, alkoxy group, aryl group, aryloxy group, halogen atom, or hydrogen atom) in the molecule, and
(C) a photopolymerization initiator.
2. Composition according to claim 1, further comprising at least one compound selected from the group consisting of, (D) an ethylenically unsaturated monomer having at least one amino or amide group in the molecule, and (E) a (meth) acrylate compound other than the component (A) or component (D) , having at least one (meth) acryloyl group in the molecule.
3. Composition according to any one of claims 1-2 wherein the composition when cured has a Young's modulus of 10 kg/mm or higher.
4. Composition according to claim 3 wherein the Young's modulus is between 15-100 kg/mm .
5. Composition according to any one of claims 1-3 wherein the composition when cured has a 90° peel strength of 20 g/cm or higher.
6. Composition according to claim 5 wherein the adhesion to copper is between 30-500 g/cm.
7. Composition according to any one of claims 2-6 wherein the composition comprises
30-80 parts by weight (A) 0.05-5 parts by weight (B)
0.1-10 parts by weight (C)
2-20 parts by weight (D)
10-68 parts by weight (E) per 100 parts by weight of the total of components (A) , (D) and (E)
8. Tension member for an optical fiber unit having a cured coating which coating before curing is the photo curable resin composition according to any one of claims 1-7.
9. Tension member according to claim 8 wherein the tension member is a steel wire coated with copper.
10. Optical fiber unit comprising at least one tension member according to any one of claims 8-9, and at least one coated optical glass fiber.
PCT/NL1999/000629 1998-10-15 1999-10-12 Photo curable resin composition for tension members Ceased WO2000022022A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP29395598 1998-10-15
JP10/293955 1998-10-15
JP30447398 1998-10-26
JP10/304473 1998-10-26

Publications (1)

Publication Number Publication Date
WO2000022022A1 true WO2000022022A1 (en) 2000-04-20

Family

ID=26559627

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000629 Ceased WO2000022022A1 (en) 1998-10-15 1999-10-12 Photo curable resin composition for tension members

Country Status (1)

Country Link
WO (1) WO2000022022A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014092270A1 (en) * 2012-12-12 2014-06-19 제일모직 주식회사 Photocurable composition and device including barrier layer formed from composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726649A (en) * 1985-08-19 1988-02-23 Ocean Cable Co., Ltd. Optical fiber cable
US4849462A (en) * 1983-11-10 1989-07-18 Desoto, Inc. Ultraviolet-curable coatings for optical glass fibers having improved adhesion
JPH03199217A (en) * 1989-12-27 1991-08-30 Desoto Inc Liquid curable resin composition
US5146531A (en) * 1989-05-11 1992-09-08 Borden, Inc. Ultraviolet radiation-curable coatings for optical fibers and optical fibers coated therewith
JPH09167524A (en) * 1995-12-18 1997-06-24 Hitachi Cable Ltd Ultra-thin multi-core cable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849462A (en) * 1983-11-10 1989-07-18 Desoto, Inc. Ultraviolet-curable coatings for optical glass fibers having improved adhesion
US4726649A (en) * 1985-08-19 1988-02-23 Ocean Cable Co., Ltd. Optical fiber cable
US5146531A (en) * 1989-05-11 1992-09-08 Borden, Inc. Ultraviolet radiation-curable coatings for optical fibers and optical fibers coated therewith
JPH03199217A (en) * 1989-12-27 1991-08-30 Desoto Inc Liquid curable resin composition
JPH09167524A (en) * 1995-12-18 1997-06-24 Hitachi Cable Ltd Ultra-thin multi-core cable

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199141, Derwent World Patents Index; Class A14, AN 1991-299692, XP002126059 *
DATABASE WPI Section Ch Week 199735, Derwent World Patents Index; Class A14, AN 1997-383112, XP002126058 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014092270A1 (en) * 2012-12-12 2014-06-19 제일모직 주식회사 Photocurable composition and device including barrier layer formed from composition
US10392459B2 (en) 2012-12-12 2019-08-27 Cheil Industries, Inc. Photocurable composition and device including barrier layer formed from composition

Similar Documents

Publication Publication Date Title
US6180741B1 (en) Liquid curable resin composition
US6063888A (en) Liquid curable resin composition
US5986018A (en) Liquid curable resin compositions
JP3196269B2 (en) Liquid curable resin composition
JP3882028B2 (en) Liquid curable resin composition
EP1268678B1 (en) Liquid curable resin composition and double layer film
JPH11106448A (en) Liquid curable resin composition and cured product thereof
EP0785961A1 (en) Optical glass fiber coating composition
JP4341872B2 (en) Curable liquid resin composition
JP4250308B2 (en) Liquid curable resin composition
US5913004A (en) Optical glass fiber coating composition
KR20070041670A (en) Curable Liquid Resin Composition
WO2001047824A1 (en) Optical fiber coating compositions
JP4789329B2 (en) Double layer film
EP1320563B1 (en) Liquid curable resin composition and cured products
US20080167432A1 (en) Curable Liquid Resin Composition
JP4212076B2 (en) Photocurable resin composition and cured product
CN1930252B (en) curable liquid resin composition
WO2000022022A1 (en) Photo curable resin composition for tension members
JP3383361B2 (en) Liquid curable resin composition
JP3292326B2 (en) Liquid curable resin composition
KR100475843B1 (en) Liquid curable resin composition
JP2004067866A (en) Radiation-curable resin composition
JPH11302329A (en) Liquid curable resin composition and cured product thereof
JP2004292739A (en) Radiation-curable liquid resin composition for optical fiber coating materials

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 09593947

Country of ref document: US

122 Ep: pct application non-entry in european phase