CA2118421A1 - Liquid curable resin composition - Google Patents
Liquid curable resin compositionInfo
- Publication number
- CA2118421A1 CA2118421A1 CA 2118421 CA2118421A CA2118421A1 CA 2118421 A1 CA2118421 A1 CA 2118421A1 CA 2118421 CA2118421 CA 2118421 CA 2118421 A CA2118421 A CA 2118421A CA 2118421 A1 CA2118421 A1 CA 2118421A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- acrylate
- composition
- compound
- polyols
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/483—Polyacrylates
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
-
- 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
-
- 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
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
2118421 9321248 PCTABS00027 A liquid curable resin composition comprising a urethane (meth)acrylate obtained by the reaction of: (A) a polyether polyol compound containing, as structural units, groups represented by the following formulas: (1) -CH2CH2O-, (2) -CH2CH(R)O-, and (3) one or more groups selected from groups (a) -CH2CH2CH2CH2O-, (b), and (c) as shown above, wherein R represents an alkyl group containing two or more carbon atoms, and R1 and R2 are independently selected from a hydrogen atom or a methyl group; (B) a polyisocyanate compound; and (C) a (meth)acrylate compound having a hydroxy group. The composition exhibits a high curing rate, its cured material has a low Young's modulus and a high gel ratio, provides superior heat resistance and light resistance, and generates only a small amount of hydrogen gas. It is thus particularly suitable as a material for optical fiber coating.
Description
WO 93/21248 1 2 1 1 ~ 4 ~ 1 PCI/US93/02037 .
LIQUID CUR~BLE RESIN COMPOSITION
F; el d nf th~ Tnvention The present invention relates to a liquid curable resin composition which has superior curing characteristics, durability, and the like, adheres well to various types of substrates, and is therefore useful as a coating material for plastics, wood, porcelain, glass, paper, and the like, and as an optical molding material, three-dimensional molding material, printing plate material, and the like. :~
.`:
0 Descrl~t~ on of the Prior Art Generally, an optical fiber is provided with a re~in coating comprising a flexible primary coating layer on the `.
8urface of the optical fiber, with the object of protecting and reinforcing the bare optical fiber threads immediately ~
15 after hot melt spinn~ng of the glas~ fiber, the outside of ~:
which is covered in turn by a secondary coating layer. The coating material used to form these coatings must have the -`
following characteristics:
(1) be a:liquid at room temperature and have high ~: 20 process~ability;
LIQUID CUR~BLE RESIN COMPOSITION
F; el d nf th~ Tnvention The present invention relates to a liquid curable resin composition which has superior curing characteristics, durability, and the like, adheres well to various types of substrates, and is therefore useful as a coating material for plastics, wood, porcelain, glass, paper, and the like, and as an optical molding material, three-dimensional molding material, printing plate material, and the like. :~
.`:
0 Descrl~t~ on of the Prior Art Generally, an optical fiber is provided with a re~in coating comprising a flexible primary coating layer on the `.
8urface of the optical fiber, with the object of protecting and reinforcing the bare optical fiber threads immediately ~
15 after hot melt spinn~ng of the glas~ fiber, the outside of ~:
which is covered in turn by a secondary coating layer. The coating material used to form these coatings must have the -`
following characteristics:
(1) be a:liquid at room temperature and have high ~: 20 process~ability;
(2) pro~ide good productivity at a high curing rate;
(3) show superior flexi~ility;
(4) exhibit very little physical change during a wide range of temperature changes ; ~:
(5) have superior thermal resistance and superior resistance to hydrolysis;
(6) show superior long term reliability with little physical chan~es over time;
(7), show superior resistance to chemicals such as acids and alkalis;
18) exhibit low moisture and water absorption; and - 19) exhibit superior light resistance.
To meet these requiremen~s various liquid coating ; materials of the radiation curable type have been de~eloped. :~
. .
W093/212~ 2 1 ~ ~ 'I 2 1 PCT/US93/02037 They are compositions containing urethane acrylate using, for example, tetrahydrofuranethylene oxide ring opening copolymers (Japanese patent Laid-open (ko-kai) No.
86450/1986), tetrahydrofuranpropylene oxide ring opening copolymer (Japanese Patent Laid-open (ko-kai) No.
181170/1985), or tetrahydrofuranalkyltetrahydrOfuran copol~mers (Japanese ~atent Laid-open (ko-kai) No.
115964/1989).
Compositions in which these polyether copolymers are used have drawbacks still to be solved. That is, urethane acrylates using these polyether copolymers are insufficient in one or more of the characteristics, including resistance to ultraviolet light, heat resistance, light resistance (resistance against changing its color into yellow under light radiation~, heat resistance (resistance against changing its color into yellow when heated), and flexibility.
Accordingly, an ob~ect of the present invention is to provide, with due considexation to the drawbacks of such conventional compositions, a ~iquid curable resin composition ideal as a covering material for optical fiber, which has a low viscosity at room t~mperature and exhi~its good processability when used to coYer optical fibers, has good optical curing characteristics r can accommodate high speed optical fiber production, and in the cured state shows excellent flexibility, good resistance to heat~ ultraviolet light, and oil, and exhibits suitable adherence to optical fiber.
This object is achieved in the presen~ inven~_on by the ! provision of a liquid curable resin composition comprising a urethane (meth)acrylate obtained by the reaction of:
(A) a polyether polyol compound containing, as a structural units, ~roups represented by the following formulae (1), ~2), and (3), (1) -CH2CH20-WO93/212~ 2 1 1 ~ ~ 2 1 PCT/US93/02037 (2) -CH2CH(R)O-, and (3) one or more groups selected from groups (a), (b), and (c) below, -CH2CH2CI 12CH20- (a) R
C--~ (b) ~
Rl :
,.
{~1~~ (c) wherein R represents an alkyl group containing two or more carbon atoms, and R1 and R2 are independently se~ected $rom a hydrogen atom or ~ methyl group; :~
(B) a polyisocyanate compound; and (C3 a ~meth~acrylate compound having a hydroxy group.
The liquid cur2ble resin compQsition of the present invention has an extxemely low Young's modulus at roo~ tempexature, shows a suitable adher.ing strength to glass fiber, has super~or durability, exhibits high speed curing performance, and is thus suitable as a coating material for optical fiber.
~m~
A polyether polyol compound (here~nafter referred to as polyol compound ~A)) used in the present invention must contain structural uni~s of th~ above formulae (1), (2), and t3). There are ~o limitations as to the manner in which WO~3/212~ ~ 2 1 PCT/US93/02037 these structural units are polymerized. They may be polymerized by random, block, or graft polymerization.
Such a polyol compound (A) can be prepared by the ring-opening polymerization of ethylene oxide, l,2-alkylene oxides with 4 or more carbon atoms, e.g, 1,2-butylene oxide, l,2-hexene oxide, or the iike, and one or more compounds selected ~;
from polytetramethylene glycol, bisphenol A, and bisphenol F, `~
by a known method.
The proportion of structural unit (1) contained in polyol compound (A) is 5 to 50% by weight, and preferably 10 to 45%. If the amount of the structural unit ~1) is less than 5%, improvement in the oil resistance of the composition after curing is insufficient; if greater than 50%, water resistance and flexibility of the composition after curing tend to be.lowered. A preferable proportion of structural unit ~2) is 10 to 90%, with a particularly preferable range being 20 to 80%. The proportion of structural unit (3) is preferably 5 to 85%, and more preferably 10 to 70%.
The num`ber of carbon atoms of R in the unit of formula (2) conta~ned in ~meth)acrylate (A) is preferably 2 to 12, with a particularly preferable range being 2 to 4.
The number average molecular weight of the polyol compound (A) is usually in a range of 200 to 10,0~0, and preferably S00 to 8,000. If the number average molecular weight is less than 200~ the Young's modulus of the cured material at room temperature or at lower temperatures increases, and there is a tendency toward an increase in transmission losses from ~ide pressure when it is applied to optical fiber; if greater than 10, t the viscosity of the resulting composition tends to increase, resulting in impaired coa~ing performance of the composition when it is coated onto the optical fiber.
The polyol compound (A) may contain any structural units other than the above structural units of the formulae ~1) to ~3), to the extent that the effects of the present invention are not affected, so long as polyol compound (A) contains all .
WO93J21248 2 1 1 ~ '1 2 I PCT/US93/02037 ` 5 of these 3 structural units. Examples of such other structural units include -CH2CH2CH20-, -CH2CH(CH3)O-, and the :;
like.
In addition, polyols which do not have the above S structural units (l), (2) and (33 can be used in combination.
Examples of such polyols include polyether polyols, polyester polyols, polycarbonate polyols, polycapralactone polyols, and other polyols.
Examples of polyether polyols which do not ha~e the above structural units (l), (2~ and (3~ include, for example, polyethylene glycolO l,2-polypropylene glycol, l,3- :
polypropylene glycol, l,2-polybutylene glycol, `
polyisobutylene glycol, propylene oxide-te~rahydrofuran copolymers, methyl tetrahydrofuran-tetrahydrofuran ..
copolymers, and the like.
Examples which can be given of polyester polyols include polyester polyols obtained by reacting a polyvalent alcohol .
such as ethylene glycol, polyethylene glycol, pxopylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, l,6-hexane diol, neopentyl glycol, l,4-cyclohexanedimethanol, 3-methyl-l,5-pentanediol, l,9-nonanediol, 2-methyl-lr8-octanediol, or the like with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, or the like; and commercial produ ts such as Kurapol P-2010, PMIPA, PR~-A, P~A-A2, PNA2000 (manufactured by Xuraray C5. ), and the like.
Examples which can be given of polycarbon~te polyols include 1,6-hexanepolycarbonate and produ ts available on the market, such as DN-980, DN-981, DN-982, DN-983 ~manufactured ~y Nihon Polyurethane Co., Ltd.~, PC-8000 (manufactured by PPG of the US), and the like.
Examples of polycaprolactone polyols include polycaprolactonediols obtained by reacting ~-caprolactone with a divalent diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, W093/21248 2 1 1 ~ 1 2 ~ PCT/US93/02037 tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl ~lycol, 1,4-butanediol, or the like, as well as PLACCEL-205, 205Ah, 212, 212AL, 220, 220AL (manufactured by Daicel Co.), and the like.
Examples of other polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4~cyclohexanedimethanol, ethylene oxide and/or propylene oxide-addition diols to bisphenol-A, ethylene oxide and/or propylene oxide-addition diols to bisphenol-F, ethylene oxide and/or propylene oxide-addition diols to hydrogenated bisphenol-Ar ethylene oxide and/or propylene oxide-addition diols to hydrogenated bisphenol-F, dimethylol compounds of dicyclopentadiene, tricyclodecanedimethanol, poly ~-methyl-d-valerolactone polyol with a terminal hydroxy group, polybutadiene with a terminal hydroxy group, hydrogenated polybutadiene with a terminal hydroxy group, castor oil-modified polyols, polydimethylsiloxane with a diol terminal group, polydimethylsiloxane carbitol-modified polyols, and the like.
~he number average molecular weight of these polyols is usually 200 to 10,000, and preferably 500 to 8,000.
Given as examples of polyisocy~nate compound (B) which can be used in the present invQn~ion are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, l,4-xylylene diisocyanate, 1,5-naphthalene diis~cyanate, m-phenylene diisocyanate, p-phenylene diis~cyanate, 3,3'-dimethyl-4,4'-diphenylmethane dtisocyanate, 4,4'-diphenylme~hane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene 3Q diisocyanate, l,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-tximethylhexamethylene diisocyanate, bis(2~
isocyanateethyl)fumarate, 6-isopropyl-i,3-phenyl diisocyanate, 2,2-bis(4'-isocyanic acid)propane, lysine diisocyanate, and the like. Of these particularly preferable
18) exhibit low moisture and water absorption; and - 19) exhibit superior light resistance.
To meet these requiremen~s various liquid coating ; materials of the radiation curable type have been de~eloped. :~
. .
W093/212~ 2 1 ~ ~ 'I 2 1 PCT/US93/02037 They are compositions containing urethane acrylate using, for example, tetrahydrofuranethylene oxide ring opening copolymers (Japanese patent Laid-open (ko-kai) No.
86450/1986), tetrahydrofuranpropylene oxide ring opening copolymer (Japanese Patent Laid-open (ko-kai) No.
181170/1985), or tetrahydrofuranalkyltetrahydrOfuran copol~mers (Japanese ~atent Laid-open (ko-kai) No.
115964/1989).
Compositions in which these polyether copolymers are used have drawbacks still to be solved. That is, urethane acrylates using these polyether copolymers are insufficient in one or more of the characteristics, including resistance to ultraviolet light, heat resistance, light resistance (resistance against changing its color into yellow under light radiation~, heat resistance (resistance against changing its color into yellow when heated), and flexibility.
Accordingly, an ob~ect of the present invention is to provide, with due considexation to the drawbacks of such conventional compositions, a ~iquid curable resin composition ideal as a covering material for optical fiber, which has a low viscosity at room t~mperature and exhi~its good processability when used to coYer optical fibers, has good optical curing characteristics r can accommodate high speed optical fiber production, and in the cured state shows excellent flexibility, good resistance to heat~ ultraviolet light, and oil, and exhibits suitable adherence to optical fiber.
This object is achieved in the presen~ inven~_on by the ! provision of a liquid curable resin composition comprising a urethane (meth)acrylate obtained by the reaction of:
(A) a polyether polyol compound containing, as a structural units, ~roups represented by the following formulae (1), ~2), and (3), (1) -CH2CH20-WO93/212~ 2 1 1 ~ ~ 2 1 PCT/US93/02037 (2) -CH2CH(R)O-, and (3) one or more groups selected from groups (a), (b), and (c) below, -CH2CH2CI 12CH20- (a) R
C--~ (b) ~
Rl :
,.
{~1~~ (c) wherein R represents an alkyl group containing two or more carbon atoms, and R1 and R2 are independently se~ected $rom a hydrogen atom or ~ methyl group; :~
(B) a polyisocyanate compound; and (C3 a ~meth~acrylate compound having a hydroxy group.
The liquid cur2ble resin compQsition of the present invention has an extxemely low Young's modulus at roo~ tempexature, shows a suitable adher.ing strength to glass fiber, has super~or durability, exhibits high speed curing performance, and is thus suitable as a coating material for optical fiber.
~m~
A polyether polyol compound (here~nafter referred to as polyol compound ~A)) used in the present invention must contain structural uni~s of th~ above formulae (1), (2), and t3). There are ~o limitations as to the manner in which WO~3/212~ ~ 2 1 PCT/US93/02037 these structural units are polymerized. They may be polymerized by random, block, or graft polymerization.
Such a polyol compound (A) can be prepared by the ring-opening polymerization of ethylene oxide, l,2-alkylene oxides with 4 or more carbon atoms, e.g, 1,2-butylene oxide, l,2-hexene oxide, or the iike, and one or more compounds selected ~;
from polytetramethylene glycol, bisphenol A, and bisphenol F, `~
by a known method.
The proportion of structural unit (1) contained in polyol compound (A) is 5 to 50% by weight, and preferably 10 to 45%. If the amount of the structural unit ~1) is less than 5%, improvement in the oil resistance of the composition after curing is insufficient; if greater than 50%, water resistance and flexibility of the composition after curing tend to be.lowered. A preferable proportion of structural unit ~2) is 10 to 90%, with a particularly preferable range being 20 to 80%. The proportion of structural unit (3) is preferably 5 to 85%, and more preferably 10 to 70%.
The num`ber of carbon atoms of R in the unit of formula (2) conta~ned in ~meth)acrylate (A) is preferably 2 to 12, with a particularly preferable range being 2 to 4.
The number average molecular weight of the polyol compound (A) is usually in a range of 200 to 10,0~0, and preferably S00 to 8,000. If the number average molecular weight is less than 200~ the Young's modulus of the cured material at room temperature or at lower temperatures increases, and there is a tendency toward an increase in transmission losses from ~ide pressure when it is applied to optical fiber; if greater than 10, t the viscosity of the resulting composition tends to increase, resulting in impaired coa~ing performance of the composition when it is coated onto the optical fiber.
The polyol compound (A) may contain any structural units other than the above structural units of the formulae ~1) to ~3), to the extent that the effects of the present invention are not affected, so long as polyol compound (A) contains all .
WO93J21248 2 1 1 ~ '1 2 I PCT/US93/02037 ` 5 of these 3 structural units. Examples of such other structural units include -CH2CH2CH20-, -CH2CH(CH3)O-, and the :;
like.
In addition, polyols which do not have the above S structural units (l), (2) and (33 can be used in combination.
Examples of such polyols include polyether polyols, polyester polyols, polycarbonate polyols, polycapralactone polyols, and other polyols.
Examples of polyether polyols which do not ha~e the above structural units (l), (2~ and (3~ include, for example, polyethylene glycolO l,2-polypropylene glycol, l,3- :
polypropylene glycol, l,2-polybutylene glycol, `
polyisobutylene glycol, propylene oxide-te~rahydrofuran copolymers, methyl tetrahydrofuran-tetrahydrofuran ..
copolymers, and the like.
Examples which can be given of polyester polyols include polyester polyols obtained by reacting a polyvalent alcohol .
such as ethylene glycol, polyethylene glycol, pxopylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, l,6-hexane diol, neopentyl glycol, l,4-cyclohexanedimethanol, 3-methyl-l,5-pentanediol, l,9-nonanediol, 2-methyl-lr8-octanediol, or the like with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, or the like; and commercial produ ts such as Kurapol P-2010, PMIPA, PR~-A, P~A-A2, PNA2000 (manufactured by Xuraray C5. ), and the like.
Examples which can be given of polycarbon~te polyols include 1,6-hexanepolycarbonate and produ ts available on the market, such as DN-980, DN-981, DN-982, DN-983 ~manufactured ~y Nihon Polyurethane Co., Ltd.~, PC-8000 (manufactured by PPG of the US), and the like.
Examples of polycaprolactone polyols include polycaprolactonediols obtained by reacting ~-caprolactone with a divalent diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, W093/21248 2 1 1 ~ 1 2 ~ PCT/US93/02037 tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl ~lycol, 1,4-butanediol, or the like, as well as PLACCEL-205, 205Ah, 212, 212AL, 220, 220AL (manufactured by Daicel Co.), and the like.
Examples of other polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4~cyclohexanedimethanol, ethylene oxide and/or propylene oxide-addition diols to bisphenol-A, ethylene oxide and/or propylene oxide-addition diols to bisphenol-F, ethylene oxide and/or propylene oxide-addition diols to hydrogenated bisphenol-Ar ethylene oxide and/or propylene oxide-addition diols to hydrogenated bisphenol-F, dimethylol compounds of dicyclopentadiene, tricyclodecanedimethanol, poly ~-methyl-d-valerolactone polyol with a terminal hydroxy group, polybutadiene with a terminal hydroxy group, hydrogenated polybutadiene with a terminal hydroxy group, castor oil-modified polyols, polydimethylsiloxane with a diol terminal group, polydimethylsiloxane carbitol-modified polyols, and the like.
~he number average molecular weight of these polyols is usually 200 to 10,000, and preferably 500 to 8,000.
Given as examples of polyisocy~nate compound (B) which can be used in the present invQn~ion are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, l,4-xylylene diisocyanate, 1,5-naphthalene diis~cyanate, m-phenylene diisocyanate, p-phenylene diis~cyanate, 3,3'-dimethyl-4,4'-diphenylmethane dtisocyanate, 4,4'-diphenylme~hane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene 3Q diisocyanate, l,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-tximethylhexamethylene diisocyanate, bis(2~
isocyanateethyl)fumarate, 6-isopropyl-i,3-phenyl diisocyanate, 2,2-bis(4'-isocyanic acid)propane, lysine diisocyanate, and the like. Of these particularly preferable
8 2 1 1 ~ 4 2 1 PCT/US93/02037 are 2,4-tolylene diisocyanate, isophorone diisocyanate, .-2,2,4-trimethylhexamethylene diisocyanate, and the like.
Examples of (meth)acrylates with a hydroxyl group, component (C~ used in the present invention, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, l,4-butanediol mono~meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, -~
4-hydroxycyclohexyl(meth)acrylate, 1,6-hexanediol monotmeth)acrylate, neopentylglycol mono(meth)acrylate, tr~methylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates :
represented by the following formula (4), CH2--C(Rl)-COOCH2CH2-(0C=OCH2CH2CH2CH2CH2)n~OH (4) wherein Rl is a hydrogen atom or a methyl group and n is an integer from 1 to 15, preferably 1 to 4.
In addition, compounds obtained by an addition reaction between compounds containing a glycidyl group, such as, a}kyl glycldyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, or the like, and ~meth)acrylic acid can be used. Among these, particularly desirable are 2-hydroxyethyl ~meth)acrylate, 2-hydroxypropyl lmeth)acrylate, and the like.
The urethane (meth)acrylates used in the present in~ention can be prepared by the reaction of the abovement~oned polyol compound (A), polyisocyanate compound ~B), and ~meth)acrylate compound containing a hydroxy group ~C~; specifically, by reacting the isocyanate group in ~he polyisocyanate compound ~B) with the hydroxy group of polyol compound (A) and the hydroxy group of the (meth)acrylate compound ~C). The reaction can be carried out, for example, by the following manners.
(1) All of polyol compound (A), polyisocyanate compound ~B), and (meth)acrylate compound containing a hydroxy group ~C) are charged in the reactor for the reaction.
;
wo 93,2l248 2 1 1 ~ ~ ~ I PCT/US93/02037 (2) Polyol compound (A) and polyisocyanate compound ~B) are first reacted, and then the resulting reaction product is reacted with (meth)acrylate compound containing a hydroxy group ~C).
(3) Polyisocyanate c~mpound (B) and (meth)acrylate compound containing a hydroxy grou~ (C) are first reacted, and then the resulting reaction product is reacted with polyol compound (A).
(4) Polyisocyanate compound ~B) and (meth)acrylate compound containing a hydroxy group (C) are first reacted, then wi~h polyol compound ~A), and the resulting reaction product is finally reacted again w~th (meth)acxylate con~pound containing a hydroxy group (C).
The propsrtions of polyol compound ~A), p~lyisocyanate 15 compound (B), and (meth)acrylate compound containing a -hydroxy group (C) used for the reaction are such that l.l to .-3 equivalents of isocyanate groups in polyiso~yanate cQmpound (B) and O.l to l.5 equi~alents of hydroxy groups in (meth)acrylate compound containing a hydroxy group (C) are u8ed for l equivalent of the hydroxy group contained in polyol compound ~A).
In the reaction of these compounds, O.Ol to l.0 parts by weight of a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-25 butyltindilaurate, triethylamine, triethylenediamine, 2-methyltriethylenediamine, or the like, is used usually to lO0 parts by weight of the total reactants used in these reactions. The reaction temperature is normall~ lO ~o 90C, and preferably 30 to 8QC.
The amount of urethane (meth)acrylate thus obtained used in the composition of the present invention is preferably 5 to 93%, but 20 to 87% is considered ideal in maintaining the coating characteristics when covering the optical fibex wire~
and in maintaining the flexibility and long term reliability of the coated material after curing.
W O 93/21248 2 1 1 ~ 4 2 1 PC~r/US93/~2037 The molecular weight of urethane (meth)acrylate isusually 700 to 20,000, and preferably 1,000 to 10,000 (number average molecular weight). `
To the liquid curable composition of the present invention, radiation curable compounds other than urethane (meth)acrylates, reaction diluents, and other additives may optionally be incorporated to the extent that the effects of the present inventlon are not adversely affected. ~;~
Other radiation curable compounds than the urethane (meth)acrylates of the present ~nvention such as other urethane (meth)acrylates, polyester (meth)acrylates, epoxy ~meth)acrylates, polyamide ~meth)acrylates, polysiloxanes with~~meth)acryloyloxy group, and the like can be incorporated in the compos~tions of the present in~ention.
They may be. added either singly or two or more may be added together.
Examples of reaction diluents include monofunctional and polyfunctional compounds. Specific examples of monofunctional compounds which can be given include 2- ;~
20 hydroxyethyl tmeth)acrylate, 2-hydroxypropyl ~meth)acrylate, ;.
2-hydroxybutyl lmeth)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)acrylatel isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl ~meth)acrylate, octyl ~meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth~acrylate, nonyl (meth)acrylate, decyl (meth~acrylate, isodecyl (meth)acrylate, undecyl ~meth)acrylate, dodecyl ~meth)acrylate, lauryl (meth~acrylate, octadecyl tmeth)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, polypxopylene glycol mono~meth)acrylate, methoxyethylene glycol (meth)acrylate, WO93/21248 2 1 1 ~ ~ 2 i PCT/US93/02037 ethoxyethoxyethyl (meth)acrylate, methoxypolyethylene glycol ~meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadiene (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth?acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, d~acetone ~meth)acrylamide, isobutoxymethyl (meth ) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl ~meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7~dimethyloctyl (meth~acrylate, N,N-diethyl (meth)acrylamide, N,N'-dimethylaminopropyl (meth)acrylamide, (met~acryloylmorphoxine; vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ethex, 2-ethylhexyl vinyl et~er, and the like; maleic acid esters,fumaric acid esters, and compounds represented by the following formulas ~5) to (7~.
CH2=C(R3)-C-o-(R40)m~
O (5) wherein R3 indicates a hydrogen atom or a methyl group; R4 is an alkylene group with 2 to 6, preferably 2 to 41 carbon atoms; R5 is z hydrogen atom or an alkyl group with 1 to 12, preferably 1 to 9, carbon atoms; and m is an integer from O
25 to 12, preferably from 1 to 8.
I' - I
CH2=C(R3)-C-(o-R6-c)poCH2 ~ ) (6) O O
W093/2124B PCT/I~S93/02037 Il 211~21 wherein R3 is the same as above, and R6 is an alkylene group with 2 to 8, preferably 2 to 5, carbon atoms, and p is an integer from 1 to 8, preferably from 1 to 4.
~7 CH3 o-CH ~7 CH2=CH(R3~l C-(ORj-C3p-o-cH2-cicH ," C~ ~, CH3 ~ \ (7) R R ~`
wherein R3, R6, and p are the same as above, R7 is a hydrogen atom or a methyl gxoup.
Examples of commercial products which can be used are ARONIX M111, M113, M114, M117 (manufactured by Toa Go~ei Chemical Co.), KAYARAD TCllOS, R629, R~44 ~manufactured by Nippon Rayaku Co.) and OISCO~T 3700 (manufactured by Osaka -:~
Organic Chemicals Co.) and the like. :
, Examples of polyfunctional compounds include 15 trimethylolpropane tri~meth)acrylate, pentaerythritol ~:
tri(meth)acrylate, ethylene glycol di(meth)~crylate, tetraethylene glycol di(me~h)acxylate, polyethylene glycol di(meth)acxylate, 1,4-butanediol di~meth?acrylate, 1,6- -hexanediol di(me~h)acrylate, neopentyl ~lycol di(meth)acrylate, trimethylolpropanetrioxyethyl ~meth)acryla~e, tris(2-hydroxye~hyl)isocyanurate tri~meth)acrylate, tris~2 hydroxyethyl)isocyanurate di~meth)acrylate, ~ricyclodecanedimethanol di~me~h)acrylate, epoxy (meth~acrylates ob~ained by the addition of a ~meth)acrylate to bisphenol A diglycidyl ether, triethylene glycol divinyl ether, epoxy compounds, cyclic epoxy compounds, vinyl sulfides, vinyl urethanes, vinyl ureas, and the like.
W093/21~ 2 1 1 8 ~ 2 ~ PCT/US93/0~037 Examples of commercial products which can be used are COPIMA- W, SAl002, SA2007 ~manufactured by Mitsubishi Petrochemical Co.), BISCOAT 700 ~manufactured by Osaka Organic Chemical Co.), R604, DPCA-20, DPCA-30, DPC.A-60, DPCA-120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku Co.), ARONIX M210, M215, M315, M325, (manufactured by Toa Gosei Chemical Co.), and the like.
An appropriate reaction diluent can be used for a composition depending on the characteristics to be demanded of the composition.
When flexibility, especially flexibility at low temperatures, is required, ~meth)acrylate compounds, of which the homopolymer have a glass transition temperature of -10C
or below, are preferably used among the above-mentioned reaction diluents.
Given as-preferable examples of such (meth)acrylate compounds are commercial products such as A~ONIX ~102, ~111, M1~3, M114, M117 (manufactured by Toa Gosei Chemical Co.), RRYARAD TCllOS, R629, R644 (manufactured by Nippon Rayaku Co.)~ and the like.
When good adhesion and ~uring characteristics are required, N-~inyl pyrrolidone and N-~inyl caprolactam among the above-mentioned reaction ~iluents are preferably used.
These reaction diluents can be incorporated in the 25 composition of the present in~Jention preferably in an amount of 5 to 60%, and particularly preferably lû to 40%. The composition of.the pre~ent invention is cured by heat and/or :~
radiation Radiation in this case means the application of infrared, visible light, and ultraviolet rays, as well as ionized rays such as X-rays, electron rays, a rays, ~-rays, T-rays, and the l~ke.
When the composition of the present invention is cured by heat, a radical polymerization initi~tor, for example peroxides, azo compounds or the like, is generally used.
Specific examples are benzoyl peroxide, t-butyloxybenzoate, ~zobis~sobutyronitrile, and the like.
WO93/21248 2 1 1 ~ '1 2 1 PCr/US93/02037 ! 13 !
When the compositi~n of the present invention is cured by light, a photopolymerization initiator, and, as required, a photosensitizin~ agent are used. Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro-benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diamino-benzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethylketal, 1-~4-isopropyl-phenol)-2-hydroxy-2-methylpropane-1-on, 2-hydroxy-2-methyl-1-phenylpropane-l-on, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-l4-(methylthio)phenyll-2-morpholinopropane-1-on, 2,4,6- `~
trimethylbepzoyldiphenylphosphine oxide, and commercial products such as Irugacure 184, 651, 500, 907, 369, CG24-61 ~all manufactured by Ciba Geigy), Lucirine LR8728 ~manufactured by OASF), Darocure 1116, 1173 (manufactured by Merck), Ubecryl-P36 (manufactured by U~0 Co.), and the like.
Exam~les of photosensitization agents are triethylamine, diethylamin~, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminomethyl benzoatet 4-dimethylaminoethyl benzoate, 4 dimethylaminoisoamyl benzoate, and commercial products such as Ubecryl-P102, 103, 104, 105 manufactured by the UCB Co., and the like. These polymerization initiators and photosensitization agents can be added individually or in mixture~ of two or more. In the ca-~e where the composition of the present invention is cured by both heat and ultra~iolet lightr the above-mentioned radical polymerization initiators can be used in combination.
; The amount of polymer~zation initiator used is preferably 0.1 to 10% of the composition.
In addition, other additives may optionally be added to the composition of the present invention. Such additives include epoxy resins, polyamides, polyamidoim~des, polyurethanes~ polybutadienes, chloroprene, polyethers, .
W093/2t2~ 2 ~ 1 8 ~ 2 1 PCT/US93/02037 polyesters, pentadiene derivatives, styrene/~utadiene/styrene block copolymers, styrene/ethylene/butene/styrene block copolymers, styrene/isoprene/styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine 5 containing oligomers, silicone-type oligomers, polysulfide .
type oligomers, and the like. .
Other types of additives which can be used as required in addition to those listed above $nclude antioxidants, :
coloring agents, ultraviolet absorbers, photostabilizers, 10 silane coupling agents, heat polymerization inhibitors, -leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging inhibitors, wetting `
agents, coating surface improvers, and the like. Commerc1al .~-antioxidants which can be used are Irganox l0l0, 1035, 1076, ~:
15 I222 ~manufactured by Ciba Geigy), and the like. Given as -~
examples of commercial absorbers are Tinuvin P234, 320, 326, 327, 328, 213 (manufactured by Ciba Geigy), Sumisorb ll0, .
130, 200 ~Sumitomo Chemical Co.), and the like. Commercial photo~tab~lizers which can be used include Tinuvin 292, 144, -`
622LD::(manufactured by Ciba Geigy), Sanol LS7 70 - ~(manufactured by Sankyo Chemical Co.), and the like.
Examples of silane coupling agents which can be given are t- ~^
aminopropyltriethoxy silane, t-mercaptopropyltrimethoxy silane, t-methacryloxypropyltrimethoxy silane, and commercial products such as SH6062, 6030 (manufactured by Toray Silicone :~
Co.~, XBE903/ 603, 403 (manufactured by Shin-Etsu Chemical Co.), and the like. :
The liquid curable resi~ composition of the present invention can be manufactured by mixing the abo~e components using commonly known methods.
The viscosity of the liquid curable resin composition of the present invention obtained in this manner is usually 200 to 20,000 cp at 25C, and preferably 2,000 to l0,000 cp at 25C.
: 35 When the composition of the present invention is used as ;~
:~: a~primary coatlng material for optical fiber, the Young's WO93/2124~ 2 1 18 1 21 Pcr/vss3/o2o37 modulus after curing is 0.05 to 0.5 kg/mm2, and particularly preferable is C.06 to 0.13 kg/mm2. The Young's modulus of the cured material at -40 to 60C i5 usually 0.01 to 10 kg/mm2.
:
EXAMPLES
The present invention will now be explained with reference to the following examples, which ar~ in no way limiting of the scope of the invention. In the examples below "parts" means "parts by weight".
Example 1 Preparation of urethane acrylate [A-l~
Into a reaction ve~sel equipped with a stirrer, 170.0 gm of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 59.2 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20~C. After the addition, the mixture was stirxed for 1 hour while maintaining the temperature at 10 to 20C, followed by the addition of 1,020.8 gm of copolymer diol of ethylene oxide, 1,2-butylene oxide, and polytetramethylene glycol (1:5:4 by weight) with a number average molecular weight of 2,000, while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to 60C to complete the reaction, thus obtain`ing urethane acrylate [A-1~ with a number a~erage molecular weight of 4,900.
Example 2 Preparation of urethane acrylate [A-2]
Into a reac~ion vessel equipped with a stirrer, 168.2 gm of isophorone diisocyanate, 1,044.6 gm of copolymer of ethylene oxide, 1,2-butylene oxide, and bisphenol A (1:7;1 hy weight) with a number a~erage molecular weight of 2,0521 and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a w0~3/212~ 2 1 1 ~ ll 2 1 PCT/VS93/02037 polymerization inhibitor, were charged. After cooling the mixture to 15C in an ice-cooled bath, 1 gm of dibutyltindilaurate was added to initiate the reaction at 30 to 40C for 2 hours. After the addition of 47.2 gm of hydroxyethyl acrylate, the mixture was stirred for 5 hours at a temperature of 50 to 60C to obtain urethane acrylate [A-2]
with a number average molecular weight of 6,140.
Example 3 Preparation of urethane acrylate [A-3]
Into a reaction vessel equipped with a stirrer, 100 gm ARONIX M113TM (manufactured by Toa Gosei Chemical Co.), 153.3 gm of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 1,056.6 gm of copolymer diol of ethylene oxide, 1,2-butylene oxide, and hydrogenated b~sphenol A (47.1 : 41.2 ~ 8 by weight) wi~h a number average molecular weight of 2,040 was added to the mixture while controlling the temperature at 40 to 50C.
Afte~ the addition, the mixture was reacted for 2 hours.
40.1 gm of hydroxyethyl acrylate was added and the stirring was continued for a further 5 hours at 50 to 60C to complete the reaction, thus obtaining urethane acrylate [A-3~ with a number average molecular weight of 7,240.
Example 4 Preparation of urethane acrylate lA-4]
Into a reaction vessel equipped with a stirrer, 331.1 gm of isophorone diisocyana~e, ~ gm of dibutyltindilaurate, and 0.3 gm of 2,6 di~text-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 173.0 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20C. After the addition, the mixture was ~tirred for 1 hour while maintaining the temperature at 10 to 20C, followed by the addition of 745.8 gm of polytetramethylene glycol with a number average WO93/21248 17 2 I 1~ 4 ~ ~ PCT/US93/02037 molecular weight of l,000, while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to ~0C to complete the reaction, thus obtaining urethane acrylate [A-4] with a number average molecular weight of l,680.
Example 5 Preparation of comparative urethane acrylate [B-l~
Into a reaction vessel equipped with a stirrer, 170.0 ~m of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methy~ phenol, as a polymerization inhibitor, were charged. Then, 59.2 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20C. After the addition, the mixture was stirred for l hour while maintaining the temperature at lO to 20C, followed by the addition of 1~0~0.8 gm of a copolymer diol of tetrahydrofuran and propylene oxide (3:7 by weight) with a number average molecular weight of 2,000 (PPTG lOOO,~manufactured by Hodogaya Chemical Co.) while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to 60C to complete the reaction, thus obtaining urethane acrylate ~B-l] with a number average molecular weight of 4,900.
Example 6 Preparation of comparative urethane acrylate ~B-2 ]
Into a reaction vessel equipped with a stirrer, 130 . 3 gm of 2, 4-tolylene diisocyanate, 1 gm of d~butyltindilaurate, and 9.3 gm of 2, 6-di-tert-butyl-4 methyl phenol, as a polymerization inhibltor~ were charged. To the mixture was added 1070.0 gm of poly~etramethylene glycol with a number average molecular weight of 2,000 (PPTG 2000, manuf~ctured by Hodogaya Chemical Co.) was added while controlling the temperature at 40 to 50C, followed by the reaction for 2 hours. Then, 49.6 gm of hydroxyethyl acrylate was added and W093/21~ 1 8 ~ 2 ~ PCT/US93/02037 the reaction was continued 5 hours at a temperature of 50 to 60C while stirring, thus obtaining urethane acrylate [B-2]
with a number average molecular weight of 5,840.
Example 7 Into a reaction vessel equipped with a stirrer, 55 parts of urethane acrylate [A-l], 30 parts of ARONIX Ml13, as a reaction diluent, 7 parts of Kayarad TCllOS ~a product of Nippon Kayaku Co.), 5 parts of N-vinyl pyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 0.3 part of Irganox lO35 ~manufactured by Ciba Geigy), O.l part of Sumisorb llO (manufactured by Sumitomo Chemical Co.), as a absorber, O.l p~rt of diethylamine, as a photosensi~izing agent, and l part of silane coupling agent (SH 6062, manufactured by Toray Silicone Co.) were charged and mixed with stirring at 50~ to 50C to obtain a transparent liquid composition with a viscosity of 3,700 cp at 25~C.
Example 8 ~Into a reaction vessel equipped with a stirrer, 55 parts of urethane acrylate [A-2], 25 parts of ARONIX Ml13, 12 parts of isobornyl acrylate, 5 part~ of N-~inyl caprolactam, l.5 parts of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), O.l part of diethylamine, and 1 part of SH 6062 were charged and mixed with stixring at 50 to 60C to obtain a transparent liquid composition with a ~iscosity of 3,000 cp at 25~C.
Example 9 Into a reaction ~essel equipped with a stirrer, 60.5 parts of urethane acrylate [A-3~, 37 parts of ARONIX M~13, 5 parts of N-vinyl pyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), O.l part of diethylamine, and l ~art of SH 6062 were charged and mixed with stirring at WO93/21248 ~ 2 1 PCT/US93/02~37 50 to 60C to obtain a transparent liquid composition with a viscosity of 5,000 cp at 25C.
Example 10 Into a reaction vessel equipped with a stirrer, 60 parts of urethane acrylate [A-4], 20 parts of tricyclodecanedimethanol diacrylate, 10 parts of isobornyl acrylate, 10 parts of N-vinyl caprolactam, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 0.3 part of Irganox 1035 (manufactured by Ciba Geigy) were charged and mixed with stirring at 50 to 60C to obtain a transparent liquid composition with a viscosity of 2,000 cp at 25C:.
~ . .
Comparative Example 1 A composition was prepared in the same manner as in Example 7, except that 55 parts of the urethane acrylate ~B-1~ was u~ed instead of the urethane acrylate [A-l ] ~ A
transparent liquid composition with a ~iscosity of 3,000 cp at 25C was obtained.
Comparative Example 2 A composition was prepared in ~he same manner as in ~xample 8, except that 30 parts of the urethane acrylate ~B-2] was used instead of the urethane acrylate [A-2). A
transparent liquid composition with a viscosity of 11 r 00O cp a~ 25C was obtained.
Test Examples 1. Film Tests Test leaves were prepared from compositions obtained in the above Examples and Comparative Examples and served to the evaluations according to the following met~ods.
~1) Preparation of test leaves The liquid compositions were applied to glass plates using a 150 applicator to obtain cured films by irradiation WO93/21248 2 ~ 2 1 PCT/VS93/02037 with ultraviolet rays at 25 mJ/cm2 or 500 mJ/cm2. Next, the cured films were peeled from the glass plates and tempered for 24 hours at a temperature of 23C and 50% RH, to obtain the test leaves.
(2) Measurement of Young's modulus (conforming to JIS K7127 Standard) The Young's modulus of each test leaf was measured in a tension tester at 23C or -40C at a drawing rate of l mm/min and a bench line interval of 25 mm.
(3) Gel Proportion The initial weight (Wo) of the cured film was measured, then the film was extracted for 12 hours in a Soxhlet extraction flask using methyl ethyl ketone as a solvent.
After extraction, the film was dried in a vacuum drier at 50C for 12 hours, then after standing for one hour at room temperature the final weight (WI~ was measured. The gel proportion was calculated using the following formula.
Gel proportion = Wl/Wo x lO0 (%) (4) Weight Change -The weight of the cured films obtained by irradiation with ultraviolet light at 500 mJ/cm2 was determined ~initial weight: Wo). After the heat resistant and light resistant tests, the films were left for l hour at room temperature to determine ~ts weight (dry weight: Wl~. The weight change was calculated according to the following formula.
Weight Change = (Wl-Wo)/Wo x lO0 (%) (5~ Heat Resistance Te~t The cured films obtained by irradiation with ultraviolet light at 500 mJ/cm2 were held in a thermostat at 120~C for 15 days. The Young's modulus and gel proportion of the films were then measured. The results are shown in Table l.
(6) Light Resistance Test ~ ight resistance tests were performed on the films cured at 500 mJ/cm2 using a Q W weathering acceleration machine (manufactured by Q-panel Co.). The lamp used was a UV0-3I3.
After 200 hours in the machine, the outer appearance of the WO93/21~48 2 1 1 ~ PCT/US93/02037 film was examined and the Young's modulus and gel proportion were measured. The results are ~hown in Table l.
___________________________________________________________ Comparati~e Examples __ExamDles Evaluation Item l 2 3 l 2 _________________________ ___ _________________________ ___ t~3C]
Young's modulus (kg/mm2) 25 m/cm2 0.06 0.06 0.06 0.05 0.11 500 m/cm2 0.07 0.06 0.06 0.08 0.18 Gel proportion (%) 25 m/cm2 88 90 88 82 85 S00 m/cm2 89 91 89 88 90 ___________________________________________________________ a~e~ eat R~esl ~tant Te~t 500 r~ 2 Young's mo~ulus 25 (kg/mm2) 0.05 0.06 0.05 0~05 0.07 -Cel Proportion ~)86 - 87 86 82 6S
Color change into yellow Non Non Non Non Changed _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ = _ _ _ _ _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 500 m/cm2 Gel Proportion (%)84 83 83 50 83 We~ght 5hange -0.3 -O.l -0.2 -lO -l.5 Color change into yellow Non Non Non Non Changed ____________ ______________________________________________ WO~3/~ 2 1 1 S ~ 2 1 PCT/U593/~2U37 2. Drawing Tests Using an optical fiber drawing machine, two layers of a composition, according to the combination in Table 2, was applied to optical fibers and then cured by irradiation with ultraviolet rays to obtain coated optical fibers. The mean diameter of the optical fiber core was 125 ~m, that of the fiber covered with the primary layer 200 ~m, and that of the fiber covered with the secondary layer 250 ~m.
The covered optical fibers were prepared at drawing speeds of 180t 360, and 720 mimin, and subjected to the tests `
according to the following methods. The results are shown ~n Table 2..
.. ...
(1) Gel Proportion The initial weight ~Wo) of the coated fibers, cut to a length of 4 cm, was determined (initial weight: Wo), and the f~bers were extracted for 12 hours in a Soxhlet extract;ion flask using methyl ethyl ketone as a solvent.
After extraction, the fibers were dried in a vacuum drier at 50C for 12 hours, then after-standing for one hour at r~om temperature the final weight ~dry weight: Wl) was determined.
Thereafter, the optical fibers were calcined for 30 :
minutes in an electric ~urnace at ~00C to remove the coated layers and to collect the optical fiber material, of which the we~ght ~Wf) was determined.
The gel proportion was calculated using the following formula.
Gel proportion = tWl-Wf)/(Wo-wf) x 100 (%~
3. En~ironment Test (1) Light Resistance ! Coated optical fibers drawn at 360 m/min were exposed to fluorescent light (2,000 lux) for 30 days t~ evaluate their external appearance, and to determine the change in weight and the a unt of hydrogen gas generated.
, WO93/21248 2 ~ 1 ~ 'I 2 L
~ PCT/US93/02037 ~3 Method of Evaluation ~a) External Appearance Coated layers, fibers~ and their interface were mlcroscopically observed to investigate the presence or absence of vacant spaces, peeled portions, liquid drops, and foreign materials.
~b) Change in Weight The change in weight by the exposure to fluorescent light was determined according to the following formula.
Change in Weight = (Wb-Wa)/(Wa-Wf) x 100 (%) wherein Wa is the weight of the coated fiber before exposure to fluorescent light, Wb after the exposure, and WE is the weight of the optical fiber obtained after removal of covered material by calcination in the an electric furnace at 700C
for 30 min~tes.
~c) Generation of Hydrogen Gas The amounts of hydrogen gas before and after the light resistant test were determined by the following method. The coated optical fiber was accurately weighed, placed in a vial wit~ a known weight, and heated at 100C for 4 hours. The air in the head space of the vial was collected by means of a gas ~ight syringe and the air was introduced to a gas chromatography to qua~titatively analyze the amount of hydrogen gas. An absolu~e calibration curve was used for the analysis. The resul~s are shown in Table 2.
WO 93/2124~ L'l 21 P(:~US93/02037 Te~t Example No. 1 2 3 4 5 Cc~mp. Comp. ':
Soft material for Example 1 Example 2 ~xample 3 ~xample 1 Example 2 primary layer Hard material for Example 4 Example 4 Example 4 Example 4 Example 4 0 ~econdary layer Re~ult~ of Evaluation 1. Curing Rate Gel Proportion (%~
at Dra~ing Rate (m/min ) 180 90 9~ 90 85 90 2. Environm~ntal Te~t ~Light Re~istance) EXternal Appear~nce No change No change No change No change Ch~nged ~eight Chantge ~ 0.5 -0.2 -0.3 -2.5 -0.3 Kydrogen Ga~
Generation ~l/gm) Initi~l 0.2 0.2 0.2 0.2 8.0 After Te~t 5 6 4 300 20 The liquld curable resin composition of the present invention exhibits a high curing rater its cured materials has ~ low Young's modulus and a high gel ratio, provides superior heat resistance and light resistance, and generates 35 Qnly a small amount of hydrogen gas. It is thus particularl~
suitable as a material for optical fiber coating. Oec~use of its superior heat resistance, curability, and adherence f the composition is not only applicable to an optical fiber coating, but also useful as a protective coating material for ~arious types of substrates such as metals, plastics, wood, WO93/21248 ~ 2 1 ~CTII~S93/02037 porcelain, glass, and the like, and as an optical molding matérial, three~dimensional molding material~ printing plate material, and the like.
Examples of (meth)acrylates with a hydroxyl group, component (C~ used in the present invention, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, l,4-butanediol mono~meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, -~
4-hydroxycyclohexyl(meth)acrylate, 1,6-hexanediol monotmeth)acrylate, neopentylglycol mono(meth)acrylate, tr~methylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates :
represented by the following formula (4), CH2--C(Rl)-COOCH2CH2-(0C=OCH2CH2CH2CH2CH2)n~OH (4) wherein Rl is a hydrogen atom or a methyl group and n is an integer from 1 to 15, preferably 1 to 4.
In addition, compounds obtained by an addition reaction between compounds containing a glycidyl group, such as, a}kyl glycldyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, or the like, and ~meth)acrylic acid can be used. Among these, particularly desirable are 2-hydroxyethyl ~meth)acrylate, 2-hydroxypropyl lmeth)acrylate, and the like.
The urethane (meth)acrylates used in the present in~ention can be prepared by the reaction of the abovement~oned polyol compound (A), polyisocyanate compound ~B), and ~meth)acrylate compound containing a hydroxy group ~C~; specifically, by reacting the isocyanate group in ~he polyisocyanate compound ~B) with the hydroxy group of polyol compound (A) and the hydroxy group of the (meth)acrylate compound ~C). The reaction can be carried out, for example, by the following manners.
(1) All of polyol compound (A), polyisocyanate compound ~B), and (meth)acrylate compound containing a hydroxy group ~C) are charged in the reactor for the reaction.
;
wo 93,2l248 2 1 1 ~ ~ ~ I PCT/US93/02037 (2) Polyol compound (A) and polyisocyanate compound ~B) are first reacted, and then the resulting reaction product is reacted with (meth)acrylate compound containing a hydroxy group ~C).
(3) Polyisocyanate c~mpound (B) and (meth)acrylate compound containing a hydroxy grou~ (C) are first reacted, and then the resulting reaction product is reacted with polyol compound (A).
(4) Polyisocyanate compound ~B) and (meth)acrylate compound containing a hydroxy group (C) are first reacted, then wi~h polyol compound ~A), and the resulting reaction product is finally reacted again w~th (meth)acxylate con~pound containing a hydroxy group (C).
The propsrtions of polyol compound ~A), p~lyisocyanate 15 compound (B), and (meth)acrylate compound containing a -hydroxy group (C) used for the reaction are such that l.l to .-3 equivalents of isocyanate groups in polyiso~yanate cQmpound (B) and O.l to l.5 equi~alents of hydroxy groups in (meth)acrylate compound containing a hydroxy group (C) are u8ed for l equivalent of the hydroxy group contained in polyol compound ~A).
In the reaction of these compounds, O.Ol to l.0 parts by weight of a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-25 butyltindilaurate, triethylamine, triethylenediamine, 2-methyltriethylenediamine, or the like, is used usually to lO0 parts by weight of the total reactants used in these reactions. The reaction temperature is normall~ lO ~o 90C, and preferably 30 to 8QC.
The amount of urethane (meth)acrylate thus obtained used in the composition of the present invention is preferably 5 to 93%, but 20 to 87% is considered ideal in maintaining the coating characteristics when covering the optical fibex wire~
and in maintaining the flexibility and long term reliability of the coated material after curing.
W O 93/21248 2 1 1 ~ 4 2 1 PC~r/US93/~2037 The molecular weight of urethane (meth)acrylate isusually 700 to 20,000, and preferably 1,000 to 10,000 (number average molecular weight). `
To the liquid curable composition of the present invention, radiation curable compounds other than urethane (meth)acrylates, reaction diluents, and other additives may optionally be incorporated to the extent that the effects of the present inventlon are not adversely affected. ~;~
Other radiation curable compounds than the urethane (meth)acrylates of the present ~nvention such as other urethane (meth)acrylates, polyester (meth)acrylates, epoxy ~meth)acrylates, polyamide ~meth)acrylates, polysiloxanes with~~meth)acryloyloxy group, and the like can be incorporated in the compos~tions of the present in~ention.
They may be. added either singly or two or more may be added together.
Examples of reaction diluents include monofunctional and polyfunctional compounds. Specific examples of monofunctional compounds which can be given include 2- ;~
20 hydroxyethyl tmeth)acrylate, 2-hydroxypropyl ~meth)acrylate, ;.
2-hydroxybutyl lmeth)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)acrylatel isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl ~meth)acrylate, octyl ~meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth~acrylate, nonyl (meth)acrylate, decyl (meth~acrylate, isodecyl (meth)acrylate, undecyl ~meth)acrylate, dodecyl ~meth)acrylate, lauryl (meth~acrylate, octadecyl tmeth)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, polypxopylene glycol mono~meth)acrylate, methoxyethylene glycol (meth)acrylate, WO93/21248 2 1 1 ~ ~ 2 i PCT/US93/02037 ethoxyethoxyethyl (meth)acrylate, methoxypolyethylene glycol ~meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadiene (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth?acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, d~acetone ~meth)acrylamide, isobutoxymethyl (meth ) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl ~meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7~dimethyloctyl (meth~acrylate, N,N-diethyl (meth)acrylamide, N,N'-dimethylaminopropyl (meth)acrylamide, (met~acryloylmorphoxine; vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ethex, 2-ethylhexyl vinyl et~er, and the like; maleic acid esters,fumaric acid esters, and compounds represented by the following formulas ~5) to (7~.
CH2=C(R3)-C-o-(R40)m~
O (5) wherein R3 indicates a hydrogen atom or a methyl group; R4 is an alkylene group with 2 to 6, preferably 2 to 41 carbon atoms; R5 is z hydrogen atom or an alkyl group with 1 to 12, preferably 1 to 9, carbon atoms; and m is an integer from O
25 to 12, preferably from 1 to 8.
I' - I
CH2=C(R3)-C-(o-R6-c)poCH2 ~ ) (6) O O
W093/2124B PCT/I~S93/02037 Il 211~21 wherein R3 is the same as above, and R6 is an alkylene group with 2 to 8, preferably 2 to 5, carbon atoms, and p is an integer from 1 to 8, preferably from 1 to 4.
~7 CH3 o-CH ~7 CH2=CH(R3~l C-(ORj-C3p-o-cH2-cicH ," C~ ~, CH3 ~ \ (7) R R ~`
wherein R3, R6, and p are the same as above, R7 is a hydrogen atom or a methyl gxoup.
Examples of commercial products which can be used are ARONIX M111, M113, M114, M117 (manufactured by Toa Go~ei Chemical Co.), KAYARAD TCllOS, R629, R~44 ~manufactured by Nippon Rayaku Co.) and OISCO~T 3700 (manufactured by Osaka -:~
Organic Chemicals Co.) and the like. :
, Examples of polyfunctional compounds include 15 trimethylolpropane tri~meth)acrylate, pentaerythritol ~:
tri(meth)acrylate, ethylene glycol di(meth)~crylate, tetraethylene glycol di(me~h)acxylate, polyethylene glycol di(meth)acxylate, 1,4-butanediol di~meth?acrylate, 1,6- -hexanediol di(me~h)acrylate, neopentyl ~lycol di(meth)acrylate, trimethylolpropanetrioxyethyl ~meth)acryla~e, tris(2-hydroxye~hyl)isocyanurate tri~meth)acrylate, tris~2 hydroxyethyl)isocyanurate di~meth)acrylate, ~ricyclodecanedimethanol di~me~h)acrylate, epoxy (meth~acrylates ob~ained by the addition of a ~meth)acrylate to bisphenol A diglycidyl ether, triethylene glycol divinyl ether, epoxy compounds, cyclic epoxy compounds, vinyl sulfides, vinyl urethanes, vinyl ureas, and the like.
W093/21~ 2 1 1 8 ~ 2 ~ PCT/US93/0~037 Examples of commercial products which can be used are COPIMA- W, SAl002, SA2007 ~manufactured by Mitsubishi Petrochemical Co.), BISCOAT 700 ~manufactured by Osaka Organic Chemical Co.), R604, DPCA-20, DPCA-30, DPC.A-60, DPCA-120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku Co.), ARONIX M210, M215, M315, M325, (manufactured by Toa Gosei Chemical Co.), and the like.
An appropriate reaction diluent can be used for a composition depending on the characteristics to be demanded of the composition.
When flexibility, especially flexibility at low temperatures, is required, ~meth)acrylate compounds, of which the homopolymer have a glass transition temperature of -10C
or below, are preferably used among the above-mentioned reaction diluents.
Given as-preferable examples of such (meth)acrylate compounds are commercial products such as A~ONIX ~102, ~111, M1~3, M114, M117 (manufactured by Toa Gosei Chemical Co.), RRYARAD TCllOS, R629, R644 (manufactured by Nippon Rayaku Co.)~ and the like.
When good adhesion and ~uring characteristics are required, N-~inyl pyrrolidone and N-~inyl caprolactam among the above-mentioned reaction ~iluents are preferably used.
These reaction diluents can be incorporated in the 25 composition of the present in~Jention preferably in an amount of 5 to 60%, and particularly preferably lû to 40%. The composition of.the pre~ent invention is cured by heat and/or :~
radiation Radiation in this case means the application of infrared, visible light, and ultraviolet rays, as well as ionized rays such as X-rays, electron rays, a rays, ~-rays, T-rays, and the l~ke.
When the composition of the present invention is cured by heat, a radical polymerization initi~tor, for example peroxides, azo compounds or the like, is generally used.
Specific examples are benzoyl peroxide, t-butyloxybenzoate, ~zobis~sobutyronitrile, and the like.
WO93/21248 2 1 1 ~ '1 2 1 PCr/US93/02037 ! 13 !
When the compositi~n of the present invention is cured by light, a photopolymerization initiator, and, as required, a photosensitizin~ agent are used. Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro-benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diamino-benzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethylketal, 1-~4-isopropyl-phenol)-2-hydroxy-2-methylpropane-1-on, 2-hydroxy-2-methyl-1-phenylpropane-l-on, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-l4-(methylthio)phenyll-2-morpholinopropane-1-on, 2,4,6- `~
trimethylbepzoyldiphenylphosphine oxide, and commercial products such as Irugacure 184, 651, 500, 907, 369, CG24-61 ~all manufactured by Ciba Geigy), Lucirine LR8728 ~manufactured by OASF), Darocure 1116, 1173 (manufactured by Merck), Ubecryl-P36 (manufactured by U~0 Co.), and the like.
Exam~les of photosensitization agents are triethylamine, diethylamin~, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminomethyl benzoatet 4-dimethylaminoethyl benzoate, 4 dimethylaminoisoamyl benzoate, and commercial products such as Ubecryl-P102, 103, 104, 105 manufactured by the UCB Co., and the like. These polymerization initiators and photosensitization agents can be added individually or in mixture~ of two or more. In the ca-~e where the composition of the present invention is cured by both heat and ultra~iolet lightr the above-mentioned radical polymerization initiators can be used in combination.
; The amount of polymer~zation initiator used is preferably 0.1 to 10% of the composition.
In addition, other additives may optionally be added to the composition of the present invention. Such additives include epoxy resins, polyamides, polyamidoim~des, polyurethanes~ polybutadienes, chloroprene, polyethers, .
W093/2t2~ 2 ~ 1 8 ~ 2 1 PCT/US93/02037 polyesters, pentadiene derivatives, styrene/~utadiene/styrene block copolymers, styrene/ethylene/butene/styrene block copolymers, styrene/isoprene/styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine 5 containing oligomers, silicone-type oligomers, polysulfide .
type oligomers, and the like. .
Other types of additives which can be used as required in addition to those listed above $nclude antioxidants, :
coloring agents, ultraviolet absorbers, photostabilizers, 10 silane coupling agents, heat polymerization inhibitors, -leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging inhibitors, wetting `
agents, coating surface improvers, and the like. Commerc1al .~-antioxidants which can be used are Irganox l0l0, 1035, 1076, ~:
15 I222 ~manufactured by Ciba Geigy), and the like. Given as -~
examples of commercial absorbers are Tinuvin P234, 320, 326, 327, 328, 213 (manufactured by Ciba Geigy), Sumisorb ll0, .
130, 200 ~Sumitomo Chemical Co.), and the like. Commercial photo~tab~lizers which can be used include Tinuvin 292, 144, -`
622LD::(manufactured by Ciba Geigy), Sanol LS7 70 - ~(manufactured by Sankyo Chemical Co.), and the like.
Examples of silane coupling agents which can be given are t- ~^
aminopropyltriethoxy silane, t-mercaptopropyltrimethoxy silane, t-methacryloxypropyltrimethoxy silane, and commercial products such as SH6062, 6030 (manufactured by Toray Silicone :~
Co.~, XBE903/ 603, 403 (manufactured by Shin-Etsu Chemical Co.), and the like. :
The liquid curable resi~ composition of the present invention can be manufactured by mixing the abo~e components using commonly known methods.
The viscosity of the liquid curable resin composition of the present invention obtained in this manner is usually 200 to 20,000 cp at 25C, and preferably 2,000 to l0,000 cp at 25C.
: 35 When the composition of the present invention is used as ;~
:~: a~primary coatlng material for optical fiber, the Young's WO93/2124~ 2 1 18 1 21 Pcr/vss3/o2o37 modulus after curing is 0.05 to 0.5 kg/mm2, and particularly preferable is C.06 to 0.13 kg/mm2. The Young's modulus of the cured material at -40 to 60C i5 usually 0.01 to 10 kg/mm2.
:
EXAMPLES
The present invention will now be explained with reference to the following examples, which ar~ in no way limiting of the scope of the invention. In the examples below "parts" means "parts by weight".
Example 1 Preparation of urethane acrylate [A-l~
Into a reaction ve~sel equipped with a stirrer, 170.0 gm of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 59.2 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20~C. After the addition, the mixture was stirxed for 1 hour while maintaining the temperature at 10 to 20C, followed by the addition of 1,020.8 gm of copolymer diol of ethylene oxide, 1,2-butylene oxide, and polytetramethylene glycol (1:5:4 by weight) with a number average molecular weight of 2,000, while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to 60C to complete the reaction, thus obtain`ing urethane acrylate [A-1~ with a number a~erage molecular weight of 4,900.
Example 2 Preparation of urethane acrylate [A-2]
Into a reac~ion vessel equipped with a stirrer, 168.2 gm of isophorone diisocyanate, 1,044.6 gm of copolymer of ethylene oxide, 1,2-butylene oxide, and bisphenol A (1:7;1 hy weight) with a number a~erage molecular weight of 2,0521 and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a w0~3/212~ 2 1 1 ~ ll 2 1 PCT/VS93/02037 polymerization inhibitor, were charged. After cooling the mixture to 15C in an ice-cooled bath, 1 gm of dibutyltindilaurate was added to initiate the reaction at 30 to 40C for 2 hours. After the addition of 47.2 gm of hydroxyethyl acrylate, the mixture was stirred for 5 hours at a temperature of 50 to 60C to obtain urethane acrylate [A-2]
with a number average molecular weight of 6,140.
Example 3 Preparation of urethane acrylate [A-3]
Into a reaction vessel equipped with a stirrer, 100 gm ARONIX M113TM (manufactured by Toa Gosei Chemical Co.), 153.3 gm of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 1,056.6 gm of copolymer diol of ethylene oxide, 1,2-butylene oxide, and hydrogenated b~sphenol A (47.1 : 41.2 ~ 8 by weight) wi~h a number average molecular weight of 2,040 was added to the mixture while controlling the temperature at 40 to 50C.
Afte~ the addition, the mixture was reacted for 2 hours.
40.1 gm of hydroxyethyl acrylate was added and the stirring was continued for a further 5 hours at 50 to 60C to complete the reaction, thus obtaining urethane acrylate [A-3~ with a number average molecular weight of 7,240.
Example 4 Preparation of urethane acrylate lA-4]
Into a reaction vessel equipped with a stirrer, 331.1 gm of isophorone diisocyana~e, ~ gm of dibutyltindilaurate, and 0.3 gm of 2,6 di~text-butyl-4-methyl phenol, as a polymerization inhibitor, were charged. Then, 173.0 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20C. After the addition, the mixture was ~tirred for 1 hour while maintaining the temperature at 10 to 20C, followed by the addition of 745.8 gm of polytetramethylene glycol with a number average WO93/21248 17 2 I 1~ 4 ~ ~ PCT/US93/02037 molecular weight of l,000, while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to ~0C to complete the reaction, thus obtaining urethane acrylate [A-4] with a number average molecular weight of l,680.
Example 5 Preparation of comparative urethane acrylate [B-l~
Into a reaction vessel equipped with a stirrer, 170.0 ~m of isophorone diisocyanate, 1 gm of dibutyltindilaurate, and 0.3 gm of 2,6-di-tert-butyl-4-methy~ phenol, as a polymerization inhibitor, were charged. Then, 59.2 gm of hydroxyethyl acrylate was added to the mixture while controlling the temperature below 20C. After the addition, the mixture was stirred for l hour while maintaining the temperature at lO to 20C, followed by the addition of 1~0~0.8 gm of a copolymer diol of tetrahydrofuran and propylene oxide (3:7 by weight) with a number average molecular weight of 2,000 (PPTG lOOO,~manufactured by Hodogaya Chemical Co.) while controlling the temperature at 40 to 50C. The mixture was stirred for a further 5 hours at 50 to 60C to complete the reaction, thus obtaining urethane acrylate ~B-l] with a number average molecular weight of 4,900.
Example 6 Preparation of comparative urethane acrylate ~B-2 ]
Into a reaction vessel equipped with a stirrer, 130 . 3 gm of 2, 4-tolylene diisocyanate, 1 gm of d~butyltindilaurate, and 9.3 gm of 2, 6-di-tert-butyl-4 methyl phenol, as a polymerization inhibltor~ were charged. To the mixture was added 1070.0 gm of poly~etramethylene glycol with a number average molecular weight of 2,000 (PPTG 2000, manuf~ctured by Hodogaya Chemical Co.) was added while controlling the temperature at 40 to 50C, followed by the reaction for 2 hours. Then, 49.6 gm of hydroxyethyl acrylate was added and W093/21~ 1 8 ~ 2 ~ PCT/US93/02037 the reaction was continued 5 hours at a temperature of 50 to 60C while stirring, thus obtaining urethane acrylate [B-2]
with a number average molecular weight of 5,840.
Example 7 Into a reaction vessel equipped with a stirrer, 55 parts of urethane acrylate [A-l], 30 parts of ARONIX Ml13, as a reaction diluent, 7 parts of Kayarad TCllOS ~a product of Nippon Kayaku Co.), 5 parts of N-vinyl pyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 0.3 part of Irganox lO35 ~manufactured by Ciba Geigy), O.l part of Sumisorb llO (manufactured by Sumitomo Chemical Co.), as a absorber, O.l p~rt of diethylamine, as a photosensi~izing agent, and l part of silane coupling agent (SH 6062, manufactured by Toray Silicone Co.) were charged and mixed with stirring at 50~ to 50C to obtain a transparent liquid composition with a viscosity of 3,700 cp at 25~C.
Example 8 ~Into a reaction vessel equipped with a stirrer, 55 parts of urethane acrylate [A-2], 25 parts of ARONIX Ml13, 12 parts of isobornyl acrylate, 5 part~ of N-~inyl caprolactam, l.5 parts of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), O.l part of diethylamine, and 1 part of SH 6062 were charged and mixed with stixring at 50 to 60C to obtain a transparent liquid composition with a ~iscosity of 3,000 cp at 25~C.
Example 9 Into a reaction ~essel equipped with a stirrer, 60.5 parts of urethane acrylate [A-3~, 37 parts of ARONIX M~13, 5 parts of N-vinyl pyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), O.l part of diethylamine, and l ~art of SH 6062 were charged and mixed with stirring at WO93/21248 ~ 2 1 PCT/US93/02~37 50 to 60C to obtain a transparent liquid composition with a viscosity of 5,000 cp at 25C.
Example 10 Into a reaction vessel equipped with a stirrer, 60 parts of urethane acrylate [A-4], 20 parts of tricyclodecanedimethanol diacrylate, 10 parts of isobornyl acrylate, 10 parts of N-vinyl caprolactam, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 0.3 part of Irganox 1035 (manufactured by Ciba Geigy) were charged and mixed with stirring at 50 to 60C to obtain a transparent liquid composition with a viscosity of 2,000 cp at 25C:.
~ . .
Comparative Example 1 A composition was prepared in the same manner as in Example 7, except that 55 parts of the urethane acrylate ~B-1~ was u~ed instead of the urethane acrylate [A-l ] ~ A
transparent liquid composition with a ~iscosity of 3,000 cp at 25C was obtained.
Comparative Example 2 A composition was prepared in ~he same manner as in ~xample 8, except that 30 parts of the urethane acrylate ~B-2] was used instead of the urethane acrylate [A-2). A
transparent liquid composition with a viscosity of 11 r 00O cp a~ 25C was obtained.
Test Examples 1. Film Tests Test leaves were prepared from compositions obtained in the above Examples and Comparative Examples and served to the evaluations according to the following met~ods.
~1) Preparation of test leaves The liquid compositions were applied to glass plates using a 150 applicator to obtain cured films by irradiation WO93/21248 2 ~ 2 1 PCT/VS93/02037 with ultraviolet rays at 25 mJ/cm2 or 500 mJ/cm2. Next, the cured films were peeled from the glass plates and tempered for 24 hours at a temperature of 23C and 50% RH, to obtain the test leaves.
(2) Measurement of Young's modulus (conforming to JIS K7127 Standard) The Young's modulus of each test leaf was measured in a tension tester at 23C or -40C at a drawing rate of l mm/min and a bench line interval of 25 mm.
(3) Gel Proportion The initial weight (Wo) of the cured film was measured, then the film was extracted for 12 hours in a Soxhlet extraction flask using methyl ethyl ketone as a solvent.
After extraction, the film was dried in a vacuum drier at 50C for 12 hours, then after standing for one hour at room temperature the final weight (WI~ was measured. The gel proportion was calculated using the following formula.
Gel proportion = Wl/Wo x lO0 (%) (4) Weight Change -The weight of the cured films obtained by irradiation with ultraviolet light at 500 mJ/cm2 was determined ~initial weight: Wo). After the heat resistant and light resistant tests, the films were left for l hour at room temperature to determine ~ts weight (dry weight: Wl~. The weight change was calculated according to the following formula.
Weight Change = (Wl-Wo)/Wo x lO0 (%) (5~ Heat Resistance Te~t The cured films obtained by irradiation with ultraviolet light at 500 mJ/cm2 were held in a thermostat at 120~C for 15 days. The Young's modulus and gel proportion of the films were then measured. The results are shown in Table l.
(6) Light Resistance Test ~ ight resistance tests were performed on the films cured at 500 mJ/cm2 using a Q W weathering acceleration machine (manufactured by Q-panel Co.). The lamp used was a UV0-3I3.
After 200 hours in the machine, the outer appearance of the WO93/21~48 2 1 1 ~ PCT/US93/02037 film was examined and the Young's modulus and gel proportion were measured. The results are ~hown in Table l.
___________________________________________________________ Comparati~e Examples __ExamDles Evaluation Item l 2 3 l 2 _________________________ ___ _________________________ ___ t~3C]
Young's modulus (kg/mm2) 25 m/cm2 0.06 0.06 0.06 0.05 0.11 500 m/cm2 0.07 0.06 0.06 0.08 0.18 Gel proportion (%) 25 m/cm2 88 90 88 82 85 S00 m/cm2 89 91 89 88 90 ___________________________________________________________ a~e~ eat R~esl ~tant Te~t 500 r~ 2 Young's mo~ulus 25 (kg/mm2) 0.05 0.06 0.05 0~05 0.07 -Cel Proportion ~)86 - 87 86 82 6S
Color change into yellow Non Non Non Non Changed _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ = _ _ _ _ _ _ _ _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 500 m/cm2 Gel Proportion (%)84 83 83 50 83 We~ght 5hange -0.3 -O.l -0.2 -lO -l.5 Color change into yellow Non Non Non Non Changed ____________ ______________________________________________ WO~3/~ 2 1 1 S ~ 2 1 PCT/U593/~2U37 2. Drawing Tests Using an optical fiber drawing machine, two layers of a composition, according to the combination in Table 2, was applied to optical fibers and then cured by irradiation with ultraviolet rays to obtain coated optical fibers. The mean diameter of the optical fiber core was 125 ~m, that of the fiber covered with the primary layer 200 ~m, and that of the fiber covered with the secondary layer 250 ~m.
The covered optical fibers were prepared at drawing speeds of 180t 360, and 720 mimin, and subjected to the tests `
according to the following methods. The results are shown ~n Table 2..
.. ...
(1) Gel Proportion The initial weight ~Wo) of the coated fibers, cut to a length of 4 cm, was determined (initial weight: Wo), and the f~bers were extracted for 12 hours in a Soxhlet extract;ion flask using methyl ethyl ketone as a solvent.
After extraction, the fibers were dried in a vacuum drier at 50C for 12 hours, then after-standing for one hour at r~om temperature the final weight ~dry weight: Wl) was determined.
Thereafter, the optical fibers were calcined for 30 :
minutes in an electric ~urnace at ~00C to remove the coated layers and to collect the optical fiber material, of which the we~ght ~Wf) was determined.
The gel proportion was calculated using the following formula.
Gel proportion = tWl-Wf)/(Wo-wf) x 100 (%~
3. En~ironment Test (1) Light Resistance ! Coated optical fibers drawn at 360 m/min were exposed to fluorescent light (2,000 lux) for 30 days t~ evaluate their external appearance, and to determine the change in weight and the a unt of hydrogen gas generated.
, WO93/21248 2 ~ 1 ~ 'I 2 L
~ PCT/US93/02037 ~3 Method of Evaluation ~a) External Appearance Coated layers, fibers~ and their interface were mlcroscopically observed to investigate the presence or absence of vacant spaces, peeled portions, liquid drops, and foreign materials.
~b) Change in Weight The change in weight by the exposure to fluorescent light was determined according to the following formula.
Change in Weight = (Wb-Wa)/(Wa-Wf) x 100 (%) wherein Wa is the weight of the coated fiber before exposure to fluorescent light, Wb after the exposure, and WE is the weight of the optical fiber obtained after removal of covered material by calcination in the an electric furnace at 700C
for 30 min~tes.
~c) Generation of Hydrogen Gas The amounts of hydrogen gas before and after the light resistant test were determined by the following method. The coated optical fiber was accurately weighed, placed in a vial wit~ a known weight, and heated at 100C for 4 hours. The air in the head space of the vial was collected by means of a gas ~ight syringe and the air was introduced to a gas chromatography to qua~titatively analyze the amount of hydrogen gas. An absolu~e calibration curve was used for the analysis. The resul~s are shown in Table 2.
WO 93/2124~ L'l 21 P(:~US93/02037 Te~t Example No. 1 2 3 4 5 Cc~mp. Comp. ':
Soft material for Example 1 Example 2 ~xample 3 ~xample 1 Example 2 primary layer Hard material for Example 4 Example 4 Example 4 Example 4 Example 4 0 ~econdary layer Re~ult~ of Evaluation 1. Curing Rate Gel Proportion (%~
at Dra~ing Rate (m/min ) 180 90 9~ 90 85 90 2. Environm~ntal Te~t ~Light Re~istance) EXternal Appear~nce No change No change No change No change Ch~nged ~eight Chantge ~ 0.5 -0.2 -0.3 -2.5 -0.3 Kydrogen Ga~
Generation ~l/gm) Initi~l 0.2 0.2 0.2 0.2 8.0 After Te~t 5 6 4 300 20 The liquld curable resin composition of the present invention exhibits a high curing rater its cured materials has ~ low Young's modulus and a high gel ratio, provides superior heat resistance and light resistance, and generates 35 Qnly a small amount of hydrogen gas. It is thus particularl~
suitable as a material for optical fiber coating. Oec~use of its superior heat resistance, curability, and adherence f the composition is not only applicable to an optical fiber coating, but also useful as a protective coating material for ~arious types of substrates such as metals, plastics, wood, WO93/21248 ~ 2 1 ~CTII~S93/02037 porcelain, glass, and the like, and as an optical molding matérial, three~dimensional molding material~ printing plate material, and the like.
Claims
1. A liquid curable resin composition comprising a urethane (meth)acrylate obtained by the reaction of, (A) a polyether polyol compound containing, as a structural unity, groups represented by the following formulas (1), (2), and (3), (1) -CH2CH2O-(2) -CH2CH(R)O-, and (3) one or more groups selected from groups (a), (b), and (c) below, -CH2CH2CH2CH2O- (a) (b) (c) wherein R represents an alkyl group containing two or more carbon atoms, and R1 and R2 axe independently selected from a hydrogen atom or a methyl group;
(B) a polyisocyanate compound; and (C) a (meth)acrylate compound having a hydroxy group.
2. A composition as in claim 1 wherein the polyol is prepared by the ring-opening polymerization of ethylene oxide, 1,2-alkylene oxides with four or more carbon atoms and one or more compounds selected from polydetramethylene glycol, bisphenol A and bisphenol F.
3. A composition as in claim 1 that further comprises another polyol.
4. A composition as in claim 1 that further comprises at least one of polyether polyols, polyester polyols, polycarbonate polyols and polycarprolactone polyols.
5. A composition as in claim 1 wherein the polyisocyanate compound is selected from 2,4-tolylene diisocyanate, isophorone diisocyanate and 2,2,4-trimethylhexane methylene diisocyanate.
6. A composition as in claim 1 wherein the (meth)acrylate compound having a hydroxy group is 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.
7. A composition as in claim 1 that further comprises N-vinyl pyrrolidone or N-vinyl caprolactam.
8. A composition as in claim 1 that further comprises a polymerization initiator.
9. An optical fiber coated with the composition of
claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP99596/04 | 1992-04-20 | ||
| JP09959692A JP3220221B2 (en) | 1992-04-20 | 1992-04-20 | Liquid curable resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2118421A1 true CA2118421A1 (en) | 1993-10-28 |
Family
ID=14251484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2118421 Abandoned CA2118421A1 (en) | 1992-04-20 | 1993-03-09 | Liquid curable resin composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0638100A1 (en) |
| JP (1) | JP3220221B2 (en) |
| AU (1) | AU671442B2 (en) |
| CA (1) | CA2118421A1 (en) |
| WO (1) | WO1993021248A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5373578A (en) * | 1993-12-21 | 1994-12-13 | At&T Corp. | Strippable coating for optical fiber |
| JP3288869B2 (en) * | 1994-10-14 | 2002-06-04 | ジェイエスアール株式会社 | Liquid curable resin composition |
| JPH09143233A (en) * | 1995-11-28 | 1997-06-03 | Japan Synthetic Rubber Co Ltd | Photocuring liquid resin composition |
| JP3756585B2 (en) * | 1996-09-05 | 2006-03-15 | Ｊｓｒ株式会社 | Photo-curable liquid resin composition |
| JP3634592B2 (en) * | 1997-01-08 | 2005-03-30 | セイコーエプソン株式会社 | Bonding fixtures, electronic devices and watches |
| US6023547A (en) * | 1997-06-09 | 2000-02-08 | Dsm N.V. | Radiation curable composition comprising a urethane oligomer having a polyester backbone |
| US6085010A (en) * | 1997-06-11 | 2000-07-04 | Dsm N.V. | Optical glass fiber ribbon assemblies and radiation-curable compositions for use in forming ribbon assemblies |
| US6048911A (en) * | 1997-12-12 | 2000-04-11 | Borden Chemical, Inc. | Coated optical fibers |
| US6391936B1 (en) | 1997-12-22 | 2002-05-21 | Dsm N.V. | Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies |
| JP4141613B2 (en) | 2000-03-09 | 2008-08-27 | 富士通株式会社 | Closed cycle refrigerator and dry evaporator for closed cycle refrigerator |
| JP2003246826A (en) * | 2002-02-19 | 2003-09-05 | Dsm Nv | Liquid curable resin composition |
| JP2012038499A (en) * | 2010-08-05 | 2012-02-23 | Jsr Corp | Radiation curable resin composition for wire coating layer formation |
| JP2013151678A (en) * | 2011-12-29 | 2013-08-08 | Sanyo Chem Ind Ltd | Active energy ray-curable composition |
| JP7439761B2 (en) * | 2018-09-10 | 2024-02-28 | 株式会社レゾナック | Epoxy resin, epoxy resin composition, epoxy resin cured product and composite material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54129034A (en) * | 1978-03-30 | 1979-10-06 | Kao Corp | Coating resin composition curable with actinic energy radiation |
| US4507458A (en) * | 1983-04-14 | 1985-03-26 | Takeda Chemical Industries, Ltd. | Urethane acrylate compositions |
| JPS62148514A (en) * | 1985-12-24 | 1987-07-02 | Yokohama Rubber Co Ltd:The | Ultraviolet-curing resin composition |
| JPS63109699A (en) * | 1986-10-28 | 1988-05-14 | Yokohama Rubber Co Ltd:The | Composite substance for radiation and ultraviolet curing type damping material |
| JPH07113104B2 (en) * | 1987-11-13 | 1995-12-06 | 日本合成ゴム株式会社 | Curable bundling material for optical fiber |
| US5093386A (en) * | 1989-05-16 | 1992-03-03 | Stamicarbon B.V. | Liquid curable plastic composition |
| JP2893135B2 (en) * | 1990-10-19 | 1999-05-17 | ジェイエスアール株式会社 | Liquid curable resin composition for optical fiber coating |
-
1992
- 1992-04-20 JP JP09959692A patent/JP3220221B2/en not_active Expired - Lifetime
-
1993
- 1993-03-09 EP EP93907275A patent/EP0638100A1/en not_active Withdrawn
- 1993-03-09 WO PCT/US1993/002037 patent/WO1993021248A1/en not_active Application Discontinuation
- 1993-03-09 CA CA 2118421 patent/CA2118421A1/en not_active Abandoned
- 1993-03-09 AU AU37933/93A patent/AU671442B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JP3220221B2 (en) | 2001-10-22 |
| WO1993021248A1 (en) | 1993-10-28 |
| AU3793393A (en) | 1993-11-18 |
| EP0638100A4 (en) | 1994-12-15 |
| EP0638100A1 (en) | 1995-02-15 |
| JPH0680756A (en) | 1994-03-22 |
| AU671442B2 (en) | 1996-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0554404B1 (en) | Curable liquid resin composition | |
| US6023547A (en) | Radiation curable composition comprising a urethane oligomer having a polyester backbone | |
| US6136880A (en) | Radiation-curable liquid resin composition for coating optical fibers | |
| US8242202B2 (en) | Curable liquid resin composition | |
| US5712035A (en) | Liquid curable resin composition | |
| US5998497A (en) | Liquid photocurable resin composition | |
| AU705686B2 (en) | Optical glass fiber coating composition | |
| CA2118421A1 (en) | Liquid curable resin composition | |
| US5804311A (en) | Liquid curable resin composition for optical fibers | |
| EP1456312A1 (en) | Radiation-curable compositions for optical fiber coating materials | |
| WO1999018043A1 (en) | Optical fiber coatings | |
| KR20020093885A (en) | Liquid curable resin composition and double layer | |
| WO2001083393A2 (en) | Liquid curable resin composition for optical fibers | |
| WO1997014737A1 (en) | Liquid curable resin composition | |
| WO2001047824A1 (en) | Optical fiber coating compositions | |
| EP0746530B1 (en) | Liquid curable resin composition for optical fibers | |
| WO2000020478A1 (en) | Liquid curable resin composition | |
| JP3607748B2 (en) | Multilayer coating | |
| WO1998009923A1 (en) | Photo-curable liquid resin composition | |
| KR100626509B1 (en) | Radiation-curable compositions for optical fiber coating materials | |
| KR100475843B1 (en) | Liquid curable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |