EP0638100A4 - Composition de resine liquide durcissable. - Google Patents

Composition de resine liquide durcissable.

Info

Publication number
EP0638100A4
EP0638100A4 EP19930907275 EP93907275A EP0638100A4 EP 0638100 A4 EP0638100 A4 EP 0638100A4 EP 19930907275 EP19930907275 EP 19930907275 EP 93907275 A EP93907275 A EP 93907275A EP 0638100 A4 EP0638100 A4 EP 0638100A4
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP19930907275
Other languages
German (de)
English (en)
Other versions
EP0638100A1 (fr
Inventor
Tohru Ohtaka
Shinichirou Jsr Apartm Iwanaga
Tsuyoshi Watanabe
Katutoshi Jsr Apartme Igarashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Desotech Inc
Original Assignee
DSM Desotech Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM Desotech Inc filed Critical DSM Desotech Inc
Publication of EP0638100A4 publication Critical patent/EP0638100A4/fr
Publication of EP0638100A1 publication Critical patent/EP0638100A1/fr
Withdrawn legal-status Critical Current

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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

Definitions

  • 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.
  • an optical fiber is provided with a resin coating comprising a flexible primary coating layer on the surface of the optical fiber, with the object of protecting and reinforcing the bare optical fiber threads immediately after hot melt spinning of the glass 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 :
  • liquid coating materials of the radiation curable type have been developed. 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.
  • 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.
  • an object of the present invention is to provide, with due consideration to the drawbacks of such conventional compositions, a liquid curable resin composition ideal as a covering material for optical fiber, which has a low viscosity at room temperature and exhibits good processability when used to cover optical fibers, has good optical curing characteristics, 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.
  • R represents an alkyl group containing two or more carbon atoms, and R- ⁇ and R ⁇ are independently selected from a hydrogen atom or a methyl group; (B) a polyisocyanate compound; and
  • the liquid curable resin composition of the present invention has an extremely low Young's modulus at room temperature, shows a suitable adhering strength to glass fiber, has superior durability, exhibits high speed curing performance, and is thus suitable as a coating material for optical fiber.
  • polyol compound (A) ) used in the present invention must contain structural units of the above formulae (1), (2), and (3) . There are no limitations as to the manner in which 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, 1,2-alkylene oxides with 4 or more carbon atoms, e.g, 1,2-butylene oxide, 1,2- hexene oxide, or the like, and one or more compounds selected from polytetramethylene glycol r 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 number of carbon atoms of R in the unit of formula (2) contained 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 10,000, and preferably 500 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 side pressure when it is applied to optical fiber; if greater than 10,000, the viscosity of the resulting composition tends to increase, resulting in impaired coating 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 of these 3 structural units.
  • Examples of such other structural units include -CH2CH2CH2O-, -CH2CH(CH3)0-, and the like.
  • polyols which do not have the above structural units (1), (2) and (3) can be used in combination.
  • examples of such polyols include polyether polyols, polyester polyols, polycarbonate polyols, polycapralactone polyols, and other polyols.
  • polyether polyols which do not have the above structural units (1), (2) and (3) include, for example, polyethylene glycol, 1,2-polypropylene glycol, 1,3- polypropylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, propylene oxide-tetrahydrofuran copolymers, methyl tetrahydrofuran-tetrahydrofuran copolymers, and the like.
  • polyester polyols examples include polyester polyols obtained by reacting a polyvalent alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane diol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-l,5-pentanediol, 1,9- nonanediol, 2-methyl-l,8-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 products such as Kurapol P-2010, PMIPA, PRA-A, PHA-A2, PNA2000 (manufactured by Kuraray Co.) , and the like.
  • a polyvalent alcohol such as ethylene
  • polycarbonate polyols examples include 1, 6-hexanepolycarbonate and products available on the market, such as DN-980, DN-981, DN-982, DN-983 (manufactured by Nihon Polyurethane Co., Ltd.), PC-8000 (manufactured by PPG of the US), and the like.
  • polycaprolactone polyols examples include polycaprolactonediols obtained by reacting ⁇ -caprolactone with a divalent diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2- polybutylene glycol, 1, -hexanediol, neopentyl glycol, 1,4- butanediol, or the like, as well as PLACCEL-205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel Co.), and the like.
  • a divalent diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2- polybutylene glycol, 1, -hexanediol, neopentyl glycol
  • polystyrene resin examples 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-A, 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
  • polyisocyanate compound (B) which can be used in the present invention are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl- ,4'-diphenylmethane diisocyanate, , *-diphenylmethane diisocyanate, 3,3'- dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate) , 2,2,4- trimethylhexamethylene diisocyanate, bis(2- isocyanateethyl)fum
  • Examples of (meth)aerylates with a hydroxyl group, component (C) used in the present invention include 2- hydroxyethyl (meth)acrylate, 2-hydroxy ⁇ ropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3- phenyloxypropyl(meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentylglycol mono(meth)acrylate, tri ethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates represented by the following formula
  • the urethane (meth)acrylates used in the present invention can be prepared by the reaction of the abovementioned polyol compound (A) , polyisocyanate compound (B) , and (meth)acrylate compound containing a hydroxy group (C) ; specifically, by reacting the isocyanate group in the 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.
  • polyol compound (A) , polyisocyanate compound (B) , and (meth)acrylate compound containing a hydroxy group (C) are charged in the reactor for the reaction.
  • 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) .
  • Polyisocyanate compound (B) and (meth)acrylate compound containing a hydroxy group (C) are first reacted, and then the resulting reaction product is reacted with polyol compound (A) .
  • the proportions of polyol compound (A) , polyisocyanate compound (B) , and (meth)acrylate compound containing a hydroxy group (C) used for the reaction are such that 1.1 to 3 equivalents of isocyanate groups in polyisocyanate compound (B) and 0.1 to 1.5 equivalents of hydroxy groups in (meth)acrylate compound containing a hydroxy group (C) are used for 1 equivalent of the hydroxy group contained in polyol compound (A) .
  • urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n- butyltindilaurate, triethylamine, triethylenediamine, 2- methyltriethylenediamine, or the like
  • the reaction temperature is normally 10 to 90°C, and preferably 30 to 80°C.
  • 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 fiber wire, and in maintaining the flexibility and long term reliability of the coated material after curing.
  • the molecular weight of urethane (meth)acrylate is usually 700 to 20,000, and preferably 1,000 to 10,000 (number average molecular weight) .
  • 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 invention are not adversely affected.
  • urethane (meth)acrylates of the present invention 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 compositions of the present invention. They may be added either singly or two or more may be added together.
  • reaction diluents include monofunctional and polyfunctional compounds.
  • monofunctional compounds which can be given include 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, de
  • (meth)acrylate stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate. ethoxyethoxyethyl (meth)acrylate, methoxypolyethylene glycol
  • (meth)acrylate dicyclopentenyl (meth) crylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth ) acrylamide, N-vinyl pyrrolidone, N- vinyl caprolactam, N,N-dimethyl (meth)acrylamide, t-octyl
  • crylamide dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl
  • (meth)acryloylmorphorine vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2- ethylhexyl vinyl ether, and the like; maleic acid esters, fumaric acid esters, and compounds represented by the following formulas (5) to (7) .
  • R ⁇ indicates a hydrogen atom or a methyl group
  • R ⁇ is an alkylene group with 2 to 6, preferably 2 to 4, carbon atoms
  • R ⁇ is a hydrogen atom or an alkyl group with 1 to 12, preferably 1 to 9, carbon atoms
  • m is an integer from 0 to 12, preferably from 1 to 8.
  • R ⁇ is the same as above, and R> 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.
  • R ⁇ is a hydrogen atom or a methyl group.
  • Examples of commercial products which can be used are ARONIX Mill, M113, M114, M117 (manufactured by Toa Gosei Chemical Co.), KAYARAD TC110S, R629, R644 (manufactured by Nippon Kayaku Co.) and OISCOAT 3700 (manufactured by Osaka Organic Chemicals Co.) and the like.
  • polyfunctional compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6- hexanediol di(meth)acrylate, neopentyl glycol di(meth) crylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, epoxy (meth)acrylates obtained by the addition of a (meth)acrylate to bisphenol A diglycidyl ether, triethylene glycol divinyl ether
  • Examples of commercial products which can be used are COPIMA-UV, SA1002, SA2007 (manufactured by Mitsubishi Petrochemical Co.), BISCOAT 700 (manufactured by Osaka Organic Chemical Co.), R604, DPCA-20, DPCA-30, DPCA-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.
  • (meth)acrylate compounds of which the homopolymer have a glass transition temperature of -10°C or below, are preferably used among the above-mentioned reaction diluents.
  • (meth)acrylate compounds are commercial products such as ARONIX M102, Mill, M113, M114, M117 (manufactured by Toa Gosei Chemical Co.), KAYARAD TC110S, R629, R64 (manufactured by Nippon Kayaku Co.), and the like.
  • N-vinyl pyrrolidone and N-vinyl caprolactam among the above-mentioned reaction diluents are preferably used.
  • reaction diluents can be incorporated in the composition of the present invention preferably in an amount of 5 to 60%, and particularly preferably 10 to 40%.
  • the composition of.the present 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, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • a radical polymerization initiator for example, peroxides, azo compounds or the like. Specific examples are benzoyl peroxide, t-butyloxybenzoate, azobisisobutyronitrile, and the like.
  • a photopolymerization initiator and, as required, a photosensitizing agent are used.
  • 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-methy1-1- phenylpropane-1-on, thioxanthone, diethylthioxanthone, 2- isopropylthioxanthone, 2-chlorothioxanthone,
  • photosensitization agents are triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4- dimethylaminobenzoic acid, 4-dimethylaminomethyl benzoate, 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 mixtures of two or more.
  • the above-mentioned radical polymerization initiators can be used in combination.
  • the amount of polymerization initiator used is preferably 0.1 to 10% of the composition.
  • additives may optionally be added to the composition of the present invention.
  • additives include epoxy resins, polyamides, polyamidoimides, polyurethanes, polybutadienes, chloroprene, polyethers. polyesters, pentadiene derivatives, styrene/butadiene/styrene block copolymers, styrene/ethylene/butene/styrene block copolymers, styrene/isoprene/styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine containing oligomers, silicone-type oligomers, polysulfide type oligomers, and the like.
  • antioxidants coloring agents, ultraviolet absorbers, photostabilizers, silane coupling agents, heat polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging inhibitors, wetting agents, coating surface improvers, and the like.
  • antioxidants which can be used are Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy) , and the like.
  • Tinuvin P234, 320, 326, 327, 32a, 213 manufactured by Ciba Geigy
  • Sumisorb 110, 130, 200 Sumitomo Chemical Co.
  • commercial photostabilizers which can be used include Tinuvin 292, 144, 622LD (manufactured by Ciba Geigy) , Sanol LS7 70
  • 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.), KBE903, 603, 403 (manufactured by Shin-Etsu Chemical Co.) , and the like.
  • the liquid curable resin composition of the present invention can be manufactured by mixing the above 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 25°C, and preferably 2,000 to 10,000 cp at 25°C.
  • the Young's modulus after curing is 0.05 to 0.5 kg/mm 2 , and particularly preferable is 0.06 to 0.13 kg/mm 2 .
  • the Young's modulus of the cured material at -40° to 60°C is usually 0.01 to 10 kg/mm 2 .
  • the mixture was stirred for 1 hour while maintaining the temperature at 10 to 20°C, 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 50°C.
  • the mixture was stirred for a further 5 hours at 50 to 60°C to complete the reaction, thus obtaining urethane acrylate [A-l] with a number average molecular weight of 4,900.
  • the mixture was stirred for 1 hour while maintaining the temperature at 10 to 20°C, followed by the addition of 1,020.8 gm of a copolymer diol of tetrahydrofuran and propylene oxide (3:7 by weight) with a number average molecular weight of 2,000 (PPTG 1000, manufactured by Hodogaya Chemical Co.) while controlling the temperature at 40 to 50°C.
  • the mixture was stirred for a further 5 hours at 50 to 60°C to complete the reaction, thus obtaining urethane acrylate [B-l] with a number average molecular weight of 4,900.
  • Example 8 Into a reaction vessel equipped with a stirrer, 55 parts of urethane acrylate [A-2], 25 parts of ARONIX M113, 12 parts of isobornyl acrylate, 5 parts of N-vinyl caprolactam, 1.5 parts of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), 0.1 part of diethylamine, and 1 part of SH 6062 were charged and mixed with stirring at 50° to 60°C to obtain a transparent liquid composition with a viscosity of 3,000 cp at 25°C.
  • Example 9 Into a reaction vessel equipped with a stirrer, 60.5 parts of urethane acrylate [A-3], 37 parts of ARONIX MI13, 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), 0.1 part of diethylamine, and 1 part of SH 6062 were charged and mixed with stirring at 50° to 60°C to obtain a transparent liquid composition with a viscosity of 5,000 cp at 25°C.
  • 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 60°C to obtain a transparent liquid composition with a viscosity of 2,000 cp at 25°C.
  • 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 used instead of the urethane acrylate [A-l] .
  • a transparent liquid composition with a viscosity of 3,000 cp at 25°C was obtained.
  • a composition was prepared in the same manner as in Example 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 11,000 cp at 25°C was obtained.
  • Test leaves were prepared from compositions obtained in the above Examples and Comparative Examples and served to the evaluations according to the following methods.
  • test leaves The liquid compositions were applied to glass plates using a 150 applicator to obtain cured films by irradiation with ultraviolet rays at 25 mJ/cm 2 or 500 mJ/cm 2 . Next, the cured films were peeled from the glass plates and tempered for 24 hours at a temperature of 23°C and 50% RH, to obtain the test leaves .
  • Young's modulus (conforming to JIS K7127 Standard)
  • 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.
  • Weight Change (Wl-Wo) /Wo x 100 (%)
  • the cured films obtained by irradiation with ultraviolet light at 500 mJ/cm 2 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 1.
  • 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 ⁇ , 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 180, 360, and 720 m/min, and subjected to the tests according to the following methods. The results are shown in Table 2.
  • the fibers were dried in a vacuum drier at 50°C for 12 hours, then after standing for one hour at room temperature the final weight (dry weight: Wl) was determined.
  • the optical fibers were calcined for 30 minutes in an electric furnace at 700°C to remove the coated layers and to collect the optical fiber material, of which the weight (Wf) was determined.
  • the gel proportion was calculated using the following formula.
  • Coated optical fibers drawn at 360 m/min were exposed to fluorescent light (2,000 lux) for 30 days to evaluate their external appearance, and to determine the change in weight and the amount of hydrogen gas generated.
  • Coated layers, fibers, and their interface were microscopically observed to investigate the presence or absence of vacant spaces, peeled portions, liquid drops, and foreign materials.
  • 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 with a known weight, and heated at 100°C for 4 hours.
  • the air in the head space of the vial was collected by means of a gas tight syringe and the air was introduced to a gas chromatography to quantitatively analyze the amount of hydrogen gas.
  • An absolute calibration curve was used for the analysis. The results are shown in Table 2.
  • the liquid curable resin composition of the present invention exhibits a high curing rate, its cured materials 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. Oecause of its superior heat resistance, curability, and adherence, the composition is not only applicable to an optical fiber coating, but also useful as a protective coating material for various types of substrates such as metals, plastics, wood, porcelain, glass, and the like, and as an optical molding material, three-dimensional molding material, printing plate material, and the like.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (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

L'invention concerne une composition de résine liquide durcissable comprenant du (méth)acrylate de polyuréthane que l'on obtient en faisant réagir: (A) un polyol de polyéther contenant, en tant qu'unités structurales, des groupes représentés par les formules suivantes: (1) -CH2CH2O-, (2) -CH2CH(R)O-, et (3) un ou plusieurs groupes sélectionnés parmi les groupes suivants: (a) -CH2CH2CH2CH2O-, (b) et (c) dans lesquels R représente un groupe alkyle contenant deux atomes de carbone ou plus, et R1 et R2 sont sélectionnés indépendamment parmi un atome d'hydrogène ou un groupe méthyle, (B) un composé de polyisocyanate, et (C) un composé de (méth)acrylate présentant un groupe hydroxy. Ladite composition présente une vitesse de durcissement élevée, sa matière durcie présentant un module d'Young faible et une proportion de gel élevée, une résistance à la chaleur et à la lumière élevée, et ne dégage qu'un faible volume de gaz hydrogène. Elle est particulièrement appropriée à l'enduction de fibres optiques.
EP93907275A 1992-04-20 1993-03-09 Composition de resine liquide durcissable Withdrawn EP0638100A1 (fr)

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JP09959692A JP3220221B2 (ja) 1992-04-20 1992-04-20 液状硬化性樹脂組成物
JP99596/92 1992-04-20
PCT/US1993/002037 WO1993021248A1 (fr) 1992-04-20 1993-03-09 Composition de resine liquide durcissable

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EP0638100A4 true EP0638100A4 (fr) 1994-12-15
EP0638100A1 EP0638100A1 (fr) 1995-02-15

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US5373578A (en) * 1993-12-21 1994-12-13 At&T Corp. Strippable coating for optical fiber
JP3288869B2 (ja) * 1994-10-14 2002-06-04 ジェイエスアール株式会社 液状硬化性樹脂組成物
JPH09143233A (ja) * 1995-11-28 1997-06-03 Japan Synthetic Rubber Co Ltd 光硬化性液状樹脂組成物
JP3756585B2 (ja) * 1996-09-05 2006-03-15 Ｊｓｒ株式会社 光硬化性液状樹脂組成物
JP3634592B2 (ja) * 1997-01-08 2005-03-30 セイコーエプソン株式会社 接着固定物、電子機器および時計
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 (ja) 2000-03-09 2008-08-27 富士通株式会社 密閉サイクル冷凍装置および密閉サイクル冷凍装置用乾式蒸発器
JP2003246826A (ja) * 2002-02-19 2003-09-05 Dsm Nv 液状硬化性樹脂組成物
JP2012038499A (ja) * 2010-08-05 2012-02-23 Jsr Corp 電線被覆層形成用放射線硬化性樹脂組成物
JP2013151678A (ja) * 2011-12-29 2013-08-08 Sanyo Chem Ind Ltd 活性エネルギー線硬化性組成物
EP3851474B1 (fr) * 2018-09-10 2023-07-19 Resonac Corporation Résine époxyde, composition de résine époxyde, produit durci à base de résine époxyde et matériau composite

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AU671442B2 (en) 1996-08-29
AU3793393A (en) 1993-11-18
WO1993021248A1 (fr) 1993-10-28
CA2118421A1 (fr) 1993-10-28
JPH0680756A (ja) 1994-03-22
EP0638100A1 (fr) 1995-02-15
JP3220221B2 (ja) 2001-10-22

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