CN102159656A - Photocurable coating composition which provides a coating layer having improved hot water resistance - Google Patents

Photocurable coating composition which provides a coating layer having improved hot water resistance Download PDF

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Publication number
CN102159656A
CN102159656A CN2009801359837A CN200980135983A CN102159656A CN 102159656 A CN102159656 A CN 102159656A CN 2009801359837 A CN2009801359837 A CN 2009801359837A CN 200980135983 A CN200980135983 A CN 200980135983A CN 102159656 A CN102159656 A CN 102159656A
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weight
coating
acrylate
composition according
composition
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金民政
闵庚范
崔海郁
金龙敏
崔瑛珍
金相还
成五铉
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SSCP Co Ltd
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SSCP Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08G18/67—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a photocurable coating composition comprising a urethane acrylate oligomer which is synthesized using a polyol copolymer, a polyisocyanate, an acrylate alcohol, a urethane reaction catalyst, and a polymerization inhibitor, and an optical fiber using the same, the optical fiber showing improved water resistance and excellent thermal, mechanical and chemical stabilities.

Description

The photo curable coating composition of the coating with improved hot water resistance is provided
Technical field
The present invention relates to a kind of photo curable coating composition, it provides the coating with improved hot water resistance when solidifying, the present invention relates to comprise the optical fiber of above-mentioned coating.
Background technology
In preparation during optical fiber, even require the coating that on fiber glass core, forms also to have high bond strength after in immersing hot water with fiber glass core.
So far, reported the multiple photo curable coating composition that is used to form above-mentioned coating.Yet, wherein,, carrying out undesirable crystallization at low temperatures by the coating that comprises by the coating composition preparation of the uV curable of crystallization polyvalent alcohol synthetic oligopolymer, this causes the remarkable loss of resulting optical fiber optical efficiency.
In order to reduce zero pour that is used for fibre-optic coating and the low-temperature stability that improves it, U.S. Patent No. 6,599,956 disclose a kind of comprising by the crystallization polyvalent alcohol of specified quantitative and the photo curable coating composition of noncrystalline polyvalent alcohol synthetic oligopolymer.In addition, EP patent No.1362016 discloses a kind of photo curable coating composition that comprises the photo curable oligourethane of being made by the polyester polyol of the amount of 50～70 weight %, and this coating composition is provided at the coating that has good water resistance when immersing in 60 ℃ of water when solidifying.
Although the coating that is formed by above-mentioned composition is showing some improvement aspect the bond strength of fiber glass core or hot water resistance, but set time that they need prolong and during long-term dipping, still experiencing the variation gradually of hot water resistance, thereby be easy to break away from glass fibre.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of photo curable coating composition, it provides a kind of coating when solidifying, even after this coating immerses in the hot water during long-time, still have improved physical properties at hot water resistance and aspect the bond strength of glass fibre substrate.
Another object of the present invention is to provide a kind of optical fiber that comprises described coating.
According to an aspect of the present invention, a kind of photo curable coating composition is provided, and it comprises: (A) urethane acrylate oligomer of the use polyol copolymer of 30～90 weight %, polyisocyanates, acrylate alcohol, urethane reaction catalyzer and the photopolymerization of stopper synthetic; (B) reactive monomer that comprises at least one acrylate, methacrylic ester or vinyl groups of 5～60 weight %; (C) light trigger of 1～15 weight %.
Description of drawings
In conjunction with the accompanying drawings 1, above-mentioned and other purpose of the present invention and feature will become apparent from following description of the present invention, and Fig. 1 shows the synoptic diagram that is coated on the solidification process of the coating composition on the fibre-optic fiber glass core by uviolizing.
Embodiment
Photo curable coating composition of the present invention is characterised in that and comprises the urethane acrylate oligomer of being made up of the pure and mild polyether glycol of polyester polyols of copolymerization that the pure and mild polyether glycol of the polyester polyols of described copolymerization uses polyol copolymer, polyisocyanates, acrylate alcohol, urethane reaction catalyzer and stopper to synthesize.
Photo curable coating composition of the present invention mainly by the reactive monomer that comprises at least one acrylate, methacrylic ester or vinyl groups of the urethane acrylate oligomer of the photopolymerization of (A) 30～90 weight %, (B) 5～60 weight % and (C) light trigger of 1～15 weight % form, but can also comprise the amine additive of (D) 0.01～0.5 weight % and (E) monomer based on silane, stablizer or its mixture of 1～5 weight %.
Hereinafter, describe each component in detail.
(A) urethane acrylate oligomer of photopolymerization
The urethane acrylate oligomer of photopolymerization used in the present invention uses (i) polyol copolymer, (ii) polyisocyanates, (iii) acrylate alcohol, (iv) urethane reaction catalyzer and (v) stopper synthesizes.Preferably, the urethane acrylate oligomer of described photopolymerization can be that 10: 90～30: 70 polyether glycol and polyester polyol formed by weight ratio, and number-average molecular weight is 5,000～50,000 (determining) by gel permeation chromatography (GPC), viscosity is 10,000～30,000cps (at 40 ℃ of employing Brookfield viscometer HB types, rotor (spindle) #51 measures).
The urethane acrylate oligomer of described photopolymerization, based on the gross weight of this coating composition, with the consumption of 30～90 weight % use.When this consumption during, during microbend, may lose, and when this consumption during greater than 90 weight %, workability is because of the high viscosity variation less than 30 weight %.
(i) polyol copolymer
The number-average molecular weight of described polyol copolymer (i) is 100～10,000, and preferably comprises-CH 2CH 2O-or-CH 2CH (CH 2CH 3) repeating unit of O-.
The preferred embodiment of described polyol copolymer comprises polyester polyol, polyether glycol, polycarbonate polyol, polycaprolactone polyvalent alcohol, tetrahydrofuran (THF) propylene oxide ring opening copolymer thing, ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1, pure and mild their mixture of 6-hexylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, bisphenol A-type two.Wherein, the mixture of the tetrahydrofuran (THF) propylene oxide ring opening copolymer thing of more preferably polyether glycol, and 10～30 weight % and the polyester polyol of 70～90 weight %.
Described polyol copolymer based on the gross weight of the urethane acrylate oligomer of photopolymerization, preferably uses with the amount of 30～75 weight %.
(ii) polyisocyanates
Polyisocyanates used in the present invention preferred embodiment (ii) comprises 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-Xylene Diisocyanate, 1,4-Xylene Diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane diisocyanate, isoflurane chalcone diisocyanate (IPDI) and their mixture.Described polyisocyanates based on the gross weight of the urethane acrylate oligomer of photopolymerization, preferably uses with the amount of 10～40 weight %.
(iii) acrylate alcohol
The acrylate alcohol preferred embodiment (iii) that comprises at least one (methyl) acrylate and oh group comprises (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, vinylformic acid 4-hydroxy butyl ester, neopentyl glycol single (methyl) acrylate, (methyl) vinylformic acid 4-hydroxyl cyclohexyl, 1,6-hexylene glycol list (methyl) acrylate, tetramethylolmethane five (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and their mixture.Described acrylate alcohol based on the gross weight of the urethane acrylate oligomer of photopolymerization, preferably uses with the amount of 10～35 weight %.
(iv) urethane reaction catalyzer
Employed urethane reaction catalyzer preferred embodiment (iv) comprises copper naphthenate, cobalt naphthenate, zinc naphthenate, lauric acid normal-butyl tin, dibutyl tin laurate, triethylamine, 2-methyl triethylene diamide (2-methyltriethylenediamide) and their mixture in urethane reaction.Described urethane reaction catalyzer based on the gross weight of the urethane acrylate oligomer of photopolymerization, preferably uses with the amount of 0.01～1 weight %.
(v) stopper
(preferred embodiment v) comprises quinhydrones, Hydroquinone monomethylether, para benzoquinone, thiodiphenylamine and their mixture to described stopper.Described stopper based on the gross weight of the urethane acrylate oligomer of photopolymerization, preferably uses with the amount of 0.01～1 weight %.
The urethane acrylate oligomer of described photopolymerization (A) can use said components to come as follows to synthesize:
Polyisocyanates is (ii) added in the round-bottomed flask that agitator is housed.When stirring, add (iv) part or all of urethane reaction catalyzer, and slowly add polyol copolymer (i).Make this mixture reaction reach predeterminated level at about 70～80 ℃, thereby obtain carbamate prepolymer up to the NCO of the product that obtains concentration.(v), (iii) slow adding contains in the flask of carbamate prepolymer acrylate alcohol with urethane reaction catalyzer residual content (if necessary) (iv), makes this mixture reaction at 80 ℃ with stopper.Confirm at about 2270cm by infrared spectrometer -1The NCO peak make this reaction terminating after disappearing, thereby obtain the urethane acrylate oligomer of photopolymerization.
(B) reactive monomer
Employed in the present invention have reactive monomer (B) of at least one acrylate-based, methacrylate based or vinyl as thinner, therefore the viscosity that is used for regulating above-mentioned oligopolymer component preferably have 100～300 low number-average molecular weight to suitable level of processing.
Acrylate-based, the methacrylate based or vinyl except at least one, described reactive monomer can also comprise one or more and different functional groups, preferred 1～8 propylidene oxygen base (propylene oxide group) (OC 3H 6-).The reactive monomer of the film with high tensile and low cure shrinkage preferably can be provided especially.Its preferred examples comprises vinylformic acid phenoxy group ethyl ester; the phenoxy group EDIA; phenoxy group TEG acrylate; phenoxy group six EDIAs; isobornyl acrylate (IBOA); isobornyl methacrylate; N-vinyl pyrrolidone (N-VP); N-caprolactam (N-VC); acryloyl morpholine (ACMO); bis-phenol ethoxylation diacrylate; the ethoxylated phenol mono acrylic ester; the poly(oxyethylene glycol) 400 diacrylate; tripropylene glycol diacrylate; TMPTA (TMPTA); polyethyleneglycol diacrylate; oxyethane adduction triethyl propane triacrylate; tetramethylol methane tetraacrylate (PETA); 1; the 4-butylene glycol diacrylate; 1,6 hexanediol diacrylate; the ethoxylation tetramethylol methane tetraacrylate; the ethoxylated nonylphenol acrylate; the 2-phenoxyethyl acrylate; ethoxylated bisphenol a diacrylate; alkoxylate nonylphenol acrylate; alkoxylate trifunctional acrylate; the diacrylate metal-salt; the trifunctional acrylate; trifunctional methacrylic ester and their mixture.
If desired, can also use the monomer of the bond strength of raising and substrate.
Described reactive monomer uses with the amount of 5～60 weight % based on the gross weight of this coating composition.When this measures less than 5 weight %, may be difficult to the viscosity drop of oligopolymer component is low to moderate the level that is suitable for processing, promptly 3,000～10, in the scope of 000cps (25 ℃), and when this amount during greater than 60 weight %, because cure shrinkage high temperature under and thermostability reduce to occur the character of difference, the air spots when becoming big, curing such as high viscosity, particle weighs and light loss.
(C) light trigger
In the present invention, described light trigger (C) is used to help the fast setting speed of resin itself, and keeping and 1,500m/min or higher optical fiber surface covered are synchronous.Described light trigger can form free radical by ultraviolet and attack two keys in the resin to bring out polymerization.Its preferred examples comprises and can buy the Irgacure#184 (hydroxy-cyclohexyl phenyl ketone) that obtains from Ciba Geigy Co; Irgacure#907 (2-methyl isophthalic acid [4-(methylthio group) phenyl]-2-morpholinyl-third-1-ketone); Irgacure#500 (hydroxyketone and benzophenone); Irgacure#651 (benzyl dimethyl ketone); Darocure#11173 (2-hydroxy-2-methyl-1-phenyl-third-1-ketone); Darocure TPO (2; 4,6-trimethylbenzoyl xenyl phosphine oxide); Darocure CGI#1800 (diacyl phosphine oxide) and Darocure CGI#1700 (diacyl phosphine oxide and hydroxy-cyclohexyl phenyl ketone) and their mixture.
Described light trigger uses with the amount of 1～15 weight % based on the gross weight of this coating composition.
(D) amine additive
Nonessential component amine additive is used to prevent the polymerization that coating composition causes because of high temperature or light before curing, the hydrogen after preventing to solidify discharges, and prevents transmission loss, and is used to provide fast setting speed.Its preferred examples comprises diallyl amine, Diisopropylamine, diethylamine, diethylhexyl amine, triethylamine, N methyldiethanol amine, thanomin, diethanolamine and their mixture.Described amine additive preferably uses with the amount of 0.01～0.5 weight % based on the gross weight of this coating composition.
(E) other additive-based on monomer, stablizer or its mixture of silane
In addition, photo curable coating composition of the present invention can comprise monomer, stablizer or its mixture based on silane, with reducing of the bond strength between inhibition coating and the glass fibre substrate.Described monomer based on silane, stablizer or its mixture based on the gross weight of this coating composition, can use with the amount of 1～5 weight %.When this amount is outside above-mentioned scope, curing speed may take place reduce.
Described monomer based on silane plays bond strength that improves between coating and the glass fibre substrate and the effect that reduces the water-intake rate of resin combination.Should comprise vinyltrimethoxy silane (can obtain), vinyltrimethoxy silane (can obtain), vinyl three (methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxy propyl group methoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan and their mixture based on the monomeric representative example of silane from other company from Chisso Co. (Japan) purchase.
Described stablizer plays the effect of heat, oxidation and the stability in storage of improving coating composition, its representational example comprises and can buy Irganox 1010, Irganox 1035 and the Irganox 1076 that obtains from Ciba Geigy Co, and their mixture.
The preparation method of photo curable coating composition of the present invention is as follows:
Urethane acrylate oligomer (A), reactive monomer (B), light trigger (C), nonessential amine additive (D) and other additive (E) of photopolymerization are added in the reactor.By using dispersion impeller, stir this mixture under 000rpm or the higher uniform acceleration in 15～50 ℃ temperature, 60% or be lower than 60% humidity and 1.When this is reflected at when carrying out under the temperature that is lower than 15 ℃, the viscosity of the urethane acrylate oligomer of photopolymerization (A) reduces, cause technology to have some setbacks, and be reflected at when carrying out under the temperature that is higher than 50 ℃ when this, light trigger (C) may cause undesirable curing owing to the formation of free radical.Be higher than when carrying out under 60% the humidity when this is reflected at, bubble may produce from resin combination during follow-up coating process, and the side reaction of non-reactant and airborne reaction of moisture may take place.In addition, when being lower than 1, when stirring this mixture under the speed of 000rpm, may obtain not satisfied mixing.
Coating composition of the present invention is used to prepare coating or film, and this coating or film have following feature:
If said composition is used to prepare the thick film of coating on the glass fibre substrate of 10～30 μ m by curing,, still keep closely being adhered on glass even then this film immerses in 45～85 ℃ the water after (for example, 60 days) for a long time at least.If said composition is used to prepare the thick film of coating on the glass fibre substrate of 100 μ m by curing, then 2.5% secant modulus of this film is 0.1～0.3kgf/mm 2, and with the bond strength of glass fibre substrate be 1～3N (newton).
By coating composition of the present invention is coated on the glass fibre, and solidify this coating (referring to Fig. 1), can prepare optical fiber with 10～30 μ m thickness coatings by rayed (being exposed to ultraviolet lamp).When solidifying with ultraviolet lamp, can use light intensity is 0.5～3J/cm 2And speed is the D bulb of 30～150fpm.
Optical fiber by method for preparing has improved hot water resistance, even also do not cause for a long time in the hot water that when immersing loss of optical signal or bond strength reduce.Therefore, optical fiber of the present invention shows improved heat, machinery and chemical stability, particularly, does not have delamination at least when long-time (for example, 60 days) in immersing 45～85 ℃ water.
Following examples are intended to further specify the present invention and do not limit its scope.
Preparation embodiment 1: the preparation of the urethane acrylate oligomer of photopolymerization (A)
With 138.32g (0.62 mole) isoflurane chalcone diisocyanate (IPDI; Lyondell chemical Co.) and 0.17g dibutyl tin laurate (Songwon industrial Co.) add and to be equipped with in the 2L round-bottomed flask of agitator.With this mixture heating up to 80 ℃, and with 109.03g (0.11 mole) number-average molecular weight 1000 polytetramethylene glycol polyvalent alcohol (PTMG; BASF Co.) adds wherein.Add finish after, the NCO concentration (being 8.67% in theory) of the product that obtains is adjusted to 7.5～8.5%.In addition, with the number-average molecular weight of 716.50g (0.36 mole) be 2000 polypropylene glycol polyvalent alcohol (PPG; Korea Polyol Co.) adds wherein.Add finish after, the NCO concentration (being 1.07% in theory) of the product that obtains is adjusted to 0.7～1.0%, thereby obtains carbamate prepolymer.With 2.15g Hydroquinone monomethylether (HQMME; Eastman Co.), 37.96g (0.33 mole) vinylformic acid 2-hydroxy methacrylate (2-HEA; Nippon shokubai Co.) and the 0.1g dibutyl tin laurate slowly add wherein.Make this mixture reaction 1 hour at 80 ℃.Confirm 2270cm by infrared spectrometer -1The NCO peak make reaction terminating after disappearing, thereby obtain the urethane acrylate oligomer of photopolymerization.The number-average molecular weight of the oligopolymer that obtains above is 23, and 000g/mol (determining by gel permeation chromatography (GPC)) is 14 25 ℃ viscosity, 000cps, and average carbamate bond number is 4.
Preparation embodiment 2
With 121.55g isoflurane chalcone diisocyanate (IPDI; Lyondell chemical Co.) and 0.17g dibutyl tin laurate (Songwon industrial Co.) add and to be equipped with in the 2L round-bottomed flask of agitator.With this mixture heating up to 80 ℃, and with the 112.13g number-average molecular weight 850 polytetramethylene glycol polyvalent alcohol (PTMG; Hodogaya Co.) adds wherein.Add finish after, the NCO concentration (being 8.97% in theory) of the product that obtains is adjusted to 7.5～8.5%.In addition, with the 755.33g number-average molecular weight be 2000 polypropylene glycol polyvalent alcohol (PPG; Korea Polyol Co.) adds wherein.Add finish after, the NCO concentration (being 1.08% in theory) of the product that obtains is adjusted to 0.7～1.0%, thereby obtains carbamate prepolymer.With 2.15g Hydroquinone monomethylether (HQMME; Eastman Co.), 38.51g vinylformic acid 2-hydroxy methacrylate (2-HEA; Nippon shokubai Co.) and the 0.1g dibutyl tin laurate slowly add wherein.Make this mixture reaction 1 hour at 80 ℃.Confirm 2270cm by infrared spectrometer -1The NCO peak make reaction terminating after disappearing, obtain the urethane acrylate oligomer of photopolymerization.The number-average molecular weight of the oligopolymer that obtains above is 21, and 000g/mol (determining by gel permeation chromatography (GPC)) is 12 25 ℃ viscosity, 100cps, and average carbamate bond number is 4.
Preparation embodiment 3
With 115.24g isoflurane chalcone diisocyanate (IPDI; Lyondell chemical Co.) and 0.17g dibutyl tin laurate (Songwon industrial Co.) add and to be equipped with in the 2L round-bottomed flask of agitator.With this mixture heating up to 80 ℃, and with the 102.15g number-average molecular weight 650 polytetramethylene glycol polyvalent alcohol (PTMG; Korea Polyol Co.) adds wherein.Add finish after, the NCO concentration (being 8.97% in theory) of the product that obtains is adjusted to 7.5～8.5%.In addition, with the 760.50g number-average molecular weight be 2000 polypropylene glycol polyvalent alcohol (PPG; Korea Polyol Co.) adds wherein.Add finish after, the NCO concentration (being 1.08% in theory) of the product that obtains is adjusted to 0.7～1.0%, thereby obtains carbamate prepolymer.With 2.15g Hydroquinone monomethylether (HQMME; Eastman Co.), 39.11g vinylformic acid 2-hydroxy methacrylate (2-HEA; Nippon shokubai Co.) and the 0.1g dibutyl tin laurate slowly add wherein.Make this mixture reaction 1 hour at 80 ℃.Confirm 2270cm by infrared spectrometer -1The NCO peak make reaction terminating after disappearing, obtain the urethane acrylate oligomer of photopolymerization.The number-average molecular weight of the oligopolymer that obtains above is 21, and 000g/mol (determining by gel permeation chromatography (GPC)) is 12 25 ℃ viscosity, 000cps, and average carbamate bond number is 4.
Comparative preparation embodiment 1
150.0g (2 moles) sec.-propyl vulcabond and the adding of 0.05g dibutyl tin laurate are equipped with in the 3L round-bottomed flask of agitator.With this mixture heating up to 80 ℃, and be that admixtured polyether/ester polyol of 2000 adds wherein with 771.0g (1 mole) number-average molecular weight.Add finish after, the NCO concentration (being 0.6% in theory) of the product that obtains is adjusted to 0.1～0.3%, thereby obtains carbamate prepolymer.2.13g Hydroquinone monomethylether (HQMME) and 78.0g (1 mole) vinylformic acid 2-hydroxy methacrylate are slowly added wherein.Make this mixture reaction 3 hours at 80 ℃.Confirm 2270cm by infrared spectrometer -1The NCO peak make reaction terminating after disappearing, obtain the urethane acrylate oligomer of photopolymerization.The number-average molecular weight of the oligopolymer that obtains above is 22, and 000g/mol (determining by gel permeation chromatography (GPC)) is 15 25 ℃ viscosity, 200cps, and average carbamate bond number is 4.
Comparative preparation embodiment 2
136.84g sec.-propyl vulcabond and the adding of 0.05g dibutyl tin laurate are equipped with in the 2L round-bottomed flask of agitator.With this mixture heating up to 80 ℃, and with the 821.86g number-average molecular weight 2000 polytetramethylene glycol polyvalent alcohol (PTMG; BASF Co.) adds wherein.Add finish after, the NCO concentration (being 0.6% in theory) of the product that obtains is adjusted to 0.4～0.6%, thereby obtains carbamate prepolymer.2.01g Hydroquinone monomethylether (HQMME) and 41.1g vinylformic acid 2-hydroxy methacrylate are slowly added wherein.Make this mixture reaction 3 hours at 80 ℃.Confirm 2270cm by infrared spectrometer -1The NCO peak make reaction terminating after disappearing, obtain the urethane acrylate oligomer of photopolymerization.The number-average molecular weight of the oligopolymer that obtains above is 24, and 000g/mol (determining by gel permeation chromatography (GPC)) is 18 25 ℃ viscosity, 200cps, and average carbamate bond number is 4.
Embodiment 1 to 9 and comparing embodiment 1 to 6
According to the amount shown in the table 1, urethane acrylate oligomer and other composition for preparing each photopolymerization of preparation in embodiment 1～3 and comparative preparation embodiment 1 and 2 is mixed together, make multiple photo curable coating composition.
Figure BDA0000050260450000101
Experimental example:The evaluation of photo curable coating composition character
In order to check the physical properties and the hot water resistance of the photo curable coating composition of preparation in embodiment 1～9 and the comparing embodiment 1～6, according to the viscosity of having measured these compositions as described below and the tensile strength after solidifying, with bond strength, second-order transition temperature and the hot water resistance of glass fibre substrate, it the results are shown in the table 2.
(1) viscosity
According to ASTM D-2196, use Brookfield DV III+ viscometer, #31 rotor (spindle) with the moment of torsion in 50～90% scopes, is measured the viscosity of composition sample.
(2) tensile strength after the curing: 2.5% secant modulus
Having fixed thickness by use is that the metering bar coater of 7～10mil is coated composition sample on 20 * 20cm sheet glass.After putting into fixed frame, by using 600W and 9mm D bulb (model DRS10/12-QN; Fusion Co.) with 2.5J/cm 2Light intensity and the speed of the 30fpm film that under nitrogen (40lpm), makes coating solidify, thereby obtain the thick film of solidified 100 μ m.This solidified film is separated with sheet glass, and by using the JDC cutting unit to be cut into the film of 13mm width.In the moisture eliminator of 23 ℃ and RH 50% with the membrane equilibrium of this well cutting one day.Then, use 4443UTM (Instron Co.) to measure 2.5% secant modulus with the speed membrane of 25mm/min.
(3) bond strength of curing back and glass fibre substrate
Have fixed thickness and composition sample is coated on 20 * 20cm sheet glass by using as the metering bar coater of 5mil.Then, coating thickness is second coating of 10mil thereon.After putting into fixed frame, by using 600W and 9mm D bulb (model DRS10/12-QN; Fusion Co.) with 2.5J/cm 2Light intensity and the speed of the 30fpm film that under nitrogen (40lpm), makes this coating solidify, thereby obtain the thick film of solidified 100 μ m.The solidified film is separated with sheet glass, and by using the JDC cutting unit to be cut into the film of 20mm width.In the moisture eliminator of 23 ℃ and RH 50% with the membrane equilibrium of this well cutting one day.Then, by using 4443UTM (Instron Co.) to measure bond strength with the glass fibre substrate with the speed membrane of 90 ° angles and 25mm/min.
(4) second-order transition temperature (Tg)
By using metering bar coater composition sample is coated on 20 * 20cm sheet glass.After putting into fixed frame, by using 600W and 9mm D bulb (model DRS10/12-QN; Fusion Co.) with 2.5J/cm 2Light intensity and the film curing that will be coated with down of the speed of 30fpm at nitrogen (40lpm), thereby obtain the thick film of solidified 600 μ m.The solidified film is cut into the film of long 15mm and wide 10mm.The film of this well cutting is placed DMTA IV (dynamic mechanically temperature analysis; Rheometry) in, and with the input of the geometry value of film wherein.By film being cooled to-100 ℃ approximately, then it is heated to about 60 ℃ and measure with 2 ℃/min.Test frequency is 1.0 radian per seconds.Calculate second-order transition temperature by the tangent Δ peak (tan delta peak) in the graphic representation that obtains.
(5) hot water resistance
With diameter is that the glass fibre of 125 μ m passes the syringe (2mL) that contains coating composition, and with the glass fibre ultra-violet curing of coating, as shown in Figure 1.Ultra-violet curing uses the D bulb of Fusion ultraviolet instrumentation at 1.0J/cm 2Carry out under the light intensity in (UVA zone) and the speed of 150fpm.The thickness of this coating is in the scope of 10～30 μ m.
In order to check the hot water resistance of above-mentioned coating, will being coated with also, the solidified fiber immerses in 45,65 and 85 ℃ of water separately.After immersing 10,30 and 60 days, from water, pull out fiber, at room temperature dry 10 minutes and be cut into the fragment of long 10cm.Then, to the interface between ten fiber fragment sight glass fibers and the coating, infiltrate the number of drops at interface by opticmicroscope (200 x magnification) with calculating.
Figure BDA0000050260450000131
Figure BDA0000050260450000141
As shown in table 2, the coating that makes by the composition of embodiment 1～9, even after in long-time immersion hot water, still show high hot water resistance and with the bond strength of glass fibre substrate, and those coatings that make by the composition of comparing embodiment 1～6, along with dipping time and glass fibre substrate separation (delamination).
In addition, the result who relatively comes from embodiment 1～9, the increase of amount that confirms the urethane acrylate oligomer of photopolymerization causes the reduction of second-order transition temperature (it is provided at the effect that the light loss that prevents in the final optical fiber low temperature under increases), with the bond strength increase of glass fibre substrate and at 0.2kgf/mm 2Or less than 0.2kgf/mm 2Secant modulus in the scope increases.
Although described the present invention about above-mentioned specific embodiments, should be realized that those skilled in the art can make numerous modifications and variations to the present invention, this also falls in the scope of the present invention that is defined by the following claims.

Claims (16)

1. photo curable coating composition comprises:
(A) urethane acrylate oligomer of the use polyol copolymer of 30～90 weight %, polyisocyanates, acrylate alcohol, urethane reaction catalyzer and the photopolymerization of stopper synthetic;
(B) reactive monomer that contains at least one acrylate, methacrylic ester or vinyl groups of 5～60 weight %; With
(C) light trigger of 1～15 weight %.
2. composition according to claim 1, wherein, in component (A), based on the gross weight of the urethane acrylate oligomer of described photopolymerization, described polyol copolymer, polyisocyanates, acrylate alcohol, urethane reaction catalyzer and stopper use with the amount of 30～75 weight %, 10～40 weight %, 10～35 weight %, 0.01～1 weight % and 0.01～1 weight % respectively.
3. composition according to claim 1, wherein, the number-average molecular weight of the urethane acrylate oligomer of described photopolymerization is 5,000～50, in 000 the scope.
4. composition according to claim 1, wherein, the urethane acrylate oligomer of described photopolymerization is that 10: 90～30: 70 polyether glycol and polyester polyol formed by weight ratio.
5. composition according to claim 1, wherein, the number-average molecular weight of described polyol copolymer is 100～10, in 000 the scope and comprise-CH 2CH 2O-or-CH 2CH (CH 2CH 3) the O-repeating unit.
6. composition according to claim 1, wherein, described reactive monomer has 1～8 propylidene oxygen base (OC 3H 6-) functional group.
7. composition according to claim 1; wherein; described reactive monomer is selected from vinylformic acid phenoxy group ethyl ester; the phenoxy group EDIA; phenoxy group TEG acrylate; phenoxy group six EDIAs; isobornyl acrylate; isobornyl methacrylate; the N-vinyl pyrrolidone; the N-caprolactam; acryloyl morpholine; bis-phenol ethoxylation diacrylate; the ethoxylated phenol mono acrylic ester; the poly(oxyethylene glycol) 400 diacrylate; tripropylene glycol diacrylate; TMPTA; polyethyleneglycol diacrylate; oxyethane adduction triethyl propane triacrylate; tetramethylol methane tetraacrylate; 1; the 4-butylene glycol diacrylate; 1,6 hexanediol diacrylate; the ethoxylation tetramethylol methane tetraacrylate; the ethoxylated nonylphenol acrylate; the 2-phenoxyethyl acrylate; ethoxylated bisphenol a diacrylate; alkoxylate nonylphenol acrylate; alkoxylate trifunctional acrylate; the diacrylate metal-salt; the trifunctional acrylate; in trifunctional methacrylic ester and their mixture.
8. composition according to claim 1, it also comprises: the amine additive of 0.01～0.5 weight %, or the monomer of 1～5 weight %, stablizer or their mixture based on silane, or above-mentioned both.
9. composition according to claim 8, wherein, described amine additive is selected from diallyl amine, Diisopropylamine, diethylamine, diethylhexyl amine, triethylamine, N methyldiethanol amine, thanomin, diethanolamine and their mixture.
10. composition according to claim 1, wherein, described composition is used for preparing the thick film of coating on the glass fibre substrate of 10～30 μ m by solidifying, and this film keeps closely being adhered on glass in immersing 45～85 ℃ of water at least after 60 days.
11. composition according to claim 1, wherein, described composition is used for preparing the thick film of coating on the glass fibre substrate of 100 μ m by solidifying, and 2.5% secant modulus of this film is at 0.1～0.3kgf/mm 2Scope in.
12. composition according to claim 1, wherein, described composition is used for preparing the thick film of coating on the glass fibre substrate of 100 μ m by solidifying, and the bond strength of this film and glass is 1～3N (newton).
13. an optical fiber comprises the coating of coating on the glass fibre and this coating curing being made by with the described photo curable coating composition of claim 1.
14. optical fiber according to claim 13, wherein, the thickness of described coating is in the scope of 10～30 μ m.
15. optical fiber according to claim 14, wherein, described coating keeps closely being adhered on glass in immersing 45～85 ℃ of water at least after 60 days.
16. optical fiber according to claim 13, wherein, the curing of described photo curable coating composition is 0.5～3J/cm by being exposed to light intensity 2And speed is that the D bulb of the ultraviolet lamp of 30～150fpm carries out down.
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