CN1320017C - Radiation-curable resin composition - Google Patents
Radiation-curable resin composition Download PDFInfo
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- CN1320017C CN1320017C CNB2003801063811A CN200380106381A CN1320017C CN 1320017 C CN1320017 C CN 1320017C CN B2003801063811 A CNB2003801063811 A CN B2003801063811A CN 200380106381 A CN200380106381 A CN 200380106381A CN 1320017 C CN1320017 C CN 1320017C
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Abstract
A radiation-curable resin composition comprising (A) 0.1-10 wt% of a compound including a phosphite group and a phenolic hydroxyl group was found to have excellent storage stability, produces a cured product which excels in durability and generates only a small amount of hydrogen gas, and is useful for coating optical fiber.
Description
Technical field
The present invention relates to the resin combination of radiation-hardenable.The invention still further relates to the application of this radiation-curable resin composition, through the production method of painting optic fibre, the coating composition system, through the optical fiber of coating, fibre ribbon, optical fiber cable and compound are as the application of component in the radiation-curable resin composition.
Background technology
In the production of optical fiber, the glass fibre that obtains by the spinning melten glass is coated with and is used for protection and enhanced resin.As resin coating, knownly wherein be formed with flexible primary coating on the optical fiber surface and on this primary coating, be formed with the structure of the secondary coating of inflexible.Glass fibre with primary and secondary coating is called as optical fiber.It also is known will having wherein that resin-coated optical fiber side by side arranges in one plane and use Strapping Material fixed fibre ribbon.The resin combination that is used to form primary coating is called as primary material, and the resin combination that is used to form secondary coating is called as secondary materials, and the resin combination that is used as the fibre ribbon Strapping Material is called as the ribbon matrix material.Method as resin-coated is coated to radiation-curable resin composition on the optical fiber, and by apply heat or light particularly ultraviolet ray come the method for curing composition to be widely used.
Along with time lapse, the coating of optical fiber can produce hydrogen.Hydrogen may cause the generation of optical propagation loss.If optical fiber is placed under the high temperature for a long time, conventional radiation-curable resin composition coating possibility deterioration, thus cause fiber strength to descend.
Prevent that as being used for fibre coating from producing the method for hydrogen, contains the raw-material method of the ethylenic insatiable hunger group with ad hoc structure from the known utilization of JP-A-9143233.But, because this method has limited the raw-material selection that is used for the fibre coating material, so the degree of freedom of relevant this material design is restricted.
JP-A-6372740 discloses the method for the phosphorus compound that adds phosphorous acid phenylbenzene isodecyl ester for example or tricresyl phosphite (nonyl benzene) ester in resin combination.But the radiation-curable resin composition package stability that this method obtains is poor.Therefore, radiation-curable resin composition by long time stored situation under, the amounts of hydrogen that produces from the solidifying product of said composition can increase.And, the solidifying product poor durability, particularly poor heat resistance of the radiation-curable resin composition that obtains by above method.Therefore, if this solidifying product is placed under the high temperature for a long time, the weight of solidifying product can change.
The radiation-curable resin composition that the purpose of this invention is to provide a kind of package stability excellence, it can generate excellent in te pins of durability, only produce small quantity of hydrogen and can be used as the solidifying product of fibre coating.
Another object of the present invention provides a kind of coating composition system of package stability excellence, and it can generate excellent in te pins of durability, only produce small quantity of hydrogen and can be used as the solidifying product of fibre coating.
Another object of the present invention is to use described radiation-curable resin composition as the coating material in primary coating, secondary coating, ink composite or the body material on the optical glass fibre.
Another object of the present invention provides production through the optical fiber of coating or the method for fibre ribbon or optical fiber cable.
Another object of the present invention provides and comprises that at least one is by utilizing optical fiber or fibre ribbon or the optical fiber cable through coating according to the resulting coating of radiation-curable resin composition of the present invention.
Embodiment
Now unexpectedly found to comprise the radiation curable resins of the compound (A) that contains phosphorous acid ester group and phenolic hydroxyl by use, can obtain the radiation-curable resin composition of package stability excellence, it can generate excellent in te pins of durability, particularly excellent heat resistance, even and the solidifying product long storage also only produce the solidifying product of small quantity of hydrogen.Radiation-curable resin composition of the present invention is suitable as the coated material of optical fiber, particularly as the primary material of fibre coating, secondary coated material, ribbon matrix material or ink material.
To component utilized (A) in radiation-curable resin composition of the present invention without limits, as long as component (A) is the compound that contains phosphorous acid ester group and phenolic hydroxyl.For example, component (A) can be the compound shown in the following formula (2):
(R
1O)
nP(OR
2)
3-n (2)
Wherein n is the integer of 1-3, R
1Expression comprises the organic group of phenolic hydroxyl, R
2Expression can comprise the organic group of phosphorus atom.
If use R more than one
1And/or R
2, these groups can be identical or different.R
1And R
2Can comprise carbon element in addition.Element example as beyond the carbon can provide nitrogen, sulphur, oxygen, halogen and phosphorus.At least two R
1And R
2Can form cyclic organic group by bonding.
As by R
1The organic group example that contains phenolic hydroxyl of expression can provide hydroxyl phenylic group, hydroxyl naphthyl group or hydroxyl group, and wherein phenyl ring or naphthalene nucleus can be replaced by 1～3 alkyl group, alkoxy base or halogen atom.As by R
2The organic group example of expression can provide alkyl, aryl, aralkyl etc.As the aryl example, can provide can be by one or more phenyl or naphthyls that substituting group replaced that are selected from alkyl, alkoxy or halogen atom.As the aralkyl example, can provide can be by one or more phenylalkyl groups that substituting group replaced that are selected from alkyl, alkoxy or halogen atom.R
1Can be bonded to R
2As R
2The situation that comprises phosphorus atom can provide the situation that is bonded to divalence～tetravalence alkane residue or divalence～tetravalence aromatic hydrocarbons residue comprising 2～4 phosphorous acid esters of phenolic hydroxyl.
Specific examples as the compound that contains phosphorous acid ester group and phenolic hydroxyl (A), can provide phosphorous acid 2-methyl-4-hydroxy phenyl diethyl ester, phosphorous acid 2-tert-butyl-hydroxy phenyl diethyl ester, phosphorous acid 2,5-di-tert-butyl-hydroxy phenyl diethyl ester, phosphorous acid two (2, the 5-di-tert-butyl-hydroxy phenyl) ethyl ester, tricresyl phosphite (2, the 5-di-tert-butyl-hydroxy phenyl) ester, diphosphorous acid four (2, the 5-di-tert-butyl-hydroxy phenyl) 2,5-di-t-butyl-Ya quinhydrones base ester is as shown in the formula the compound shown in (1) and (3)～(9).
By " Polymer Degradation and Stability ", 77 (2002), p.29 the method described in can be synthesized the compound (A) that contains phosphorous acid ester group and phenolic hydroxyl.As the compound commercial examples that contains phosphorous acid ester group and phenolic hydroxyl, can provide Sumilizer GP (by Sumitomo Chemical Industries Co., Ltd. produces).
As the particularly preferred compound (A) that contains phosphorous acid ester group and phenolic hydroxyl, can provide as shown in the formula the compound shown in (1) or (3).
From the effect of stability, weather resistance and minimizing hydrogen generating quantity, preferably component (A) is added to according in the radiation-curable resin composition of the present invention with the amount of 0.1～10wt%.The amount of component (A) is 0.1～5wt% more preferably, is preferably 0.1～3wt% especially.
Radiation-curable resin composition of the present invention preferably also comprise (B) carbamate (methyl) acrylate and (C) can with the reactive thinner of component (B) copolymerization.For carbamate (methyl) acrylate (B), be not particularly limited.For example, carbamate (methyl) acrylate (B) by (a) many alkylol cpds, (b) polyisocyanate compound and (c) reaction of hydroxyl (methyl) acrylic compound obtain.
As carbamate (methyl) acrylate (B) preparation method's specific examples, can provide all methods that react of (methyl) acrylate (c) with many alcohol (a), polyisocyanate compound (b) and hydroxyl; Will many alcohol (a) and polyisocyanate compound (b) reaction, the method that (methyl) acrylate (c) of products therefrom and hydroxyl is reacted again; With (methyl) acrylate (c) reaction of polyisocyanate compound (b) and hydroxyl, again with the method for products therefrom with many alcohol (a) reaction; With the reaction of (methyl) acrylate (c) of polyisocyanate compound (b) and hydroxyl, with products therefrom and many alcohol (a) reaction, the method that (methyl) acrylate (c) of products therefrom and hydroxyl is reacted again; Deng.
Example as many alcohol (a), but can provide the polyether glycol that the ring-opening polymerization by a kind of ionic polymerization ring compound obtains, for example polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-hexylene glycol, poly-heptanediol and poly-decanediol, but and the polyether glycol that obtains of the ring opening copolymer by two or more ionic polymerization ring compounds etc.But example as the ionic polymerization ring compound, can provide cyclic ethers, oxyethane for example, propylene oxide, the 1-butylene oxide ring, the epoxy Trimethylmethane, trimethylene oxide, 3,3-dimethyl trimethylene oxide, 3,3-dichloromethyl trimethylene oxide, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, the 3-methyltetrahydrofuran, dioxane, trioxane, four amylene oxide, cyclohexene oxide, Styrene oxide 98min., Epicholorohydrin, glycidyl methacrylate, allyl glycidyl ether, the allyl glycidyl carbonic ether, butadiene monoxide, one oxidation isoprene, the vinyl trimethylene oxide, the vinyl tetrahydrofuran (THF), the vinyl cyclohexene oxide, phenylglycidyl ether, butyl glycidyl base ether and phenylformic acid glycidyl ester.But can use by annular lactone acid or dimethyl annular polysiloxane and carry out the polyether glycol that ring opening copolymer obtains epimino, for example γ-propiolactone or the glycollide of these ionic polymerization ring compounds and for example ethyleneimine.But, can provide the terpolymer etc. of combination, tetrahydrofuran (THF), 1-butylene oxide ring and oxyethane of combination, 1-butylene oxide ring and oxyethane of combination, propylene oxide and oxyethane of combination, tetrahydrofuran (THF) and oxyethane of combination, tetrahydrofuran (THF) and 3-methyltetrahydrofuran of combination, tetrahydrofuran (THF) and the 2-methyltetrahydrofuran of tetrahydrofuran (THF) and propylene oxide as the specific examples of two or more ionic polymerization ring compound combination.But the ring opening copolymer thing of these ionic polymerization ring compounds can be random copolymers or segmented copolymer.In these polyether glycols, from frost resistance and water-proof viewpoint are provided for solidifying product of the present invention, polypropylene glycol is preferred.By the definite polystyrene conversion number-average molecular weight of gel permeation chromatography (GPC) is that 1000～7000 polypropylene glycol is particularly preferred.
Commercial examples as these polyether glycols, can provide PTMG650, PTMG1000, PTMG2000 (making) by Mitsubishi Chemical Corp., EXCENOL 1020,2020,3020, PREMINOL PML-4002, PML-5005 is (by Asahi Glass Co., Ltd. make), UNISAFE DC1100, DC1800, DCB1000 is (by Nippon Oil and FatsCo., Ltd. make), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PTG2000, PTG-L1000, PTG-L2000 is (by HodogayaChemical Co., Ltd. make), Z-3001-4, Z-3001-5, PBG2000 (by DaiichiKogyo Seiyaku Co., Ltd. makes), ACCLAIM 2200,2220,3201,3205,4200,4220,8200,12000 (making) etc. by Lyondell.
As the preferred above polyether glycol of many alcohol.In addition, polyester glycol, polycarbonate diol, polycaprolactone glycol etc. can use separately or unite use with polyether glycol.Polymerization methods for these structural units does not have specific limited, can be any of random polymerization, block polymerization or graft polymerization.
As being used for polyisocyanate compound (b) example of synthesis of carbamates (methyl) acrylate (B), can provide aromatic diisocyanate, alicyclic diisocyanate, aliphatic vulcabond etc.As long as compound can be used on the resin combination that is used for optical fiber, (b) just do not have specific limited to polyisocyanates.Wherein, preferably aromatic diisocyanate and alicyclic diisocyanate, more preferably 2,4 toluene diisocyanate and isophorone diisocyanate.These diisocyanate cpds can use separately or two or morely unite use.
As being used for hydroxyl (methyl) acrylate (c) example of synthesis of carbamates (methyl) acrylate (B), in view of with the reactivity of the isocyanate groups of polyisocyanates, preferred wherein hydroxyl bond be incorporated into hydroxyl (methyl) acrylate (hereinafter referred to as " containing primary hydroxyl (methyl) acrylate ") of primary carbon atom and wherein hydroxyl bond be incorporated into hydroxyl (methyl) acrylate (hereinafter referred to as " containing secondary hydroxyl (methyl) acrylate ") of secondary carbon(atom).
As the example that contains primary hydroxyl (methyl) acrylate, can provide (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, 1,6-hexylene glycol list (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, neopentyl glycol single (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolethane two (methyl) acrylate etc.
As the example that contains secondary hydroxyl (methyl) acrylate, can provide (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 4-hydroxyl cyclohexyl etc.Other example comprises the compound that obtains by (methyl) vinylformic acid and the addition reaction that contains glycidyl compound (for example alkyl glycidyl base ether, allyl glycidyl ether or (methyl) glycidyl acrylate etc.).(methyl) acrylic compound of these hydroxyls can use separately or two or morely unite use.
Be used for synthesis of carbamates (methyl) acrylate (B) many alcohol (a), polyisocyanate compound (b) and hydroxyl (methyl) acrylate make the monovalent hydroxyl that manys in the alcohol for being included in than preferably being determined to be, the isocyanate groups that is included in the polyisocyanate compound is respectively 1.1～2 equivalents and 0.1～1 equivalent with the hydroxyl that is included in hydroxyl (methyl) acrylate.
In addition, diamines can be used to many alcohol synthesis of carbamates (methyl) acrylate (B).As the example of diamines, can provide for example quadrol, tetramethylene-diamine, hexamethylene-diamine, Ursol D and 4, the diamines of 4 '-diaminodiphenyl-methane and contain heteroatomic diamines, polyether diamine etc.
Part in (methyl) acrylate of hydroxyl can be replaced by and have and can or replace with alcohol with the compound of the functional group of isocyanate groups addition.As have can with the examples of compounds of the functional group of isocyanate groups addition, can provide γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan etc.The use of this compound can further improve the adhesion to the base material of for example glass.As the example of alcohol, can provide methyl alcohol, ethanol, Virahol, propyl carbinol, the trimethyl carbinol etc.By using these compounds, the Young's modulus that can regulate resin.
In carbamate (methyl) acrylate (B) synthetic, the preferred urethane catalyzer that accounts for reagent total amount 0.01～1wt% that uses, for example copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyl tin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane or 2,6,7-trimethylammonium-1,4-diazabicyclo [2.2.2] octane.Temperature of reaction is generally 5～90 ℃, preferred 10～80 ℃.
The definite polystyrene conversion number-average molecular weight of GPC of passing through of carbamate (methyl) acrylate (B) is generally 500～40,000, preferred 700～30,000, so that guarantee that solidifying product has good elongation at break and guarantee that radiation-curable resin composition of the present invention has suitable viscosity.
The content of the carbamate in the radiation-curable resin composition of the present invention (methyl) acrylate (B) is preferably 35～85%, be preferably 55～65% especially, has excellent mechanical characteristics so that guarantee solidifying product, as Young's modulus and elongation at break, and guarantee that radiation-curable resin composition of the present invention has suitable viscosity.If this content surpasses 85wt%, because solidifying product shows the Young's modulus greater than 2.0MPa, so said composition is not suitable for use in the resin of painting optic fibre.And the viscosity of radiation-curable resin composition surpasses 6.0Pas, thereby causes workability to reduce.And, the water tolerance deterioration of solidifying product.If this content is less than 35wt%, then breaking tenacity reduces.The Young's modulus that is used as the solidifying product of optical fiber primary layer is preferably 0.1～2.0MPa.The viscosity of this radiation-curable resin composition is preferably 1.0～6.0Pas.
Be used in component (C) in the radiation-curable resin composition of the present invention and be can with the reactive thinner of component (B) copolymerization.As the example of component (C), can provide (C1) polynierizable monofunctional compounds or (C2) polymerizable polyfunctional compound.As the example of polynierizable monofunctional compounds (C1), can provide the lactan that contains vinyl, for example N-vinyl pyrrolidone and N-caprolactam; (methyl) acrylate that contains alicyclic structure, for example (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid three ring (tricyclodecanyl) ester in the last of the ten Heavenly stems and (methyl) vinylformic acid dicyclo penta (dicyclopentanyl) esters; (methyl) benzyl acrylate, (methyl) vinylformic acid 4-butyl cyclohexyl, acryloyl morpholine, vinyl imidazole, vinyl pyridine etc.Other example comprises (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) butoxyethyl acrylate, (methyl) vinylformic acid oxyethyl group binaryglycol ester, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid ethoxy ethyl ester, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, diacetone (methyl) acrylamide, isobutoxy methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, uncle's octyl group (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid 7-amino-3,7-dimethyl monooctyl ester, N, N-diethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, the hydroxybutyl vinyl ether, the lauryl vinyl ether, cetyl vinylether, 2-ethylhexyl vinyl ether, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester and the compound that is shown below:
CH
2＝C(R
3)-COO(R
4O)p-C
6H
4-R
5
R wherein
3Expression hydrogen atom or methyl, R
4Expression has 2～6, the alkylidene group of preferred 2～4 carbon atoms, R
5Expression hydrogen atom or have 1～12, the alkyl of preferred 1～9 carbon atom, p is 0～12, preferred 1～8 integer.
In these polynierizable monofunctional compounds (C1), preferably contain the lactan of vinyl, for example N-vinyl pyrrolidone and N-caprolactam, and simple function (methyl) acrylate that contains aliphatic hydrocarbyl with 10 or more carbon atoms.Fat base with 10 or more carbon atoms can be linear, branched or alicyclic ring.Carbonatoms is preferably 10～24.Wherein, more preferably (methyl) isobornyl acrylate, (methyl) isodecyl acrylate and (methyl) lauryl acrylate.Particularly preferred compound is (methyl) isobornyl acrylate and/or (methyl) isodecyl acrylate.Commercial examples as these polynierizable monofunctional compounds (C1), can provide IBXA (by OsakaOrganic Chemical Industry Co., Ltd. manufacturing), Aronix M-110, M-111, M-113, M-114, M-117 and TO-1210 are (by Toagosei Co., Ltd. make) and EpoxyEster M-600A (by Kyoeisha Chemical Co., Ltd. makes).
As long as compound can be used on the resin combination that is used for optical fiber, polymerizable polyfunctional compound (C2) just there is not specific limited.Preferred embodiment comprises two (methyl) acrylate, three (2-hydroxyethyl) chlorinated isocyanurates three (methyl) acrylate and the hexanediyl ester (HDDA) of polyethyleneglycol diacrylate, three ring subunit dimethylene in the last of the ten Heavenly stems two (methyl) acrylate, oxyethane addition dihydroxyphenyl propane.Commercial examples as polymerizable polyfunctional compound (C2), can provide Light acrylate 9EG-A, 4EG-A (by Kyoeisha Chemical Co., Ltd. manufacturing), Yupimer UV, SA 1002 (making) and Aronix M-215, M-315, M-325 (by Toagosei Co., Ltd. makes) by Mitsubishi Chemical Corp..
Polynierizable monofunctional compounds (C1) can be united use with polymerizable polyfunctional compound (C2).
Component (C) is added in the radiation-curable resin composition of the present invention with the amount of preferred 1～60wt%, preferred especially 2～45wt%.If this amount is lower than 1wt%, may damage curability.If should measure greater than 60wt%, because viscosity is low, it is inhomogeneous that coating may become, thereby cause unsettled coating.
Radiation-curable resin composition of the present invention solidifies by applying radiation.Here used radiation refers to ir radiation, visible light ray, ultraviolet rays, X-ray, α-ray, beta-rays, gamma-radiation, electron beam etc.Wherein, ultraviolet rays is particularly preferred.
Polymerization starter (D) can be added in the radiation-curable resin composition of the present invention alternatively.As component (D), use light trigger (D1) usually.If necessary, thermal polymerization can use together in conjunction with light trigger (D1).
Example as Photoepolymerizationinitiater initiater (D1); can provide 1-hydroxy-cyclohexyl phenyl ketone; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; xanthone; Fluorenone; phenyl aldehyde; fluorenes; anthraquinone; triphenylamine; carbazole; the 3-methyl acetophenone; the 4-chlorobenzophenone; 4; 4 '-dimethoxy-benzophenone; 4; 4 '-diaminobenzophenone; michaelis ketone; the st-yrax propyl ether; Benzoin ethyl ether; the benzophenone dimethyl acetal; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-1-acetone; 2-hydroxy-2-methyl-1-phenyl-1-acetone; thioxanthone; diethyl thioxanthone; the 2-isopropyl thioxanthone; the 2-clopenthixal ketone; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide etc.Commercial examples as Photoepolymerizationinitiater initiater, can provide Irgacure 184,369,651,500,907,819, CGI1700, CGI1750, CGI1850, CGI1870, CG2461, Darocur1116,1173 (by CibaSpecialty Chemical Co., Ltd. makes), Lucirin TPO (making), Ubecryl P36 (making) etc. by UCB by BASF.
As the example of thermal polymerization (D2), can provide superoxide, azo-compound etc.Specific examples comprises benzoyl peroxide, t-butyl per(oxy)benzoate, Diisopropyl azodicarboxylate etc.
Under situation, if desired, except Photoepolymerizationinitiater initiater, can add photosensitizers with photocuring radiation-curable resin composition of the present invention.As the photosensitizers example, can provide triethylamine, diethylamine, N methyldiethanol amine, thanomin, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester etc.As the commercial examples of photosensitizers, can provide Ubecryl P102,103,104,105 (making) etc. by UCB.
Polymerization starter (D) is used in the radiation-hardenable liquid resin composition of the present invention with the amount of preferred 0.1～10wt%, preferred especially 0.5～5wt%.
Except above component, can also in radiation-curable resin composition, add additive, for example tinting material, photostabilizer, silane coupling agent, antioxidant, thermal polymerization inhibitor, levelling agent, tensio-active agent, sanitas, softening agent, lubricant, solvent, filler, protective agent, wetting properties-correcting agent and coating surface modifying agent.Example as photostabilizer, can provide Tinuvin 292,144,622LD (by Ciba Specialty Chemicals Co., Ltd. manufacturing), Sanol LS770 is (by Sankyo Co., Ltd. manufacturing), SEESORB 101, SEESORB 103, SEESORB709 are (by Shipro Kasei Kaisha, Ltd. make), Sumisorb 130 (by SumitomoChemical Industries Co., Ltd. makes) etc.Example as silane coupling agent, can provide γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan and γ-methacryloxypropyl trimethoxy silane, for example SH6062, SZ6030 are (by Toray-Dow CorningSilicone Co., Ltd. make), the commodity of KBE903,603,403 (by Shin-Etsu Chemical Co., Ltd. makes) and so on etc.As the example of antioxidant, can provide Sumilizer GA-80 (by Sumitomo Chemical Industries Co., Ltd. makes), Irganox 1010,1035 (by Ciba Specialty Chemicals Co., Ltd. makes) etc.
The invention still further relates to the coating composition system, comprise that this coating composition system comprises at least a according to coating composition of the present invention as the primary coating composition and the secondary coating composition of the two coat systems of optical fiber.
The invention still further relates to the application of radiation-curable resin composition according to the present invention as primary coating, secondary coating, ink composite or body material on optical glass fibre, and relate to the method for production through the optical fiber of coating, wherein used according to radiation-curable resin composition of the present invention.
The invention still further relates to comprise glass optical fiber with primary coating through painting optic fibre, comprise glass optical fiber with primary coating and secondary coating through painting optic fibre, comprise and have primary coating, the glass optical fiber of secondary coating and hard-pressed bale coating through painting optic fibre, comprise glass optical fiber and single coating through painting optic fibre, comprise glass optical fiber, single coating and hard-pressed bale coating through painting optic fibre, each optical fiber through coating has coating ink composite thereon alternatively, and relate to comprise at least two by body material band together described through coating and optical fiber that be coated with China ink alternatively fibre ribbon and comprise at least two described through coating and the optical fiber cables of optical fiber that be coated with China ink alternatively, wherein said coating, at least a in ink composite or the body material obtained by radiation-curable resin composition according to the present invention.
The invention still further relates to the application of the compound (A) that comprises phosphorous acid ester group and phenolic hydroxyl as component in the radiation-curable resin composition.
Below will the present invention be described in more detail by example.But the present invention is not limited to these examples.
Example
Synthesizing of example I. carbamate (methyl) acrylate " UA-1 "
The number-average molecular weight that adds 831.0g in the reactor that has agitator is 2000 polypropylene glycol, the isophorone diisocyanate of 129.3g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under agitation this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 1.26wt% (with respect to the per-cent of add-on, down with) or when lower, add 38.6g vinylformic acid 2-hydroxy methacrylate.About 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-1 ").
Synthesizing of example II. carbamate (methyl) acrylate " UA-2 "
The number-average molecular weight that adds 907.2g in the reactor that has agitator is 4000 polypropylene glycol, the isophorone diisocyanate of 70.6g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under stirring this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 0.6wt% (with respect to the per-cent of add-on, down with) or when lower, add 21.1g vinylformic acid 2-hydroxy methacrylate.About 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-2 ").
Synthesizing of example III. carbamate (methyl) acrylate " UA-3 "
The number-average molecular weight that adds 950.9g in the reactor that has agitator is 8000 polypropylene glycol, the isophorone diisocyanate of 37.0g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under agitation this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 0.4wt% (with respect to the per-cent of add-on, down with) or when lower, add 11.0g vinylformic acid 2-hydroxy methacrylate.About 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-3 ").
Synthesizing of example IV. carbamate (methyl) acrylate " UA-4 "
In the reactor that has agitator, add the isophorone diisocyanate of 96.4g, 2,6 ditertiary butyl p cresol, 0.08g thiodiphenylamine and the 0.8g dibutyl tin laurate of 0.024g.When stirring, this mixture is cooled to 15 ℃.Use dropping funnel to add 86.9g vinylformic acid 2-hydroxy methacrylate through 1 hour.Under agitation this mixture slowly was heated to 35 ℃ through 1 hour.Add the 815.6g number-average molecular weight be 2000 tetrahydrofuran (THF) and 2-methyltetrahydrofuran multipolymer (" PTGL2000 ", by Hodogaya Chemical Co., Ltd. makes) afterwards, allow these mixture reactions down at about 60 ℃.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-4 ").
Synthesizing of example V. carbamate (methyl) acrylate " UA-5 "
The number-average molecular weight that adds 845.9g in the reactor that has agitator is 2000 polypropylene glycol, the 2,4 toluene diisocyanate of 112.4g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under agitation this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 1.26wt% (with respect to the per-cent of add-on, down with) or when lower, dropwise add the SH 6062 of 2.5g.About 60 ℃, allow this mixture reaction under stirring.After adding 33.5g vinylformic acid 2-hydroxy methacrylate, about 60 ℃, allow this mixture reaction under stirring.After adding 4.6g methyl alcohol, about 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-5 ").
Synthesizing of example VI. carbamate (methyl) acrylate " UA-6 "
The number-average molecular weight that adds 854.1g in the reactor that has agitator is 2000 polypropylene glycol, the tolylene diisocyanate of 106.7g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under agitation this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 1.4wt% (with respect to the per-cent of add-on, down with) or when lower, dropwise add 2.5g SH 6062.About 60 ℃, allow this mixture reaction under stirring.After adding 33.5g vinylformic acid 2-hydroxy methacrylate, about 60 ℃, allow this mixture reaction under stirring.After adding 2.3g methyl alcohol, about 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-6 ").
Synthesizing of example VII. carbamate (methyl) acrylate " UA-7 "
The number-average molecular weight that adds 832.2g in the reactor that has agitator is 2000 polypropylene glycol, the isophorone diisocyanate of 129.5g, 2,6 ditertiary butyl p cresol and the 0.08g thiodiphenylamine of 0.24g.When stirring, this mixture is cooled to 15 ℃.After adding the 0.8g dibutyl tin laurate, under agitation this mixture slowly was heated to 35 ℃ through 1 hour.With this mixture heating up to 50 ℃, and allow its reaction.When the remaining isocyanate density loss to 1.44wt% (with respect to the per-cent of add-on, down with) or when lower, add 36.7g vinylformic acid 2-hydroxyl butyl ester after, and about 60 ℃, allow this mixture reaction under stirring.After adding 0.5g methyl alcohol, about 60 ℃, allow this mixture reaction under stirring.When remaining isocyanate concentration is 0.1wt% or still less the time, termination reaction obtains carbamate (methyl) acrylate (hereinafter referred to as " UA-7 ").
The preparation of example VIII-XVI and comparison example 1-7. radiation-curable resin composition
In the reactor that has agitator, add according to the compound of forming (weight ratio) shown in table 1 and 2.Stir down these mixtures at 50 ℃, until obtaining uniform solution, thereby obtain the composition of example and comparison example.
Instance X VII. phosphorous acid four (2, the 5-di-tert-butyl-hydroxy phenyl) 2, the inferior quinhydrones base of 5-di-t-butyl ester synthetic
According to " Polymer Degradation and Stability, 77 (2002), the p.29 " method described in, synthetic diphosphorous acid four (2, the 5-di-tert-butyl-hydroxy phenyl) 2, the inferior quinhydrones base of 5-di-t-butyl ester.
Measure the method for the hydrogen generating quantity of solidifying product
Use applicator, the application of liquid composition is to the thickness of 381 μ m on sheet glass.Use 3.5kW metal halide lamp (by ORC Co., " SMX-3500/F-OS " that Ltd. makes), in air with 0.1J/cm
2Irradiation dose ultraviolet ray is applied on the liquid composition, to obtain the cured film of thick about 200 μ m.Solidifying product was left standstill 12 hours or longer under the relative humidity of 23 ℃ room temperature and 50%.Pack in the glass ampoule bottles 1g solidifying product and sealing.When 100 ℃ are heated 7 days down, make the glass ampoule bottles ageing that solidifying product is housed.Then by the amounts of hydrogen in the gas chromatographic measurement glass ampoule bottles.
Table 1 and 2 shows amounts of hydrogen (initial value) that produces under the curing situation immediately and the amounts of hydrogen that produces under the curing situation again (1 year storage back) after liquid composition is at room temperature stored 1 year after liquid composition generates.
Measure the method for cured film changes in weight
Use applicator, the application of liquid composition is to the thickness of 381 μ m on sheet glass.Use 3.5kW metal halide lamp (by ORC Co., " SMX-3500/F-OS " that Ltd. makes), in air with 0.1J/cm
2Irradiation dose ultraviolet ray is applied on the liquid composition, to obtain the cured film of thick about 200 μ m.Measure the weight of this cured film.120 ℃ down heating one month and carry out aging after, also measure the weight of cured film.Change according to the equation calculated weight.
Changes in weight (%)=(weight after the weight before aging-aging)/(weight before aging) * 100
Amounts of hydrogen (initial value) that table 1. produces under the curing situation immediately after liquid composition generates and the amounts of hydrogen that after liquid composition is at room temperature stored a year, produces under the curing situation again (1 year storage back)
| Component | Example | |||||||||
| VIII | IX | X | XI | XII | XIII | XIV | XV | XVI | ||
| Component (A) | GP | 0.5 | 1.0 | 0.5 | - | 0.5 | 1.0 | 1.0 | 1.0 | 1.0 |
| 2P5B | - | - | - | 0.5 | - | - | - | - | - | |
| Urethane acrylate (B) | UA-1 | 60 | 60 | - | - | - | - | - | - | - |
| UA-2 | - | - | 60 | - | - | - | - | - | - | |
| UA-3 | - | - | - | 40 | - | - | - | - | - | |
| UA-4 | - | - | - | - | 80 | - | - | - | - | |
| UA-5 | - | - | - | - | - | 60 | - | - | - | |
| UA-6 | - | - | - | - | - | - | 55 | - | 55 | |
| UA-7 | - | - | - | - | - | - | - | 55 | - | |
| Initiator (D) | Lucirin TPO | 1.0 | 0.5 | 5.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reactive thinner (C) | M110 | 10 | 10 | 10 | 10 | - | - | 11 | 11 | 11 |
| M113 | 20 | - | 18.5 | 11 | 18 | 32 | 18.5 | 18.5 | 15 | |
| IBXA | - | 17.5 | - | 30 | - | - | - | - | - | |
| The N-caprolactam | 7.5 | 10 | 5 | 7.5 | - | 6 | 7.5 | 7.5 | 7.5 | |
| HDDA | - | - | - | - | - | 1 | - | - | - | |
| M600A | - | - | - | - | - | - | - | - | 9.2 | |
| ACMO | - | - | - | - | - | - | 6 | 6 | - | |
| Other | DPDP | - | - | - | - | - | - | - | - | - |
| TNP-O | - | - | - | - | - | - | - | - | - | |
| SZ6030 | - | - | - | - | - | 0.5 | 1.0 | 1.0 | 1.0 | |
| SH6062 | 1.0 | 1.0 | 1.0 | - | - | - | - | - | - | |
| Seesorb101 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| GA-80 | - | - | - | - | 0.5 | 0.6 | 0.6 | 0.6 | 0.6 | |
| The amounts of hydrogen that is produced (l/g) | Initial value | 0.5 | 0.5 | 0.6 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| After storing in 1 year | 0.5 | 0.5 | 0.6 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| The changes in weight of cured film (%) | 98 | 99 | 95 | 97 | 98 | 98 | 99 | 98 | 98 | |
Amounts of hydrogen (initial value) that table 2. produces under the curing situation immediately after liquid composition generates and the amounts of hydrogen that after liquid composition is at room temperature stored a year, produces under the curing situation again (1 year storage back)
| Component | Comparison example | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| Component (A) | GP | - | - | - | - | - | - | - |
| 2P5B | - | - | - | - | - | - | - | |
| Urethane acrylate (B) | UA-1 | 60 | 60 | 60 | - | - | - | - |
| UA-2 | - | - | - | - | - | - | - | |
| UA-3 | - | - | - | - | - | - | - | |
| UA-4 | - | - | - | - | - | - | - | |
| UA-5 | - | - | - | 60 | - | - | - | |
| UA-6 | - | - | - | - | 55 | - | 55 | |
| UA-7 | - | - | - | - | - | 55 | - | |
| Initiator (D) | Lucirin TPO | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reactive thinner (C) | M110 | 10 | 10 | 10 | - | 11 | 11 | 11 |
| M113 | 20.5 | 19.5 | 20.5 | 32 | 18.5 | 18.5 | 15 | |
| IBXA | - | - | - | - | - | - | - | |
| The N-caprolactam | 7.5 | 7.5 | 7.5 | 6 | 7.5 | 7.5 | 7.5 | |
| HDDA | - | - | - | 1 | - | - | - | |
| M600A | - | - | - | - | - | - | 9.2 | |
| ACMO | - | - | - | - | 6 | 6 | - | |
| Other | DPDP | 1.0 | - | 0.5 | - | - | - | - |
| TNP-O | - | 1.0 | - | - | - | - | - | |
| SZ6030 | - | - | - | 0.5 | 1.0 | 1.0 | 1.0 | |
| SH6062 | - | 1.0 | - | - | - | - | - | |
| Seesorb 101 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| GA-80 | - | - | 0.5 | 0.6 | 0.6 | 0.6 | 0.6 | |
| The amounts of hydrogen that is produced | Initial value | 0.6 | 0.6 | 0.6 | 2.0 | 2.0 | 2.6 | 2.0 |
| After storing in 1 year | 2.7 | 2.8 | 3.0 | 3.5 | 3.0 | 4.0 | 3.0 | |
| The changes in weight of cured film (%) | 68 | 70 | 96 | 95 | 95 | 96 | 92 | |
Lucirin TPO:2,4,6-trimethylbenzoyl xenyl phosphine oxide (BASF manufacturing)
IBXA: isobornyl acrylate (by Osaka Organic Chemical Industry, Ltd. makes)
M110: phenyl EO modification acrylate (by Toagosei Co., Ltd. makes)
M113: nonyl phenyl EO modification acrylate (by Toagosei Co., Ltd. makes)
SH6062: γ-sulfydryl Trimethoxy silane (by Toray-Dow Corning Silicone Co., Ltd. makes)
2P5B: phosphorous acid four (2, the 5-di-tert-butyl-hydroxy phenyl) 2, the inferior quinhydrones base of 5-di-t-butyl ester
GP:Sumilizer GP (by Sumitomo Chemical Industries Co., Ltd. makes)
GA-80:Sumilizer GA-80 (by Sumitomo Chemical Industries Co., Ltd. makes)
DPDP: phosphorous acid phenylbenzene isodecyl ester (by Sanko Co., Ltd. makes)
TNP-O: tricresyl phosphite (nonyl phenyl) ester (by Sanko Co., Ltd. makes)
HDDA: hexanediyl ester
M600A: vinylformic acid 2-hydroxyl-3-phenoxy propyl ester
ACMO: acryloyl morpholine
SZ6030: γ-methacryloxypropyl trimethoxy silane
From table 1 and 2 as seen, radiation-curable resin composition of the present invention has excellent in storage stability, and generates excellent in te pins of durability, particularly excellent heat resistance, and only produces the solidifying product of small quantity of hydrogen.
Claims (9)
1. the resin combination of a radiation-hardenable comprises:
(A) compound that contains phosphorous acid ester group and phenolic hydroxyl of 0.1～10wt%;
(B) carbamate of 35～85wt% (methyl) acrylate and
(C) 1～60wt% can with the reactive thinner of component (B) copolymerization.。
2. radiation-curable resin composition as claimed in claim 1, wherein compound (A) is selected from the compound of have following structural formula (1) or structural formula (3):
3. coating composition system, described system comprise primary coating composition and the secondary coating composition as the two coat systems of optical fiber, and at least a in the wherein said coating composition is according to each described composition of claim 1～2.
4. according to of the application of each described radiation-curable resin composition of claim 1～2 as the primary coating on the optical glass fibre, secondary coating, ink composite or body material.
5. produce method, wherein use according to each described radiation-curable resin composition of claim 1～2 through the optical fiber of coating.
6. one kind through painting optic fibre, its be selected from by comprise glass optical fiber with primary coating through painting optic fibre, comprise glass optical fiber with primary coating and secondary coating through painting optic fibre, comprise and have primary coating, the glass optical fiber of secondary coating and hard-pressed bale coating through painting optic fibre, comprise glass optical fiber and single coating through painting optic fibre, comprise glass optical fiber, the group through the painting optic fibre composition of single coating and hard-pressed bale coating, and described optical fiber through coating has coating ink composite thereon, wherein said coating alternatively, at least a in the ink composite by obtaining according to each described radiation-curable resin composition of claim 1～2.
7. fibre ribbon, it comprise at least two by body material band together according to claim 6 through coating and the optical fiber of dope ink composition alternatively, at least a in wherein said coating, ink composite or the body material by obtaining according to each described radiation-curable resin composition of claim 1～2.
8. optical fiber cable, it comprise at least two according to claim 6 through coating and the optical fiber of dope ink composition alternatively.
9. contain of the application of the compound (A) of phosphorous acid ester group and phenolic hydroxyl as the component in the radiation-curable resin composition.
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| JP2002363908 | 2002-12-16 | ||
| JP363908/2002 | 2002-12-16 | ||
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6372740A (en) * | 1986-09-16 | 1988-04-02 | Yokohama Rubber Co Ltd:The | Ultraviolet-curing resin composition |
| US5199098A (en) * | 1991-10-09 | 1993-03-30 | Corning Incorporated | Moisture resistant optical fiber coatings with improved stability |
| US5514727A (en) * | 1994-07-13 | 1996-05-07 | Alliedsignal Inc. | Stabilizers for vinyl ether-based coating systems |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6372740A (en) * | 1986-09-16 | 1988-04-02 | Yokohama Rubber Co Ltd:The | Ultraviolet-curing resin composition |
| US5199098A (en) * | 1991-10-09 | 1993-03-30 | Corning Incorporated | Moisture resistant optical fiber coatings with improved stability |
| US5199098B1 (en) * | 1991-10-09 | 1995-02-14 | Corning Ware Inc | Moisture resistant optical fiber coatings with improved stability |
| US5514727A (en) * | 1994-07-13 | 1996-05-07 | Alliedsignal Inc. | Stabilizers for vinyl ether-based coating systems |
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