WO2016095560A1 - 一种辐射固化涂料 - Google Patents

一种辐射固化涂料 Download PDF

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Publication number
WO2016095560A1
WO2016095560A1 PCT/CN2015/087976 CN2015087976W WO2016095560A1 WO 2016095560 A1 WO2016095560 A1 WO 2016095560A1 CN 2015087976 W CN2015087976 W CN 2015087976W WO 2016095560 A1 WO2016095560 A1 WO 2016095560A1
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acrylate
meth
diisocyanate
epoxy
radiation
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PCT/CN2015/087976
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English (en)
French (fr)
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方足成
姜胜斌
马鑫
陈刚
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长飞光纤光缆股份有限公司
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Publication of WO2016095560A1 publication Critical patent/WO2016095560A1/zh

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    • 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
    • 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
    • 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
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • This invention relates to a radiation curable coating, and more particularly to an ultraviolet light initiating curable coating, which is particularly useful as a fiber optic coating and an optical fiber ribbon resin.
  • Optical fiber is the medium for information transmission in optical communication systems. Its function is to transmit optical signals to the terminal detector with as little loss as possible.
  • the commercial maturer is quartz glass fiber, which is formed by fusion drawing of quartz glass preform. Pure quartz glass fiber will inevitably be affected by various mechanical damages and environmental factors during the drawing process, which cannot meet the practical application requirements. Therefore, it is necessary to coat the protective resin, that is, the optical fiber coating, in the shortest possible time when the glass fiber is drawn out from the holding furnace.
  • thermosetting coatings and UV-curing coatings are mainly used as fiber coatings.
  • Thermosetting coatings are difficult to meet the ever-increasing drawing speed because of the slow heat curing rate. Therefore, all the major optical fiber companies use UV-curable coatings.
  • UV-curable coatings are environmentally friendly coatings because they cure at a fast rate and are essentially free of volatile organic compounds.
  • the coating process it is mainly divided into two methods: single layer coating and double layer coating.
  • the single layer coating has a large additional loss, so the current double-coating process is mainly used.
  • the first layer is in direct contact with the glass surface, referred to as the "Primary Coating"; the second layer covers the surface of the inner coating, referred to as the "Second Coating".
  • the inner coating is usually a soft, low modulus, low glass transition temperature buffer that minimizes microbend loss;
  • the outer coating is a tough, smooth, high modulus, high glass transition
  • the hard coating of temperature mainly plays a mechanical and environmental protection role on the optical fiber, so that the optical fiber has the ideal performance to withstand the external force of assembly.
  • a fiber component that is, a fiber ribbon
  • the optical fiber ribbon eliminates the assembly of a single bundle of optical fibers, simplifies the installation and maintenance of the optical fiber, and brings convenience to the collective fusion of the optical fibers.
  • the quality of the resin with the resin plays a crucial role in the performance of the fiber ribbon.
  • Radiation-cured coatings typically consist of oligomers, reactive monomer diluents, photoinitiators, and auxiliaries.
  • the oligomers in conventional radiation curable coatings are generally selected from the group consisting of polyurethane (meth) acrylates, epoxy (meth) acrylates or mechanical mixtures thereof, such as CN 1651533A, CN 1190383C.
  • the invention relates to a radiation-curable coating, wherein the oligomer adopts epoxy urethane (meth) acrylate by adding a ring with a certain hydroxyl value in the process of synthesizing polyurethane (meth) acrylate.
  • Oxygen (meth) acrylates cause them to chemically react, and the epoxy urethane (meth) acrylate thus obtained has better uniformity and stability than conventional mechanical mixtures, and has a more mechanical design. Excellent flexibility, especially suitable for use as a fiber inner and outer coating and a resin.
  • a radiation curable coating comprising an oligomer, a reactive monomer diluent, a photoinitiator and an adjuvant.
  • the content of the oligomer is 20% to 70% by weight
  • the content of the reactive monomer diluent is 20% to 70% by weight
  • the content of the photoinitiator is 1% to 10% by weight
  • the content of the auxiliary agent is 1% to 10% by weight.
  • the oligomer is selected from epoxy urethane (meth) acrylate, which is obtained by chemically reacting a (meth) acrylated polyurethane with a (meth) acrylated epoxy resin, and is specifically prepared from the following materials. Made of:
  • the molar ratio (weight ratio) between the four substances can be flexibly designed according to the required mechanical properties.
  • the polyol is mixed with the diisocyanate or the polyisocyanate in a designed ratio, and the reaction is naturally carried out for 0.5 hour in the presence of a catalyst, and then the temperature is raised to 60 ° C to 70 ° C, and the reaction is kept for 2 hours.
  • the designed amount of hydroxy (meth) acrylate and polymerization inhibitor are added to the reactor, and the reaction is continued for 2-3 hours at 60 ° C - 70 ° C.
  • epoxy (meth) acrylate is added to the reactor. In the reactor, the reaction was continued at 60 ° C to 70 ° C. After 3-4 hours, the isocyanate content was determined to be about zero percent, and the epoxy urethane (meth) acrylate oligomer was obtained at room temperature.
  • the polyol of the substance (1) is selected from the group consisting of polyether polyols, polyester polyols, hydrocarbon polyols, and polysiloxane polyols. One or a combination of two or more. Polyether polyols and polyester polyols are preferred; polytetramethylene ether glycol 1000 and polyester polyol EGBG 1000 are more preferred.
  • the diiso or polyisocyanate of the substance (2) is selected from the group consisting of toluene diisocyanate (TDI); 4,4'-diphenylmethane diisocyanate (MDI); polymethylene polyphenyl polyisocyanate (PAPI); Methyl diisocyanate (HDI); isophorone diisocyanate (IPDI); benzene dimethylene diisocyanate (XDI); trimethyl hexamethylene diisocyanate (TMDI); dimer acid diisocyanate (DDI) Lysine diisocyanate (LDI); diethyl fumarate diisocyanate (FDI); methylcyclohexyl diisocyanate (HTDI); dicyclohexylmethane diisocyanate (HMDI); tetramethylphenyldiphenyl Any one or two or more of methyl diisocyanate (TMXDI) are combined.
  • TDI toluen
  • IPDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • PAPI polymethylene polyphenyl Polyisocyanate
  • the (meth)acrylic acid hydroxyester of the substance (3) is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, 2-hydroxyoctyl methacrylate, pentaerythritol tri(meth) acrylate, glycerol di(meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, trimethylolpropane di(methyl) One or a combination of two or more of acrylate and trimethylolethane di(meth)acrylate.
  • the (meth) epoxy acrylate of the substance (4) is selected from the group consisting of CN104 series epoxy acrylate of SARTOMER, CN151 epoxy methacrylate, 621A-80 epoxy acrylate of Changxing Company, 6219-100 epoxy Methacrylate, 6105-80 epoxy acrylate of Jiangsu Sanmu Company.
  • the radiation-curable coating also contains one or more reactive monomer diluents, which act to reduce the viscosity of the oligomer and adjust the properties of the final coating, including refractive index, polarity, and curing. Speed and mechanical properties, etc. Because of the small modulus, the inner coating of the optical fiber generally uses a monomer diluent with less functionality, while the outer coating of the optical fiber and the resin with a larger resin generally use a multifunctional monomer diluent.
  • Suitable reactive monomer diluents include: alkoxylated phenol acrylates, 2(2-ethoxyethoxy)ethyl acrylate, tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, isobutyl acrylate, acrylic acid Caprolactone, ethylated nonylphenol acrylate, isobornyl acrylate, trimethylolpropane formal acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, condensed One or more of propylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate.
  • composition of the radiation-curable coating should also include from 1% to 10% by weight of the photoinitiator, preferably from 3% to 5% by weight.
  • the amount of initiator plays a crucial role in the curing speed and can also adjust the mechanical properties of the final coating.
  • the photoinitiator is selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 2-hydroxy-2-methyl-1-phenylacetone (DAROCURE 1173), 1 -hydroxycyclohexyl ketone (IRGACURE 184), benzoin dimethyl ether (IRGACURE 651), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (IRGACURE 819), 2-A One or a combination of two or more of -1-(4-methylthiophenyl)-2-morpholin-1-propanone (IRGACURE 907).
  • TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide
  • DAROCURE 1173 2-hydroxy-2-methyl-1-phenylacetone
  • IRGACURE 184 1 -hydroxycyclohexyl ketone
  • benzoin dimethyl ether phenylbis(2,4,6-trimethylbenzoyl
  • the radiation-curing coatings described above may include some conventional auxiliaries to suitably adjust the final properties of the coating, including but not limited to adhesion promoters, defoamers, leveling agents, antioxidants, stabilizers, and the like.
  • the oligomer of the present invention is an epoxy urethane (meth) acrylate which is obtained by chemically reacting a urethane (meth) acrylate with an epoxy (meth) acrylate, and has a more mechanical mixture than a conventional mechanical mixture. Good uniformity and stability.
  • by changing the content of the epoxy (meth) acrylate it is convenient to design a prepolymer having different properties, thereby flexibly adjusting the mechanical properties of the final coating.
  • the respective materials were uniformly mixed at 60 ° C to obtain an optical fiber inner layer coating.
  • the viscosity of the coating was measured to be 5,500 ⁇ 200 cps (25 ° C), the modulus of elasticity was 1.2 MPa, the tensile strength was 0.69 MPa, and the elongation at break was 120%.
  • the materials were uniformly mixed at 60 ° C to obtain an optical fiber outer coating.
  • the viscosity of the coating was measured to be 4800 ⁇ 200 cps (25 ° C), the modulus of elasticity was 810 MPa, the tensile strength was 27.5 MPa, and the elongation at break was 18%.
  • the materials were uniformly mixed at 60 ° C to obtain a fiber with a resin.
  • the viscosity of the coating was measured to be 4000 ⁇ 200 cps (25 ° C), the modulus of elasticity was 650 MPa, the tensile strength was 26 MPa, and the elongation at break was 19%.

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Abstract

一种用于光纤的辐射固化涂料，包括：环氧聚氨酯（甲基）丙烯酸酯低聚物20-70 wt%，活性单体稀释剂20-70 wt %，光引发剂1-10 wt %，助剂1-10 wt %％。该环氧聚氨酯（甲基）丙烯酸酯通过聚氨酯（甲基）丙烯酸酯与环氧（甲基）丙烯酸酯发生化学反应所得，具有更好的均匀性和稳定性。

Description

一种辐射固化涂料 技术领域
本发明涉及一种辐射固化涂料，尤其是一种紫外光引发固化的涂料，特别适用于用作光纤涂料和光纤并带树脂。
背景技术
光纤是光通信***中信息传输的介质，其功能是将光信号以尽可能小的损耗传递给端机检出器。目前商用比较成熟的是石英玻璃光纤，它是通过石英玻璃预制棒熔融拉制而成。纯的石英玻璃光纤在拉丝过程中不可避免地会受到各种机械损伤和环境因素的影响，根本无法满足实际应用需求。因此，必须在玻璃光纤从保温炉中拉出成型时以尽可能短的时间涂覆保护性树脂，即光纤涂料。
从涂料种类看，用作光纤涂料的主要有热固性涂料和紫外光固化涂料。热固性涂料因为热固化速度较慢，难以满足不断提高的拉丝速度，所以目前各大光纤企业采用的都是紫外光固化涂料。紫外光固化涂料不仅固化速度快，而且基本无挥发性有机物产生，是一种环境友好型涂料。
在涂覆工艺上主要分为单层涂覆和双层涂覆两种方式。其中单层涂覆时附加损耗较大，因此目前采用的主要是双层涂覆工艺。第一层与玻璃表面直接接触，称为光纤内层涂料(Primary Coating)；第二层覆盖在内层涂料表面，称为光纤外层涂料(Second Coating)。内层涂料通常是一种柔软、低模量、低玻璃化转变温度的缓冲层，其作用是使微弯损耗减至最小；外层涂料是一种坚韧光滑、高模量、高玻璃化转变温度的硬质涂层，主要对光纤起着机械和环境保护作用，使光纤具有理想耐受组装外力的性能。
另外，随着光纤通信***的飞速发展，尤其是FTTX(光纤到户，光纤到大楼等)的普及，光缆中光纤的芯数不断增加。为了使光缆的尺寸不致过大，必须提高光缆中光纤的密集度，一种光纤组件，即光纤带，被认为是一个理想的选择。它是将着色好的光纤通过并带树脂粘结在一起形成的。光纤带免除了单束光纤的组装，简化了光纤的安装及维护，给光纤的集体熔接带来了方便。其中，并带树脂的质量对光纤带的性能起着至关重要的作用。
辐射固化涂料通常由低聚物、活性单体稀释剂、光引发剂和助剂组成。传统的辐射固化涂料中低聚物一般选自聚氨酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯或是它们的机械混合物，如CN 1651533A，CN 1190383C。本发明涉及的一种辐射固化涂料，其中低聚物采用的是环氧聚氨酯(甲基)丙烯酸酯，它是通过在合成聚氨酯(甲基)丙烯酸酯的过程中加入带有一定羟值的环氧(甲基)丙烯酸酯，使它们发生化学反应，这样获得的环氧聚氨酯(甲基)丙烯酸酯相比传统的机械混合物具有更好均匀性和稳定性，而且在机械性能的设计上具有更佳的灵活性，特别适用于用作光纤内外层涂料和并带树脂。
发明内容
本发明的目的是提供一种适用于用作光纤涂料及并带树脂的辐射固化涂料，它具有很好的稳定性和机械性能可设计性。
本发明是通过下述技术方案得以实现的：一种辐射固化涂料，包括低聚物、活性单体稀释剂、光引发剂和助剂。其中，低聚物的含量为20％-70wt％，活性单体稀释剂的含量为20％-70wt％，光引发剂含量为1％-10wt％，助剂含量为1％-10wt％。低聚物选用环氧聚氨酯(甲基)丙烯酸酯，它是由(甲基)丙烯酸酯化的聚氨酯与(甲基)丙烯酸酯化的环氧树脂经过化学反应制得的，具体由以下物质制备而成：
(1)多元醇；
(2)二异氰酸酯或多异氰酸酯；
(3)(甲基)丙烯酸羟基酯；
(4)环氧(甲基)丙烯酸酯。
根据所需要的机械性能，可以灵活设计四种物质之间的摩尔比(重量比)。首先将多元醇与二异氰酸酯或多异氰酸酯按照设计的比例进行混合，在催化剂存在的条件下先自然反应0.5小时，然后升温至60℃-70℃，保温反应2小时。接着将设计好用量的(甲基)丙烯酸羟基酯和阻聚剂加入到反应器中，60℃-70℃条件下继续反应2-3小时，最后将环氧(甲基)丙烯酸酯加入到反应器中，60℃-70℃下继续反应，3-4小时后，测定异氰酸酯含量约为零百分比，降至室温即得环氧聚氨酯(甲基)丙烯酸酯低聚物。
物质(1)所述多元醇选自聚醚多元醇、聚酯多元醇、碳氢多元醇、聚硅氧烷多元醇 中的一种或两种以上组合。优选聚醚多元醇和聚酯多元醇；更优选聚四亚甲基醚二醇1000和聚酯多元醇EGBG 1000。
物质(2)所述二异或多异氰酸酯选自甲苯二异氰酸酯(TDI)；4,4’-二苯基甲烷二异氰酸酯(MDI)；多亚甲基多苯基多异氰酸酯(PAPI)；六亚甲基二异氰酸酯(HDI)；异佛尔酮二异氰酸酯(IPDI)；苯二亚甲基二异氰酸酯(XDI)；三甲基六亚甲基二异氰酸酯(TMDI)；二聚酸二异氰酸酯(DDI)；赖氨酸二异氰酸酯(LDI)；反丁烯二酸二乙酯二异氰酸酯(FDI)；甲基环己基二异氰酸酯(HTDI)；二环己基甲烷二异氰酸酯(HMDI)；四甲基苯二亚甲基二异氰酸酯(TMXDI)中的任意一种或两种以上组合。优选异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、4,4’-二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、多亚甲基多苯基多异氰酸酯(PAPI)。
物质(3)所述(甲基)丙烯酸羟基酯选自(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、二季戊四醇单羟基五(甲基)丙烯酸酯、(甲基)丙烯酸2-羟辛酯、季戊四醇三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、4-羟基环己基(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基乙烷二(甲基)丙烯酸酯中的一种或两种以上组合。
物质(4)所述(甲基)环氧丙烯酸酯选自SARTOMER公司的CN104系列环氧丙烯酸酯、CN151环氧甲基丙烯酸酯、长兴公司的621A-80环氧丙烯酸酯、6219-100环氧甲基丙烯酸酯、江苏三木公司的6105-80环氧丙烯酸酯等。
除了以上低聚物外，该辐射固化涂料还含有一种或多种活性单体稀释剂，它的作用主要是降低低聚物的粘度并调整最终涂料的性能，包括折光指数、极性、固化速度和机械性能等。光纤内层涂料因为模量较小，一般选用官能度较小的单体稀释剂，而光纤外层涂料和并带树脂因为模量较大，一般选用多官能团的单体稀释剂。适合的活性单体稀释剂包括：烷氧化苯酚丙烯酸酯、2(2-乙氧基乙氧基)乙基丙烯酸酯、四氢呋喃丙烯酸酯、2-苯氧乙基丙烯酸酯、丙烯酸异葵酯、丙烯酸己内酯、乙基化壬基苯酚丙烯酸酯、丙烯酸异冰片酯、三羟甲基丙烷缩甲醛丙烯酸酯、新戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯或季戊四醇四丙烯酸酯中的一种或多种。
该辐射固化涂料的组成还应包括1％-10wt％的光引发剂，优选3％-5wt％的含量。光 引发剂用量对固化速度起着至关重要的作用，对最终涂料的机械性能也能起一定的调节作用。所述的光引发剂选自2,4,6-三甲基苯甲酰基-二苯基氧化磷(TPO)、2-羟基-2-甲基-1-苯基丙酮(DAROCURE 1173)、1-羟基环已基苯甲酮(IRGACURE 184)、安息香双甲醚(IRGACURE 651)、苯基双(2,4,6-三甲基苯甲酰基)氧化膦(IRGACURE 819)、：2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮(IRGACURE 907)中的一种或两种以上组合。
以上所述辐射固化涂料可包括一些常规助剂，用以对涂料的最终性能进行适当调节，包括但不限于粘结促进剂、消泡剂、流平剂、抗氧剂和稳定剂等。
本发明低聚物采用的是环氧聚氨酯(甲基)丙烯酸酯，它是通过聚氨酯(甲基)丙烯酸酯与环氧(甲基)丙烯酸酯发生化学反应所得，相比传统的机械混合物具有更好均匀性和稳定性。另外，通过改变环氧(甲基)丙烯酸酯的含量，可以很方便地设计出具有不同性能的预聚物，进而可以灵活地对最终涂料的机械性能进行调节。
具体实施方式
实施例1
环氧聚氨酯(甲基)丙烯酸酯低聚物A的合成
Figure PCTCN2015087976-appb-000001
实施例2
环氧聚氨酯(甲基)丙烯酸酯低聚物B的合成
Figure PCTCN2015087976-appb-000002
Figure PCTCN2015087976-appb-000003
实施例3
环氧聚氨酯(甲基)丙烯酸酯低聚物C的合成
Figure PCTCN2015087976-appb-000004
实施例4
环氧聚氨酯(甲基)丙烯酸酯低聚物A的合成
Figure PCTCN2015087976-appb-000005
实施例5
光纤内层涂料的配制
Figure PCTCN2015087976-appb-000006
Figure PCTCN2015087976-appb-000007
按照上述比例，在60℃下将各物质混合均匀即得光纤内层涂料。测得该涂料的粘度为5500±200cps(25℃)，弹性模量1.2MPa，拉伸强度0.69MPa，断裂伸长率120％。
实施例6
光纤外层涂料的配制
Figure PCTCN2015087976-appb-000008
按照上述比例，在60℃下将各物质混合均匀即得光纤外层涂料。测得该涂料的粘度为4800±200cps(25℃)，弹性模量810MPa，拉伸强度27.5MPa，断裂伸长率18％。
实施例7
并带树脂的配制
Figure PCTCN2015087976-appb-000009
按照上述比例，在60℃下将各物质混合均匀即得光纤用并带树脂。测得该涂料的粘度为4000±200cps(25℃)，弹性模量650MPa，拉伸强度26MPa，断裂伸长率19％。

Claims (8)

  1. 一种辐射固化涂料，它包括低聚物、活性单体稀释剂、光引发剂和助剂，其中各组分的重量百分比为：低聚物20％-70wt％，活性单体稀释剂20％-70wt％，光引发剂1％-10wt％，助剂1％-10wt％，所述的低聚物选用环氧聚氨酯(甲基)丙烯酸酯。
  2. 根据权利要求1所述的一种辐射固化涂料，其特征是：所述的环氧聚氨酯(甲基)丙烯酸酯，由多元醇、二异氰酸酯或多异氰酸酯、(甲基)丙烯酸羟基酯、环氧(甲基)丙烯酸酯在二丁基二月桂酸锡做催化剂的条件下进行聚合反应制备而成。
  3. 根据权利要求2所述的一种辐射固化涂料，其特征是：所述多元醇选自聚醚多元醇、聚酯多元醇、碳氢多元醇、聚硅氧烷多元醇中的一种或两种以上组合。
  4. 根据权利要求2所述的一种辐射固化涂料，其特征是：所述二异或多异氰酸酯选自甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、二聚酸二异氰酸酯、赖氨酸二异氰酸酯、反丁烯二酸二乙酯二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、中的任意一种或两种以上组合。
  5. 根据权利要求2所述的一种辐射固化涂料，其特征是：所述(甲基)丙烯酸羟基酯选自(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、二季戊四醇单羟基五(甲基)丙烯酸酯、(甲基)丙烯酸2-羟辛酯、季戊四醇三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、4-羟基环己基(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基乙烷二(甲基)丙烯酸酯中的一种或两种以上组合。
  6. 根据权利要求2所述的一种辐射固化涂料，其特征是：所述(甲基)环氧丙烯酸酯选自CN104系列环氧丙烯酸酯、CN151环氧甲基丙烯酸酯、621A-80环氧丙烯酸酯、 6219-100环氧甲基丙烯酸酯或6105-80环氧丙烯酸酯。
  7. 根据权利要求1所述的一种辐射固化涂料，其特征是：所述的活性单体稀释剂包括：烷氧化苯酚丙烯酸酯、2(2-乙氧基乙氧基)乙基丙烯酸酯、四氢呋喃丙烯酸酯、2-苯氧乙基丙烯酸酯、丙烯酸异葵酯、丙烯酸己内酯、乙基化壬基苯酚丙烯酸酯、丙烯酸异冰片酯、三羟甲基丙烷缩甲醛丙烯酸酯、新戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯或季戊四醇四丙烯酸酯中的一种或多种。
  8. 根据权利要求1所述的一种辐射固化涂料，其特征是：所述的光引发剂选自2,4,6-三甲基苯甲酰基-二苯基氧化磷、2-羟基-2-甲基-1-苯基丙酮、1-羟基环已基苯甲酮、安息香双甲醚、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮(IRGACURE 907)中的一种或两种以上组合。
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