CN116731604A - Preparation method of LED-UV cured optical fiber inner coating paint - Google Patents
Preparation method of LED-UV cured optical fiber inner coating paint Download PDFInfo
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- CN116731604A CN116731604A CN202310703598.XA CN202310703598A CN116731604A CN 116731604 A CN116731604 A CN 116731604A CN 202310703598 A CN202310703598 A CN 202310703598A CN 116731604 A CN116731604 A CN 116731604A
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- optical fiber
- inner coating
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title abstract description 33
- 239000011248 coating agent Substances 0.000 title abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003973 paint Substances 0.000 title description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000008199 coating composition Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 5
- -1 aliphatic isocyanate Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 238000006845 Michael addition reaction Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 4
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical group OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 8
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- 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
Landscapes
- 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)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention relates to an LED-UV cured optical fiber inner layer coating and a preparation method thereof, and provides an LED-UV ultraviolet cured optical fiber inner layer coating composition with the wavelength of 380-420nm, which comprises the following components: an oligomer; a co-initiation resin; diluting the monomer; a pigment; an initiator; antioxidants and other auxiliary agents. Wherein the oligomer is a polyurethane modified with caprolactone acrylate. When 60-90% of the specific oligomer resin is added, the curing speed of the curing performance exceeding 3000m/min can be met, and the cured optical fiber has the characteristics of good low temperature resistance, good microbending attenuation, good stripping performance and the like. The invention also has the initiating characteristic of not using TPO, and meets the special initiating requirement of European Union REACH.
Description
Technical Field
The invention belongs to the field of preparation of UV (ultraviolet light curing) optical fiber coating materials, and particularly relates to a preparation method of a special LED-UV ultraviolet light curing optical fiber inner coating paint.
Background
With the development and popularization of 5G technology, the optical fiber communication technology is widely applied, and the modern communication mode of transmitting information point-to-point by using the optical fiber as the medium of information transmission is rapidly applied. Optical fibers are typically coated with two or more radiation curable coatings. Typically, the optical fiber coating determines the signal transmission attenuation and mechanical and aging resistance properties of the optical fiber, and the inner coating determines the optical fiber bending and signal attenuation cold resistance properties. Radiation suitable for curing such coatings is well known and includes ultraviolet light (hereinafter "UV") and electron beam ("EB"). In the preparation of coated optical fibers, the preferred type of radiation used to cure the coating is UV curing. In recent years, the energy-efficient and environment-friendly LED-UV is the development trend of UV curing.
The UV curing optical fiber coating is instantly cured by utilizing an ultraviolet curing technology, and the technology has the characteristics of high efficiency, environmental protection and excellent performance, but the traditional UV curing mode adopts a mercury lamp as a wave source, and the curing mode has the defects of high equipment price, high maintenance cost, quick attenuation of UV illumination intensity, high surface temperature of an irradiated element, large volume, high consumable material, mercury pollution, low energy utilization rate and the like. The LED-UV single-band curing light source has the characteristics of constant illumination intensity, excellent temperature control, portability and environmental protection, has relatively low purchase cost and almost zero maintenance cost, and plays a promotion role in improving the quality of a UV curing process, saving energy and reducing consumption.
The fibers in an optical fiber are often coated with two or more superimposed radiation curable coatings immediately after they are made by drawing. And then the final cable is formed by coloring and curing, which is an efficient production mode, and has been used as a main stream production mode by domestic and foreign manufacturers, and the development of LED-UV curing is greatly promoted in the last years.
The previously described LED-UV optical fiber coatings suitable for use as optical fibers have inventive applications in China, but there is no special function of the invention specifically built in the LED-UV optical fiber coating invention patent:
in the published chinese patent is the inventor's own patent, application number: CN201811004904.6, "a method for preparing a uv-curable optical fiber overcoating coating material" (patentee rayleigh polymer technology (zhejiang) limited), describes and claims that this invention provides a uv-curable optical fiber overcoating composition comprising: an oligomer; a thermoplastic acrylate; diluting the monomer; an initiator; an antioxidant. Wherein the photoinitiator is an ultraviolet initiator absorbing 395nm and capable of being cured by LED-UV, and the thermoplastic resin and the low molecular weight 1500g/mol are mainly coated outside, not coated inside the optical fiber. The invention synthesizes the large molecular weight polyurethane synthesized by the modified caprolactone acrylic ester, so that the large molecular weight polyurethane is internally coated on the optical fiber with larger absorption value of an LED-UV single wave band and lower glass transition temperature, thereby improving the curing speed of the optical fiber to reach 3000m/min, improving the performance characteristics of cold resistance, microbending resistance, low attenuation signal and the like of the optical fiber.
While many LED-UV curable coatings are currently available in a relatively large number of inventions, they are all conventional formulation-based products, with oligomers and additives changed to develop products and none applied to high-speed production of optical fiber coatings. The invention utilizes and synthesizes a novel caprolactone modified acrylic ester polyurethane to improve the initiation efficiency, reduce the attenuation signal and realize good cold resistance, and the novel caprolactone modified acrylic ester polyurethane is matched with a special optical fiber inner coating which does not contain TPO initiator to be used as an LED-UV initiation curing optical fiber inner coating with 380-420nm wave band, so that the novel caprolactone modified acrylic ester polyurethane has superior initiation curing performance.
Disclosure of Invention
The LED-UV cured coloring optical fiber inner coating paint is developed for solving the problems that the existing high-speed and high-efficiency LED-UV ultraviolet cured optical fiber with 380-420nm has microbending resistance, cold resistance and low attenuation signal.
The technical scheme of the invention is as follows: an ultraviolet light curing optical fiber inner coating composition is cured under ultraviolet light with the wavelength of 380-420nm of LED-UV, and comprises the following components in parts by mass:
a) 60-90 parts of polyurethane acrylate oligomer; b) 3-5 parts of auxiliary initiation resin; c) 0.5-1 part of high temperature resistant antioxidant; d) 3-5 parts of photoinitiator; e) Diluting monomer-5-25 parts; 1-2 parts of adhesive force auxiliary agent; wherein the photoinitiator is a non-TPO ultraviolet initiator capable of absorbing 380-420 nm; the urethane acrylate oligomer is the reaction product of:
i) Caprolactone;
ii) hydroxyethyl acrylate;
iii) Polyethers of molecular weight 4000 having a hydroxyl number of 23 to 30;
iv) an organotin catalyst;
v) aliphatic diisocyanates.
vi) an auxiliary;
the molar ratio of caprolactone to hydroxyethyl acrylate to polyether to aliphatic isocyanate to organotin catalyst is 2-3:1:1:1:0.005.
the reaction mole ratio of caprolactone, hydroxyethyl acrylate, polyether, aliphatic isocyanate and organotin catalyst is 2:1:1:1:0.005.
the photoinitiator is a mixture of various phosphine oxide initiators.
The photoinitiator is a mixture of ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate and phenyl-bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
The auxiliary initiation resin is amino acrylic ester synthesized by Michael addition of acrylic ester groups of half acrylic ester of trifunctional groups and secondary amine.
The high temperature resistant antioxidant is a hindered phenol antioxidant with the molecular weight of more than 500 g/mol.
The beneficial effects are that:
the LED-UV ultraviolet light cured optical fiber inner coating prepared by the invention, wherein the oligomer is polyurethane modified by caprolactone acrylate. When 60-90% of the specific oligomer resin is added, the curing speed of the curing performance exceeding 3000m/min can be met, the cured optical fiber has the characteristics of good low temperature resistance, good microbending attenuation, good stripping performance and the like, the invention also has the initiating characteristic of not using TPO, meets the special initiating requirement of European Union REACH, and is an energy-saving and environment-friendly ultraviolet light curing optical fiber coating product.
Detailed Description
The preparation used in the present invention is a commercially available conventional product, as long as it is a qualified industrial product, not limited to a manufacturer.
Throughout this patent application, the following terms have the indicated meanings:
the invention is further illustrated below with reference to examples.
An ultraviolet light curing optical fiber inner coating composition is cured under ultraviolet light with the wavelength of 380-420nm of LED-UV, and comprises the following components in parts by mass:
a) 60-90 parts of polyurethane acrylate oligomer; b) 3-5 parts of auxiliary initiation resin; c) Antioxidant-0.5-1 part; d) 3-5 parts of photoinitiator; e) Diluting monomer-5-25 parts; 1-2 parts of adhesive force auxiliary agent.
Wherein the urethane acrylate oligomer is the reaction product of:
i) Caprolactone;
ii) hydroxyethyl acrylate;
iii) Polyethers of molecular weight 4000 having a hydroxyl number of 23 to 30;
iv) an organotin catalyst;
v) aliphatic diisocyanates;
vi) an auxiliary agent.
The molar ratio of caprolactone to hydroxyethyl acrylate to polyether to aliphatic isocyanate to catalyst is 2:1:1:1:0.005.
the photoinitiator is a non-TPO ultraviolet initiator capable of absorbing 380-420nm and is a mixture of various phosphine oxide initiators.
Polyurethane acrylic ester oligomer is synthesized by the reaction of caprolactone, hydroxyethyl acrylate, polyether, aliphatic isocyanate and an organotin catalyst, and the reactants are: the molar ratio of caprolactone to hydroxyethyl acrylate to polyether to aliphatic isocyanate to organotin catalyst is 2-3:1:1:1:0.005.
the photoinitiator is a non-TPO ultraviolet initiator capable of absorbing 380-420nm, is a mixture of various phosphine oxides, and is commercially available as ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate (TPO-L), phenyl-bis (2, 4, 6-trimethylbenzoyl (819), TMO and the like, wherein the phosphine oxides such as TPO-L, 819 and the like are preferable.
The auxiliary initiation resin is amino acrylic ester synthesized by Michael addition of acrylic ester groups of half acrylic ester of trifunctional groups and secondary amine. Generally, the active amine acrylic ester is prepared by TMPTA and diethylamine or by Michael addition of PETA and diethylamine.
The antioxidant is a high temperature resistant antioxidant, typically a hindered phenol antioxidant having a molecular weight greater than 500 g/mol. Markets 1076, 168, 1010, etc. are all preferred objects and can be selected according to the compatibility of the system.
The monomer is a monofunctional monomer with a general large molecular weight, such as isooctyl acrylate, isodecyl acrylate, polyethoxylate phenol acrylate and the like.
The adhesive force auxiliary agent is a general coupling agent, and can be selected from mercapto silane coupling agents.
The application of the ultraviolet light curing optical fiber inner coating is matched with the outer coating of the Ruitong company. The application is characterized in that the curing speed of the curing performance exceeding 3000m/min can be met, and the cured optical fiber has the characteristics of good low temperature resistance, good microbending attenuation, good stripping performance and the like.
EXAMPLE 1 Synthesis of urethane acrylate oligomer PA1
The synthesis of the oligomers was performed as set forth in the table.
Synthetic formulation of epidi-oligomers
Pumping the components 1, 2 and 3 into a flask, adding half of PA01, controlling the temperature to be between 110 and 120 ℃ for 4 hours, adding IPDI, controlling the temperature to be between 50 and 60 ℃ for one hour, then adding PPG4000 and the rest PA01, controlling the temperature to be between 70 and 80 ℃ for 4 hours, and testing the qualified NCO percent of discharged materials for later use.
EXAMPLE 2 Synthesis of urethane acrylate oligomer PA2
The synthesis of the oligomers was performed as set forth in the table.
Table tri-oligomer synthesis formulation
Pumping the components 1, 2 and 3 into a flask, adding half of PA01, controlling the temperature to be between 110 and 120 ℃ for 4 hours, adding IPDI, controlling the temperature to be between 50 and 60 ℃ for one hour, then adding PPG4000 and the rest PA01, controlling the temperature to be between 70 and 80 ℃ for 4 hours, and testing the qualified NCO percent of discharged materials for later use.
EXAMPLE 3 Synthesis of urethane acrylate oligomer PA3
The synthesis of the oligomers was performed as set forth in the table.
Table four oligomer synthesis formulation
Pumping the components 1, 2 and 3 into a flask, adding half of PA01, controlling the temperature to be between 110 and 120 ℃ for 4 hours, adding IPDI, controlling the temperature to be between 50 and 60 ℃ for one hour, then adding PPG4000 and the rest PA01, controlling the temperature to be between 70 and 80 ℃ for 4 hours, and testing the qualified NCO percent of discharged materials for later use.
EXAMPLE 3 Synthesis of urethane acrylate oligomer PA4
The synthesis of the oligomers was performed as set forth in the table. This resin is a conventional overcoated oligomer and has not been modified.
Table five oligomer synthesis formulation
Pumping the components 2 and 3 into a flask, adding half of PA01, adding IPDI, controlling the temperature to be 50-60 ℃ for one hour, then adding PPG4000 and the rest PA01, controlling the temperature to be 70-80 ℃ for 4 hours, and testing NCO% qualified discharging for standby.
Example 5 preparation of LED-UV ultraviolet light cured optical fiber inner coating paint
The ink was formulated as in Table six below
Formulation for internal coating of table six
Uniformly dispersing the components A, B and C, curing the thick film with 150um on a glass plate under the condition of UVV of 1500mj/cm < 2 >, and standing for 24 hours to be tested.
Example 6 preparation of LED-UV ultraviolet light cured optical fiber inner coating paint
The ink was formulated as in Table seven below
Formulation for internal coating of table seven
Uniformly dispersing the components A, B and C, curing a thick film of 150um prepared on a glass plate under the UVV of LED-UV of 1500mj/cm < 2 >, and standing for 24 hours to be tested.
Example 7 test of curing speed (curing energy)
Three sets of experiments were performed using the above examples 5 and 6, each of which was formed into 100um films and cured under 385nm LED-UV ultraviolet light (in a nitrogen atmosphere), the lowest curing energy was measured when the degree of cure (RAU) was greater than 90%, and each set was compared to the test
Test of tensile mechanical properties obtained by ultraviolet curing internal coating
| Project | A curing energy mj/cm 2 | B curing energy mj/cm 2 | C curing energy mj/cm2 |
| Table six formula | 800 | 850 | 800 |
| Table seven formula | 1600 | 850 | 850 |
As a result of the comparative experiments, it was found that the curing energies of the groups A/B/C and seven groups B/C were each lower than 850mj/cm 2 The curing energies are all significantly lower than those of Table seven-A, indicating that the conventional intercoat resin brings about a particular curing effect with the special oligomer resin and the co-initiated resin of the present invention. Greatly reduces the curing energy and satisfies the curing effect.
Example 8 testing of tensile properties of cure:
three sets of experiments were used for each of examples 5 and 6 above, cured to film at UV-LED according to their formulation at UVV,1500mj/cm, according to the standard: T/CEMIA009-2018 specifies the standard:
rectangular sample bars with internal coating, width and thickness of 100mm plus or minus 20mm,12.5mm plus or minus 0.1mm and 0.15 plus or minus 0.01mm are respectively prepared on a clean glass plate, and the surfaces are flat, bubble-free and crack-free.
-at the time of modulus measurement: when the inner coating is measured, the sensor 50N stretches at 20mm/min.
-when measuring elongation and tensile strength: when the inner coating is measured, the sensor 50N stretches at 20mm/min.
Specific indexes are shown in a table nine.
Test of tensile Property of the interior coating (test conditions 25 ℃ C., humidity: 50-60%)
| Sample of | Modulus mpa.s | Elongation at break% | Strength mpa.s |
| TABLE five-A | 1.0 | 120 | 0.85 |
| TABLE five-B | 0.92 | 130 | 0.65 |
| TABLE five-C | 0.96 | 128 | 0.72 |
| TABLE six-A | 1.0 | 90 | 0.7 |
| TABLE six-B | 0.98 | 120 | 0.70 |
| TABLE six-C | 0.96 | 126 | 0.69 |
As can be seen from the table, the elongation at break of the common table six-A is relatively low, only 90%, but several exceptional groups of experiments of the invention are relatively high in elongation at break, so that the glass fiber reinforced plastic composite material has good microbending resistance, relatively low attenuation and very good effect on low temperature resistance.
Claims (6)
1. An ultraviolet light curing optical fiber inner coating composition is characterized by being cured under ultraviolet light with the wavelength of 380-420nm of LED-UV, and comprises the following components in parts by mass:
a) 60-90 parts of polyurethane acrylate oligomer; b) 3-5 parts of auxiliary initiation resin; c) 0.5-1 part of high temperature resistant antioxidant; d) 3-5 parts of photoinitiator; e) Diluting monomer-5-25 parts; 1-2 parts of adhesive force auxiliary agent;
wherein the photoinitiator is a non-TPO ultraviolet initiator capable of absorbing 380-420 nm; the urethane acrylate oligomer is the reaction product of:
i) Caprolactone;
ii) hydroxyethyl acrylate;
iii) Polyethers of molecular weight 4000 having a hydroxyl number of 23 to 30;
iv) an organotin catalyst;
v) aliphatic diisocyanates.
vi) an auxiliary;
the molar ratio of caprolactone to hydroxyethyl acrylate to polyether to aliphatic isocyanate to organotin catalyst is 2-3:1:1:1:0.005.
2. the ultraviolet light curable optical fiber inner coating composition of claim 1, wherein the reaction molar ratio of caprolactone, hydroxyethyl acrylate, polyether, aliphatic isocyanate, organotin catalyst is 2:1:1:1:0.005.
3. the uv curable optical fiber inner coating composition of claim 1, wherein the photoinitiator is a mixture of a plurality of phosphine oxide based initiators.
4. The uv curable optical fiber inner coating composition of claim 1, wherein the photoinitiator is a mixture of ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate and phenyl-bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
5. The ultraviolet light cured optical fiber inner coating composition according to claim 1, wherein the auxiliary initiation resin is amino acrylate synthesized by Michael addition of acrylate groups of half three functional acrylate groups and secondary amine.
6. The uv curable optical fiber inner coating composition of claim 1, wherein the high temperature resistant antioxidant is a hindered phenol antioxidant having a molecular weight greater than 500 g/mol.
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| CN105295705A (en) * | 2015-11-27 | 2016-02-03 | 苏州市明大高分子科技材料有限公司 | UV-curing optical fiber inner coating and preparation method thereof |
| CN110358353A (en) * | 2019-07-01 | 2019-10-22 | 浙江瑞通光电材料有限公司 | A kind of ultraviolet light solidification optical fiber coloring ink composition and its application |
| CN112812265A (en) * | 2020-12-31 | 2021-05-18 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
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| CN1894291A (en) * | 2003-10-14 | 2007-01-10 | 亚什兰许可和知识产权有限公司 | Radiation-curable inks for flexographic and screen-printing applications from multifunctional acrylate oligomers |
| CN101535203A (en) * | 2006-12-14 | 2009-09-16 | 帝斯曼知识产权资产管理有限公司 | D1365 bj radiation curable primary coating for optical fiber |
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