CN117363094A - Temperature-sensitive ultraviolet curing ink and preparation method thereof - Google Patents
Temperature-sensitive ultraviolet curing ink and preparation method thereof Download PDFInfo
- Publication number
- CN117363094A CN117363094A CN202311309007.7A CN202311309007A CN117363094A CN 117363094 A CN117363094 A CN 117363094A CN 202311309007 A CN202311309007 A CN 202311309007A CN 117363094 A CN117363094 A CN 117363094A
- Authority
- CN
- China
- Prior art keywords
- parts
- temperature
- acrylate
- ultraviolet light
- sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 18
- -1 acrylic ester Chemical class 0.000 claims abstract description 20
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 15
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 15
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012860 organic pigment Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000013307 optical fiber Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
- DZHSVSBJDNJICY-UHFFFAOYSA-N bis(4-methylphenyl)phosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound C1=CC(C)=CC=C1P(=O)(C=1C=CC(C)=CC=1)C(=O)C1=C(C)C=C(C)C=C1C DZHSVSBJDNJICY-UHFFFAOYSA-N 0.000 claims description 2
- CUJPJTIBYGTKKC-UHFFFAOYSA-N cyclohexanol;diphenylmethanone Chemical compound OC1CCCCC1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 CUJPJTIBYGTKKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000003094 microcapsule Substances 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 2
- BBAGPRAUWBSYDH-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O BBAGPRAUWBSYDH-UHFFFAOYSA-N 0.000 claims 1
- 238000004134 energy conservation Methods 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CHBVGDXRMCSNPU-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCOC(C)C(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCOC(C)C(CO)(CO)CO CHBVGDXRMCSNPU-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- TZUAKKVHNFEFBG-UHFFFAOYSA-N methyl n-[[2-(furan-2-ylmethylideneamino)phenyl]carbamothioyl]carbamate Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1N=CC1=CC=CO1 TZUAKKVHNFEFBG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses temperature-sensitive ultraviolet light curing ink and a preparation method thereof, wherein the curing ink comprises the following components in parts by weight: hyperbranched urethane acrylate: 30-60 parts of epoxy acrylate: 10-20 parts of modified rosin resin: 5-10 parts of acrylic ester monomer: 15-30 parts of thermochromic slurry: 3-10 parts of an auxiliary agent: 1-5 parts of photoinitiator: 5-10 parts. The invention fully utilizes the heat energy generated by the ultraviolet light source when the ultraviolet light source is excited to generate ultraviolet light, obviously improves the curing depth and the curing rate of the printing ink, can Reach ideal curing degree under extremely low energy, does not contain various substances which are identified in European Union regulations and have irreversible influence on human bodies or environment, and has important significance for green energy conservation.
Description
Technical Field
The invention belongs to the technical field of ultraviolet light curing ink preparation, and particularly relates to temperature-sensitive ultraviolet light curing ink and a preparation method thereof.
Background
Ultraviolet (UV) curing is a mature coating curing technology widely applied to industries such as furniture building materials, electronic communication, printing and packaging and the like. The ultraviolet light curing light source technology has been developed for many years, and two directions are generated, namely, a multiband mixed light source of infrared light, ultraviolet light (200-400 nm), visible light and the like, which is generated by exciting mercury vapor of a medium-pressure mercury lamp and a high-pressure mercury lamp; and secondly, a light source with a single wave band such as 365nm, 385nm and 395nm is generated when holes and electrons formed by exciting the LED chip are combined.
At present, most downstream enterprises still use UV mercury lamp ultraviolet light sources as the main source, and a small part of the downstream enterprises use LED ultraviolet light sources. However, no matter what kind of light source, a large amount of heat energy is generated in the continuous use process, and the heat energy is used as non-energy and needs to be released to the outside through a certain heat dissipation means, so that certain waste is generated.
On the other hand, with the increasing severity of the global ecological environment, the environmental protection policies of various countries are gradually coded, wherein the environmental protection policies are further coded by Reach and Rosh of European Union; the regulations of california 65, the united states, have the most widely affected.
The existing ink has low curing depth and curing rate, can not Reach ideal curing degree under extremely low energy, contains various substances which are identified in European Union Reach regulations and have irreversible influence on human bodies or environment, and is not friendly to green energy conservation.
Therefore, development of a temperature-sensitive uv curable ink to solve the above technical problems is urgently needed.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides temperature-sensitive ultraviolet curing ink and a preparation method thereof. Based on the consideration of fully utilizing heat energy generated by using an ultraviolet light source, the temperature-sensitive ultraviolet curing ink prepared from various carefully chosen materials such as hyperbranched polyurethane acrylic ester, modified rosin resin, temperature-sensitive color-changing materials treated by a specific process and the like has outstanding practical value.
The technical scheme adopted by the invention is as follows:
the temperature-sensitive ultraviolet curing ink is characterized by comprising the following components in parts by weight:
hyperbranched urethane acrylate: 30 to 60 portions
Epoxy acrylate: 10-20 parts
Modified rosin resin: 5-10 parts
Acrylate monomer: 15-30 parts
Thermochromic slurry: 3-10 parts
Auxiliary agent: 1 to 5 parts of
And (3) a photoinitiator: 5-10 parts.
Preferably, the hyperbranched urethane acrylate is prepared according to the following steps:
firstly, mixing glycidyl methacrylate with a polymerization inhibitor, then dropwise adding the mixture into dendritic hydroxyl-terminated polyamidoamine mixed with a catalyst triethylamine and a solvent tetrahydrofuran, wherein the molecular weight of the dendritic hydroxyl-terminated polyamidoamine is 500-1500, and reacting for 6-8 hours at the temperature of 60-70 ℃ to obtain a product A;
then, dropwise adding hydroxyethyl acrylate into isophorone diisocyanate, reacting for 3-5 hours at the temperature of 40-50 ℃, adding catalyst dibutyltin dilaurate and a product A after NCO reaches 5-8, reacting until NCO is less than 0.05 at the temperature of 60-70 ℃, and removing a solvent under reduced pressure to obtain a product B;
finally, adding 5-8% of polyfunctional polythiol and 15-25% of acrylic ester monomer into the product B, and stirring for 30 minutes at the temperature of 40-50 ℃ to obtain hyperbranched polyurethane acrylic ester;
wherein, the molar ratio of the materials during the synthesis of the hyperbranched polyurethane acrylic ester meets the following conditions: glycidyl methacrylate: the dendritic hydroxyl-terminated polyamidoamine is (3.5-5.5): (1-2); hydroxyethyl acrylate: isophorone diisocyanate: the product A is (7-12): (9-13): (1-3).
Preferably, the thermochromic paste is prepared by the following steps:
heating 5-10% of transparent organic pigment, 15-25% of modified rosin resin, 45-65% of acrylic ester monomer, 3-5% of hyperdispersant and 0.1-1% of polymerization inhibitor to above 60 ℃ and uniformly dispersing at 2500 rpm, grinding to fineness less than 5 microns, and filtering to obtain organic pigment slurry; then, adding 8-20% of microcapsule pigment, 0.5-1% of fumed silica, 20-30% of acrylic ester monomer and 1-2% of controllable flocculation dispersing agent into the organic pigment slurry, stirring and dispersing for 40 minutes at the temperature of 40-50 ℃ at the rotating speed of 500 rpm, and filtering to obtain the thermochromic slurry.
Preferably, the modified rosin resin is a solid modified rosin methacrylate containing difunctional groups.
Preferably, the epoxy acrylate is an amine modified epoxy acrylate.
Preferably, the acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclotrimethylolpropane methylacrylate, propoxylated neopentyl glycol diacrylate, propoxylated trimethylolpropane triacrylate and dipentaerythritol hexaacrylate.
Preferably, the Photoinitiator is one or a combination of more than one of 2,4, 6-trimethylbenzoyl di-p-tolylphosphine oxide, 2,4, 6-trimethylbenzoyl phosphonic acid ethyl ester, hydroxycyclohexane benzophenone, 2,4, 6-trimethoxybenzoyl, photoinitiator NPI-20400 and Photoinitiator Photoshop-637C.
The preparation method of the temperature-sensitive ultraviolet curing ink is characterized in that 30-60 parts of hyperbranched polyurethane acrylic ester, 10-20 parts of epoxy acrylic ester, 5-10 parts of modified rosin resin and 15-30 parts of acrylic ester monomer are added into a container to be mixed, and then stirred at the temperature of 50-60 ℃ for 30-45 minutes at the rotating speed of 1000-1500 rpm, when the fineness is less than 1 mu m, 3-10 parts of temperature-sensitive color-changing slurry, 1-5 parts of auxiliary agent and 5-10 parts of photoinitiator are added into the container, and stirred at the rotating speed of 600-900 rpm for 30-45 minutes, and when the fineness is less than 5 mu m, the temperature-sensitive optical fiber coloring ink is obtained by filtering.
Compared with the prior art, the invention has the beneficial effects that:
1. the temperature-sensitive optical fiber coloring ink prepared by the preparation method has excellent storage stability, and only needs to be less than 30mj/cm after being uniformly coated on the surface of a carrier and the temperature of a curing furnace is higher than 50 DEG C 2 The radiation energy of the resin can Reach more than 90 percent, and simultaneously has gorgeous color, excellent solvent wiping resistance and outstanding deep curing performance of the delbant, and does not contain substances which are identified in European Union Reach regulations and have irreversible influence on human bodies or environment, and is environment-friendlyThe color energy conservation has important significance.
2. The invention fully utilizes the heat energy generated by the ultraviolet light source when exciting to generate ultraviolet light, obviously improves the curing depth and curing rate of the ink, ensures that the ink can reach ideal curing degree under lower energy in nitrogen atmosphere with lower purity, and has great significance for energy conservation and consumption reduction.
Detailed Description
The preparation used in this example is a commercially available conventional product, and is not limited to the manufacturer as long as it is a qualified industrial product.
Throughout this application, the following terms have the indicated meanings:
for a better understanding of the present invention, reference will now be made to the following examples, but the scope of the invention as claimed is not limited to the scope of the examples. The experimentally measured values are measured in adaptation to the environment and will vary according to different materials and environments.
Example 1
Preparation of hyperbranched polyurethane acrylate RA01/RA02/RA03
The synthesis of hyperbranched urethane acrylates was carried out according to the data listed in the table.
The first step: preparation of the product A1/A2/A3
Adding 1.2 g of triethylamine, 50 g of tetrahydrofuran and 312.6 g of CYD-100H into a three-neck flask to form a mixture, then mixing 284.3 g of 3 glycidyl methacrylate with 1.2 g of p-hydroxyanisole, then dropwise adding the mixture into the mixture, controlling the temperature to 60-65 ℃, reacting for 7 hours, and filtering to obtain products A1/A2/A3 which are 421 g, 433 g and 479 g respectively;
and a second step of: preparation of the product B1/B2/B3
223.4 g of IPDI is added into a three-neck flask, 98.68 g of hydroxyethyl acrylate is added into the three-neck flask dropwise, the temperature is controlled between 40 ℃ and 45 ℃, 0.5 g of dibutyltin dilaurate and 283.3 g of product A are added after the mixture is cooled to room temperature after the mixture is reacted for 4 hours, the temperature is controlled between 60 ℃ and 65 ℃, and after NCO is controlled below 0.05, the solvent is removed to obtain products B1/B2/B3 of 560 g, 571 g and 566 g respectively.
And a third step of: preparation of hyperbranched polyurethane acrylic ester RA01/RA02/RA03
400 g of the product B, 25 g of THIOCURE 440 and 75 g of propoxylated neopentyl glycol diacrylate are added into a three-neck flask, and the mixture is stirred for 30 minutes at a temperature of between 40 and 50 ℃ to obtain 477 g, 481 g and 481 g of hyperbranched polyurethane acrylate RA01/RA02/RA03 respectively.
EXAMPLE 2 preparation of thermochromic paste B01
The first step: preparation of organic pigment slurry
Adding propoxyl trimethylol propane triacrylate and modified rosin resin into a container according to the mass in a table, heating to 60 ℃, stirring at 2500 rpm for 30min, adding phthalocyanine blue BGS, SOLSPERSE 32500, stirring at 2500 rpm for 30min after the modified rosin resin is dissolved, and grinding to fineness less than 5 microns to obtain 180 g of organic pigment slurry.
And a second step of: thermochromic slurry preparation
Neopentyl glycol diacrylate, cyclotrimethylolpropane methylacrylate, organic pigment paste, thermochromic pigment, BYK-P104S and AEROSIL R972 are added into a container according to the mass in the table, stirred and dispersed for 40 minutes at 40-50 ℃ at 500 rpm, and 189 g of thermochromic paste is obtained by filtering.
Example 3 preparation of temperature-sensitive ultraviolet light curing ink C01\C02\C03
Adding 1-5 into a container according to the mass in a table, stirring at the temperature of 50-60 ℃ for 40 minutes at the rotating speed of 1200 revolutions per minute, adding 6-11 into the container according to the mass proportion in the table after the fineness is less than 1 mu m, stirring at the rotating speed of 800 revolutions per minute for 40 minutes, wherein the fineness is less than 5 mu m, and filtering to obtain the temperature-sensitive ultraviolet curing ink C01/C02/C03 which is 191 g, 191 g and 190 g respectively.
Example 4 testing physicochemical Properties
The temperature-sensitive ultraviolet light curing ink C01 and the commercial UV ink product in the example 3 are uniformly coated on the surface of the PET film through a coating film preparation device, and are respectively cured by a UV mercury lamp light source and a UV-LED light source and then tested.
The comparison experiment shows that the temperature-sensitive ultraviolet light curing ink prepared from hyperbranched polyurethane acrylate, thermochromic slurry, modified rosin resin and other preferable functional materials has excellent solvent wiping resistance, outstanding deep curing performance and oxidation resistance polymerization inhibition performance, can realize sufficient curing under extremely low curing energy, and has important significance on energy conservation and consumption reduction.
Claims (8)
1. The temperature-sensitive ultraviolet curing ink is characterized by comprising the following components in parts by weight:
hyperbranched urethane acrylate: 30 to 60 portions
Epoxy acrylate: 10-20 parts
Modified rosin resin: 5-10 parts
Acrylate monomer: 15-30 parts
Thermochromic slurry: 3-10 parts
Auxiliary agent: 1 to 5 parts of
And (3) a photoinitiator: 5-10 parts.
2. The temperature-sensitive ultraviolet light curing ink as claimed in claim 1, wherein the hyperbranched polyurethane acrylate is prepared by the following steps:
firstly, mixing glycidyl methacrylate with a polymerization inhibitor, then dropwise adding the mixture into dendritic hydroxyl-terminated polyamidoamine mixed with a catalyst triethylamine and a solvent tetrahydrofuran, wherein the molecular weight of the dendritic hydroxyl-terminated polyamidoamine is 500-1500, and reacting for 6-8 hours at the temperature of 60-70 ℃ to obtain a product A;
then, dropwise adding hydroxyethyl acrylate into isophorone diisocyanate, reacting for 3-5 hours at the temperature of 40-50 ℃, adding catalyst dibutyltin dilaurate and a product A after NCO reaches 5-8, reacting until NCO is less than 0.05 at the temperature of 60-70 ℃, and removing a solvent under reduced pressure to obtain a product B;
finally, adding 5-8% of polyfunctional polythiol and 15-25% of acrylic ester monomer into the product B, and stirring for 30 minutes at the temperature of 40-50 ℃ to obtain hyperbranched polyurethane acrylic ester;
wherein, the molar ratio of the materials during the synthesis of the hyperbranched polyurethane acrylic ester meets the following conditions: glycidyl methacrylate: the dendritic hydroxyl-terminated polyamidoamine is (3.5-5.5): (1-2); hydroxyethyl acrylate: isophorone diisocyanate: the product A is (7-12): (9-13): (1-3).
3. The temperature-sensitive ultraviolet light curing ink as claimed in claim 1, wherein the thermochromic paste is prepared by the following steps:
heating 5-10% of transparent organic pigment, 15-25% of modified rosin resin, 45-65% of acrylic ester monomer, 3-5% of hyperdispersant and 0.1-1% of polymerization inhibitor to above 60 ℃ and uniformly dispersing at 2500 rpm, grinding to fineness less than 5 microns, and filtering to obtain organic pigment slurry; then, adding 8-20% of microcapsule pigment, 0.5-1% of fumed silica, 20-30% of acrylic ester monomer and 1-2% of controllable flocculation dispersing agent into the organic pigment slurry, stirring and dispersing for 40 minutes at the temperature of 40-50 ℃ at the rotating speed of 500 rpm, and filtering to obtain the thermochromic slurry.
4. The temperature-sensitive ultraviolet light curing ink as defined in claim 1, wherein the modified rosin resin is a solid modified rosin methacrylate containing difunctional groups.
5. The temperature-sensitive uv curable ink of claim 1 wherein the epoxy acrylate is an amine modified epoxy acrylate.
6. The temperature-sensitive ultraviolet light curing ink as defined in claim 1, wherein the acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclo-trimethylol propane methylacrylate, propoxylated neopentyl glycol diacrylate, propoxylated trimethylol propane triacrylate and dipentaerythritol hexaacrylate.
7. The temperature-sensitive ultraviolet light curing ink as claimed in claim 1, wherein the Photoinitiator is one or a combination of any of 2,4, 6-trimethylbenzoyl di-p-tolylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phosphonate, hydroxycyclohexane benzophenone, 2,4, 6-trimethoxybenzoyl, photoinitiator NPI-20400 and Photoinitiator Photoshop-637C.
8. The method for preparing the temperature-sensitive ultraviolet curing ink according to the claims 1-7, wherein 30-60 parts of hyperbranched polyurethane acrylate, 10-20 parts of epoxy acrylate, 5-10 parts of modified rosin resin and 15-30 parts of acrylate monomer are added into a container for mixing, and then stirred at a temperature of 50-60 ℃ for 30-45 minutes at a rotating speed of 1000-1500 rpm, when the fineness is less than 1 μm, 3-10 parts of thermochromic paste, 1-5 parts of auxiliary agent and 5-10 parts of photoinitiator are added into the container, and stirred at a rotating speed of 600-900 rpm for 30-45 minutes, and when the fineness is less than 5 μm, the temperature-sensitive optical fiber coloring ink is obtained after filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311309007.7A CN117363094A (en) | 2023-10-11 | 2023-10-11 | Temperature-sensitive ultraviolet curing ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311309007.7A CN117363094A (en) | 2023-10-11 | 2023-10-11 | Temperature-sensitive ultraviolet curing ink and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117363094A true CN117363094A (en) | 2024-01-09 |
Family
ID=89392151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311309007.7A Pending CN117363094A (en) | 2023-10-11 | 2023-10-11 | Temperature-sensitive ultraviolet curing ink and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117363094A (en) |
-
2023
- 2023-10-11 CN CN202311309007.7A patent/CN117363094A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107286740B (en) | UV-LED offset printing ink and preparation method thereof | |
| EP2228417B1 (en) | Ink composition and inkjet recording method | |
| JP5329817B2 (en) | Color filter pigment dispersion and color filter pigment dispersion resist composition containing the same | |
| CN109749509B (en) | LED-UV ink with snowflake special effect and preparation method thereof | |
| CN101200622A (en) | Protective adhesive film, screen panel and mobile electronic terminal | |
| CN108587271B (en) | Water-based UV polyurethane coating and preparation method thereof | |
| TW200934838A (en) | Radiation curable coating compositions, related coatings and methods | |
| CN107141880B (en) | LED (light-emitting diode) curing UV (ultraviolet) offset printing ink as well as preparation method and application thereof | |
| CN105623239B (en) | A kind of photochromic composition and its application | |
| CN112239624B (en) | Ophthalmic lens comprising a visible light-cured color-changing coating | |
| CN108484871B (en) | LED photo-curing polyurethane acrylate prepolymer and synthetic method and application thereof | |
| CN111349359A (en) | Ultraviolet-cured silk-screen printing metal ink and preparation method thereof | |
| CN110922933A (en) | Ultraviolet curing adhesive for bonding aluminum alloy and thermoplastic polyurethane film and preparation method thereof | |
| JP4402590B2 (en) | Pigment dispersion composition and use thereof | |
| EP2423277A2 (en) | Ink composition for inkjet recording, inkjet recording method and inkjet printed article | |
| CN110628378A (en) | Ultraviolet light curing adhesive with high hydrophobic property and preparation method thereof | |
| CN110615861A (en) | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof | |
| CN117363094A (en) | Temperature-sensitive ultraviolet curing ink and preparation method thereof | |
| CN114058208B (en) | UV (ultraviolet) silk-screen printing ink for baking varnish surface and preparation method thereof | |
| CN110358353A (en) | A kind of ultraviolet light solidification optical fiber coloring ink composition and its application | |
| WO2012029585A1 (en) | Dispersant comprising polycarboxylic acid resin that contains unsaturated groups | |
| CN113429826B (en) | LED photocuring ink | |
| CN113387826B (en) | Water-based ultraviolet curing resin and preparation method and application thereof | |
| CN115584173A (en) | Matte coating and application thereof | |
| CN102385254A (en) | Photo-sensitivity resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |