CN116376359B - Water-based UV (ultraviolet) inkjet ink and preparation method thereof - Google Patents
Water-based UV (ultraviolet) inkjet ink and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920001661 Chitosan Polymers 0.000 claims abstract description 58
- 239000002270 dispersing agent Substances 0.000 claims abstract description 43
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000000049 pigment Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940109262 curcumin Drugs 0.000 claims abstract description 15
- 235000012754 curcumin Nutrition 0.000 claims abstract description 15
- 239000004148 curcumin Substances 0.000 claims abstract description 15
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000002994 raw material Substances 0.000 claims abstract description 7
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- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 11
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 14
- 230000032683 aging Effects 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
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- 238000007254 oxidation reaction Methods 0.000 abstract description 4
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- 230000006750 UV protection Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 72
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010019909 Hernia Diseases 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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Abstract
The invention relates to water-based UV (ultraviolet) inkjet ink and a preparation method thereof, and belongs to the technical field of UV ink. The adhesiveness, ageing resistance and ultraviolet resistance of the ink are improved through the modified chitosan, and the pigment precipitation can be reduced by the mixed dispersing agent in the color paste, so that the storage time of the ink is prolonged; the dispersant 750 and the dispersant 760 cooperate with each other to form stable steric hindrance, so that the dispersibility of the pigment is improved; the wear resistance and the adhesiveness are improved by improving the crosslinking density of the crosslinking structure, and the aging resistance can be improved by adding curcumin with oxidation resistance and antibacterial property. The hydroxypropyl acrylate is used as a core monomer, the hydroxyethyl acrylate is used as a branching monomer, and the branching structure is formed by crosslinking reaction, so that the adhesive force and durability of the ink can be improved. An aqueous UV inkjet ink comprising the following raw materials: the aqueous polyurethane resin, modified chitosan, a photoinitiator, color paste, an auxiliary agent and deionized water.
Description
Technical Field
The invention belongs to the technical field of UV ink, and relates to water-based UV ink-jet ink and a preparation method thereof.
Background
The UV curable inkjet technology refers to a modern printing technology formed by integrating an inkjet printhead, a printing device, a photo-curing system and photo-curing ink, and combines the advantages of the UV curable ink and the inkjet printing technology, which has the advantages of the UV curable ink in terms of economy and technology, and the convenience of the inkjet printing technology in terms of use and operation. These advantages include: no volatile organic compounds; low energy consumption; fast curing; is suitable for various base materials; the spray head is not blocked; the ink composition is constant; the printing quality is good; excellent comprehensive performance, etc.
The aqueous UV ink-jet ink simultaneously maintains the advantages of the aqueous ink and the UV light-cured ink, has the characteristics of rapid printing and rapid drying of the UV ink, has lower viscosity than the UV ink, and has thinner film forming than the traditional UV ink-jet ink; the very low odor is essentially capable of achieving an odorless state. In addition, the ink color paste plays a decisive role in the quality of the finished UV inkjet ink, the more stable the color paste is dispersed, the finer and uniform the prepared ink system particles are, and the more stable the performances are during inkjet; however, although the existing aqueous UV inkjet ink has good printing smoothness, the aqueous UV inkjet ink has poor pigment dispersibility, so that the adhesion performance of the inkjet ink after fixed time is poor; in addition, aqueous UV inkjet inks require long shelf life, high storage stability, and water resistance.
Disclosure of Invention
The invention aims to provide water-based UV (ultraviolet) inkjet ink and a preparation method thereof, and the scheme of the invention improves the adhesiveness, ageing resistance and ultraviolet resistance of the ink by modifying chitosan, and the mixed dispersing agent in color paste can reduce pigment precipitation and increase the storage time of the ink; the dispersant 750 and the dispersant 760 cooperate with each other to form stable steric hindrance, so that the dispersibility of the pigment is improved; the wear resistance and the adhesiveness are improved by improving the crosslinking density of the crosslinking structure, and the aging resistance can be improved by adding curcumin with oxidation resistance and antibacterial property. The hydroxypropyl acrylate is used as a core monomer, the hydroxyethyl acrylate is used as a branching monomer, and the branching structure is formed by crosslinking reaction, so that the adhesive force and durability of the ink can be improved.
The aim of the invention can be achieved by the following technical scheme:
the water-based UV inkjet ink comprises the following raw materials in parts by weight: 58-65 parts of aqueous polyurethane resin, 1-3 parts of modified chitosan, 1-5 parts of photoinitiator, 25-26 parts of color paste, 0.5-2 parts of auxiliary agent and 60-70 parts of deionized water;
the preparation method of the color paste comprises the following steps:
stirring and mixing pigment, succinic acid, a mixed dispersing agent and deionized water to obtain a mixed solution;
and step two, adding the mixture into the mixed solution, and grinding to obtain color paste.
According to the scheme, the aqueous polyurethane resin is a polymer with active functional groups, and can form a crosslinked structure through reaction, so that the ageing resistance and the adhesiveness of the ink are improved; in the photo-curing process, the succinic acid can form ester bonds, and ester products are formed through reaction with other functional groups in the ink to participate in the curing process of the ink. The hydroxy functional groups in the hydroxypropyl acrylate and the hydroxyethyl acrylate can react with free radicals in the photoinitiator to promote the reaction to form a covalent bond structure, so that the ink is cured. The photoinitiator is one of the most core components in the aqueous UV inkjet ink, and can trigger photoinitiation reaction to form active free radicals, so that the photoinitiator and other ink components are subjected to free radical polymerization reaction, and the ink is rapidly cured. The modified chitosan can provide protection for the ink, prevent the influence of ultraviolet radiation on the ink, and reduce the damage of the ink to a printer nozzle.
As a preferable technical scheme of the invention, in the step one), the mixed dispersing agent comprises a dispersing agent 750 and a dispersing agent 760 according to a mass ratio of 3.0-3.2: 0.9-1.0; in the first and second steps, the mass ratio of the pigment, the succinic acid, the mixed dispersing agent, the mixture and the deionized water is 4.8-5.0:0.8-1.1:5.0-5.2:7.8-8.0:15-16; in the second step, the mixture is prepared from hydroxypropyl acrylate and hydroxyethyl acrylate according to a mass ratio of 1:1 to 1.5; the grinding time is 6-8h; the dispersant 750 is Tego dispers750W and the dispersant 760 is Tego dispers760W, all available from Shanghai, inc.
As a preferable technical scheme of the invention, the photoinitiator is formed by mixing at least two of photoinitiator 819, TPO, TPOL and ITX; preferably, the photoinitiator consists of TPO and TPOL in a mass ratio of 10:4, mixing; preferably, the photoinitiator consists of a photoinitiator 819, TPO and TPOL according to a mass ratio of 2-3:8-10: 2-4.
As a preferable technical scheme of the invention, the auxiliary agent comprises triethanolamine and a surfactant 104 according to a mass ratio of 0.5: 1-1.5.
The preparation method of the modified chitosan comprises the following steps:
(1) Adjusting the pH value of the chitosan solution, adding 3, 4-dihydroxybenzene propionic acid, and stirring and mixing to obtain a mixed solution;
(2) Adding curcumin, EDC and NHS water solution into the mixed solution, uniformly mixing, adjusting the pH value, and stirring for reaction to obtain a prefabricated chitosan solution;
(3) And (3) dialyzing the prefabricated chitosan solution, and freeze-drying to obtain the modified chitosan.
As a preferable technical scheme of the invention, in the step (1), the concentration of the chitosan solution is 0.65-0.80mol/mL, and the pH value is 4.8-5.0; the stirring and mixing conditions are that stirring is carried out for 30-60min at the rotating speed of 300-350 r/min; the dosage ratio of the chitosan solution, the NHS aqueous solution, the curcumin, the 3, 4-dihydroxybenzene propionic acid and the EDC in the steps (1) - (3) is 45-48mL:5mL:0.03-0.12g:0.11-0.48g:0.2-0.3g; the preparation method of the chitosan solution comprises the steps of dispersing chitosan in deionized water, adding hydrochloric acid solution, and adjusting the pH value to 4.8-5.0 to obtain the chitosan solution.
As a preferred technical scheme of the invention, in the step (2), the concentration of the NHS aqueous solution is 1.8-2.2mmol/mL; the stirring reaction condition is that the rotation speed is 450-500r/min, and the stirring reaction time is 10-12h; the pH value is adjusted to 5.0-5.2.
As a preferred technical scheme of the invention, in the step (3), the dialysis treatment is to dialyze in hydrochloric acid buffer solution with pH value of 4.8-5.0 for 48-50h, and then dialyze in PBS buffer solution and deionized water for 2-3h respectively.
A method for preparing aqueous UV inkjet ink, comprising the steps of:
s1, stirring and mixing aqueous polyurethane resin and deionized water to obtain a solution A;
s2, adding modified chitosan and an auxiliary agent into the solution A, and uniformly dispersing to obtain solution B;
s3, adding color paste into the solution B, and uniformly stirring to obtain solution C;
and S4, adding a photoinitiator into the solution C and stirring at a high speed to obtain the water-based UV inkjet ink.
As a preferable technical scheme of the invention, in the step S1, the stirring and mixing condition is that stirring is carried out for 10-15min under the rotation speed of 480-500 r/min; in the step S2, the uniform dispersion condition is that stirring is carried out for 10-15min under the condition that the rotating speed is 500-550 r/min; in the step S3, stirring for 20-25min under the condition that the rotation speed is 500-550 r/min; in the step S4, the high-speed stirring condition is that stirring is carried out for 30-35min under the rotating speed of 800-1000 r/min.
The invention has the beneficial effects that:
(1) According to the scheme, the modified chitosan is added, so that the adhesiveness of the ink is improved, the anti-aging and ultraviolet protection are provided, and the color of the ink after exposure is more stable; the compounded mixed dispersing agent in the color paste can lead the pigment to be dispersed uniformly, reduce pigment precipitation and increase the storage time of the ink, thereby ensuring the quality of printed matters; the scheme of the invention adopts the aqueous polyurethane resin as the main raw material, so the invention has low content of volatile organic compounds and is environment-friendly; the surfactant in the auxiliary agent can uniformly disperse the pigment in the ink, thereby preventing pigment precipitation and delamination.
(2) The long chain contained in the dispersing agent 750 forms steric hindrance, and the dispersing agent 760 has a branched or comb-shaped structure.
(3) The photoinitiator in the aqueous UV inkjet ink can generate active free radicals under the irradiation of ultraviolet rays, the free radicals can generate free radical polymerization reaction with other ink components to enable the ink to be rapidly cured, the components in the UV ink can react to form a crosslinked structure to enhance the light resistance and the anti-adhesion property of the ink, and meanwhile, the modified chitosan can react with active functional groups of the components in the ink through the reaction initiated by the photoinitiator to form the crosslinked structure. The crosslinking structure can greatly improve the wear resistance and adhesiveness of the ink, simultaneously introduces curcumin with oxidation resistance and antibacterial property, prevents chitosan from being oxidized in the modification process, greatly improves the ageing resistance of the ink, and is beneficial to keeping the color of the ink unchanged for a long time.
(4) In the scheme of the invention, hydroxyethyl acrylate and hydroxypropyl acrylate adopt carbon chains with different lengths, and have different properties and reaction rates. In the crosslinking reaction process, the reaction rate of the hydroxyethyl acrylate is slower, and the reaction rate of the hydroxypropyl acrylate is faster, so that the hydroxypropyl acrylate can be used as a core monomer, and the hydroxyethyl acrylate can be used as a branch monomer to form a branching structure through crosslinking reaction, thereby improving the crosslinking density of the polymer and greatly improving the adhesive force and durability of the ink.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
The water-based UV inkjet ink comprises the following raw materials in parts by weight: 58 parts of aqueous polyurethane resin, 1 part of modified chitosan, 1 part of photoinitiator, 25 parts of color paste, 0.5 part of auxiliary agent and 60 parts of deionized water; wherein, the photoinitiator consists of a photoinitiator 819, TPO and TPOL according to the mass ratio of 2:8:2, mixing; the auxiliary agent comprises triethanolamine and a surfactant 104 according to the mass ratio of 0.5:1, mixing;
the preparation method of the color paste comprises the following steps:
stirring and mixing pigment, succinic acid, a mixed dispersing agent and deionized water to obtain a mixed solution; wherein, the mixed dispersing agent consists of a dispersing agent 750 and a dispersing agent 760 according to the mass ratio of 3.0:0.9, mixing;
step two, adding the mixture into the mixed solution, and grinding for 6 hours to obtain color paste;
wherein the mixture is prepared from hydroxypropyl acrylate and hydroxyethyl acrylate according to a mass ratio of 1:1, mixing; the mass ratio of the pigment, the succinic acid, the mixed dispersing agent, the mixture and the deionized water is 4.8:0.8:5.0:7.8:15.
the preparation method of the modified chitosan comprises the following steps:
(1) Adjusting the pH value of the chitosan solution with the concentration of 0.65mol/mL to 4.8, adding 3, 4-dihydroxybenzene propionic acid, and stirring for 30min at the rotating speed of 300r/min to obtain a mixed solution;
(2) Adding curcumin, EDC and NHS aqueous solution with concentration of 1.8mmol/mL into the mixed solution, uniformly mixing, adjusting the pH value to 5.0, and stirring and reacting for 10 hours at the rotating speed of 450r/min to obtain a prefabricated chitosan solution;
(3) And (3) dialyzing the prepared chitosan solution in a hydrochloric acid buffer solution with the pH value of 4.8 for 48 hours, then respectively dialyzing in a PBS buffer solution and deionized water for 2 hours, and freeze-drying to obtain the modified chitosan.
Wherein the dosage ratio of the chitosan solution to the NHS aqueous solution to the curcumin to the 3, 4-dihydroxybenzene propionic acid to the EDC is 45mL:5mL:0.03g:0.11g:0.2g.
A method for preparing aqueous UV inkjet ink, comprising the steps of:
s1, stirring and mixing aqueous polyurethane resin and deionized water at the rotating speed of 480r/min for 10min to obtain a solution A;
s2, adding modified chitosan and an auxiliary agent into the solution A, and stirring for 10min at the rotating speed of 500r/min to obtain solution B;
s3, adding color paste into the solution B, and stirring for 20min at the rotating speed of 500r/min to obtain solution C;
s4, adding a photoinitiator into the solution C, and stirring for 30min at the rotating speed of 800r/min to obtain the water-based UV inkjet ink.
Example 2
The water-based UV inkjet ink comprises the following raw materials in parts by weight: 61.5 parts of aqueous polyurethane resin, 2 parts of modified chitosan, 3 parts of photoinitiator, 25.5 parts of color paste, 1.3 parts of auxiliary agent and 65 parts of deionized water; wherein, the photoinitiator consists of photoinitiator 819, TPO and TPOL according to the mass ratio of 2.5:9:3, mixing; the auxiliary agent comprises triethanolamine and a surfactant 104 according to the mass ratio of 0.5:1.25, mixing;
the preparation method of the color paste comprises the following steps:
stirring and mixing pigment, succinic acid, a mixed dispersing agent and deionized water to obtain a mixed solution; wherein, the mixed dispersing agent consists of a dispersing agent 750 and a dispersing agent 760 according to the mass ratio of 3.1: 0.95;
step two, adding the mixture into the mixed solution, and grinding for 6-8 hours to obtain color paste;
wherein the mixture is prepared from hydroxypropyl acrylate and hydroxyethyl acrylate according to a mass ratio of 1:1.25, mixing; the mass ratio of the pigment, the succinic acid, the mixed dispersing agent, the mixture and the deionized water is 4.9:1.0:5.1:7.9:15.5.
the preparation method of the modified chitosan comprises the following steps:
(1) Adjusting the pH value of the chitosan solution with the concentration of 0.72mol/mL to 4.9, adding 3, 4-dihydroxybenzene propionic acid, and stirring for 45min at the rotating speed of 330r/min to obtain a mixed solution;
(2) Adding curcumin, EDC and NHS aqueous solution with concentration of 2.0mmol/mL into the mixed solution, uniformly mixing, adjusting the pH value to 5.1, and stirring and reacting for 11 hours at the rotating speed of 480r/min to obtain a prefabricated chitosan solution;
(3) And (3) dialyzing the prepared chitosan solution in a hydrochloric acid buffer solution with the pH value of 4.9 for 49 hours, then dialyzing the prepared chitosan solution in PBS buffer solution and deionized water for 2.5 hours respectively, and freeze-drying to obtain the modified chitosan.
Wherein the dosage ratio of the chitosan solution to the NHS aqueous solution to the curcumin to the 3, 4-dihydroxybenzene propionic acid to the EDC is 46.5mL:5mL:0.75g:0.30g:0.25g.
A method for preparing aqueous UV inkjet ink, comprising the steps of:
s1, stirring and mixing aqueous polyurethane resin and deionized water at the rotating speed of 490r/min for 13min to obtain solution A;
s2, adding modified chitosan and an auxiliary agent into the solution A, and stirring for 12min at the rotating speed of 520r/min to obtain solution B;
s3, adding color paste into the solution B, and stirring for 22min at the rotating speed of 520r/min to obtain solution C;
s4, adding a photoinitiator into the solution C, and stirring for 32min at the rotating speed of 900r/min to obtain the water-based UV inkjet ink.
Example 3
The water-based UV inkjet ink comprises the following raw materials in parts by weight: 65 parts of aqueous polyurethane resin, 3 parts of modified chitosan, 5 parts of photoinitiator, 26 parts of color paste, 2 parts of auxiliary agent and 70 parts of deionized water; wherein, the photoinitiator consists of a photoinitiator 819, TPO and TPOL according to the mass ratio of 3:10:4, mixing; the auxiliary agent comprises triethanolamine and a surfactant 104 according to a mass ratio of 1:3, mixing;
the preparation method of the color paste comprises the following steps:
stirring and mixing pigment, succinic acid, a mixed dispersing agent and deionized water to obtain a mixed solution; wherein, the mixed dispersing agent consists of a dispersing agent 750 and a dispersing agent 760 according to the mass ratio of 3.2:1.0, mixing;
step two, adding the mixture into the mixed solution, and grinding for 8 hours to obtain color paste;
wherein the mixture is prepared from hydroxypropyl acrylate and hydroxyethyl acrylate according to a mass ratio of 1:1.5, mixing; the mass ratio of the pigment, the succinic acid, the mixed dispersing agent, the mixture and the deionized water is 5.0:1.1:5.2:8.0:16.
the preparation method of the modified chitosan comprises the following steps:
(1) Adjusting the pH value of the chitosan solution with the concentration of 0.80mol/mL to 5.0, adding 3, 4-dihydroxybenzene propionic acid, and stirring for 60min at the rotating speed of 350r/min to obtain a mixed solution;
(2) Adding curcumin, EDC and NHS aqueous solution with concentration of 2.2mmol/mL into the mixed solution, uniformly mixing, adjusting the pH value to 5.2, and stirring and reacting for 12 hours at the rotating speed of 500r/min to obtain a prefabricated chitosan solution;
(3) And (3) dialyzing the prepared chitosan solution in a hydrochloric acid buffer solution with the pH value of 5.0 for 50 hours, then respectively dialyzing in PBS buffer solution and deionized water for 3 hours, and freeze-drying to obtain the modified chitosan.
Wherein the dosage ratio of the chitosan solution to the NHS aqueous solution to the curcumin to the 3, 4-dihydroxybenzene propionic acid to the EDC is 48mL:5mL:0.12g:0.48g:0.3g.
A method for preparing aqueous UV inkjet ink, comprising the steps of:
s1, stirring and mixing aqueous polyurethane resin and deionized water at the rotating speed of 500r/min for 15min to obtain a solution A;
s2, adding modified chitosan and an auxiliary agent into the solution A, and stirring for 15min at the rotating speed of 550r/min to obtain solution B;
s3, adding color paste into the solution B, and stirring for 25min at the rotating speed of 550r/min to obtain solution C;
and S4, adding a photoinitiator into the solution C, and stirring for 35min at the rotating speed of 1000r/min to obtain the water-based UV ink-jet ink.
Comparative examples 1 to 2
The difference compared to example 3 is that the amounts of dispersant 750 and dispersant 760 are as shown in Table 1, and the remaining components, preparation steps and parameters are identical.
TABLE 1
| Dispersant 750 (parts) | Dispersant 760 (part) | |
| Comparative example 1 | 0 | 4.2 |
| Comparative example 2 | 4.2 | 0 |
Comparative example 3
Stirring and mixing pigment, a mixed dispersing agent and deionized water to obtain a mixed solution; in comparison with example 3, the difference is that comparative example 3 does not use succinic acid, and the remaining components, preparation steps and parameters are identical.
Comparative example 4
The difference compared to example 3 is that comparative example 4 uses chitosan instead of modified chitosan, and the remaining components, preparation steps and parameters are identical.
Comparative example 5
Adding EDC and NHS aqueous solution with the concentration of 2.2mmol/mL into the mixed solution, uniformly mixing, adjusting the pH value to 5.2, and stirring and reacting for 12 hours at the rotating speed of 500r/min to obtain a prefabricated chitosan solution; in comparison with example 3, comparative example 5 was different in that curcumin was not used, and the remaining components, preparation steps and parameters were identical.
Comparative examples 6 to 7
The difference compared with example 3 is that comparative examples 6 to 7 are hydroxypropyl acrylate and hydroxyethyl acrylate in amounts shown in Table 2, and the remaining components, preparation steps and parameters are identical.
TABLE 2
| Hydroxypropyl acrylate (parts) | Hydroxyethyl acrylate (part) | |
| Comparative example 6 | 0 | 2.5 |
| Comparative example 7 | 2.5 | 0 |
Performance testing
The aqueous UV inkjet inks prepared in examples 1-3 and comparative examples 1-7 were printed on the surface of copper paperboard to prepare inkjet printed copper paperboard samples, and the following tests were performed on each sample:
visual inspection of the printed pattern;
aging resistance is in accordance with JC/T287-20136.4.13; irradiating with 6000w hernia lamp for 3 months, and observing the condition of the sample;
the method for detecting the adhesive force is carried out according to the specification of GB/T9286; 1 millimeter cross-hatch is adopted for the sample;
the specific test results are shown in Table 3.
TABLE 3 Table 3
| Age resistance | Adhesion (%) | Printing pattern conditions | |
| Example 1 | No pulverization, no shedding and no fading | 97 | Clear pattern and normal color development |
| Example 2 | No pulverization, no shedding and no fading | 98 | Clear pattern and normal color development |
| Example 3 | No pulverization, no shedding and no fading | 98 | Clear pattern and normal color development |
| Comparative example 1 | - | - | Pigment agglomeration and failure to print normally |
| Comparative example 2 | - | - | Pigment agglomeration and failure to print normally |
| Comparative example 3 | Small part is pulverized and shed without fading | 90 | Clear pattern and normal color development |
| Comparative example 4 | Pulverizing and substantially completely removing | 82 | Clear pattern and normal color development |
| Comparative example 5 | More chalking and falling off and dull pattern color | 93 | Clear pattern and normal color development |
| Comparative example 6 | More chalking and falling off and dull color | 76 | Clear pattern and normal color development |
| Comparative example 7 | More chalking and falling off and dull color | 73 | Clear pattern and normal color development |
From the test results of table 3, it is understood that the aqueous UV inkjet inks prepared in examples 1 to 3 were significantly superior to comparative examples 1 to 7 in aging resistance, adhesion, and pattern printing effects, as compared to comparative examples 1 to 7.
From the analysis of examples 1-3 and comparative examples 1-2, the present invention adopts the long chain structure of dispersant 750 and the branching and comb-like structure of dispersant 760 to form stable steric hindrance, and the different mechanisms are used to improve the dispersibility of the pigment and ensure the dispersion stability of the pigment.
From the analysis of examples 1-3 and comparative examples 3-5, it is known that the photoinitiator in the aqueous UV inkjet ink generates active radicals under the irradiation of ultraviolet rays, and these radicals can undergo radical polymerization reaction with other ink components to enable the ink to be rapidly cured, components in the UV ink can react to form a crosslinked structure, light resistance and anti-adhesion of the ink are enhanced, and at the same time, the modified chitosan can react with active functional groups of the components in the ink through the reaction initiated by the photoinitiator to form a crosslinked structure. The crosslinking structure can greatly improve the wear resistance and adhesiveness of the ink, simultaneously introduces curcumin with oxidation resistance and antibacterial property, prevents chitosan from being oxidized in the modification process, greatly improves the ageing resistance of the ink, and is beneficial to keeping the color of the ink unchanged for a long time.
From the analysis of examples 1-3 and comparative examples 6-7, it is known that in the crosslinking reaction process of hydroxyethyl acrylate and hydroxypropyl acrylate, hydroxypropyl acrylate can be used as a core monomer, and hydroxyethyl acrylate can be used as a branching monomer, and a branching structure is formed by the crosslinking reaction, so that the crosslinking density of the polymer is improved, and the adhesive force and durability of the ink are greatly improved.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The water-based UV inkjet ink is characterized by comprising the following raw materials in parts by weight: 58-65 parts of aqueous polyurethane resin, 1-3 parts of modified chitosan, 1-5 parts of photoinitiator, 25-26 parts of color paste, 0.5-2 parts of auxiliary agent and 60-70 parts of deionized water; the photoinitiator is formed by mixing at least two of photoinitiator 819, TPO, TPOL and ITX; the auxiliary agent comprises triethanolamine and a surfactant 104 according to the mass ratio of 0.5:1 to 1.5;
the preparation method of the color paste comprises the following steps:
stirring and mixing pigment, succinic acid, a mixed dispersing agent and deionized water to obtain a mixed solution;
step two, adding the mixture into the mixed solution, and grinding to obtain color paste;
in the first step, the mixed dispersing agent consists of a dispersing agent 750 and a dispersing agent 760 according to the mass ratio of 3.0-3.2: 0.9-1.0;
in the second step, the mixture is prepared from hydroxypropyl acrylate and hydroxyethyl acrylate according to a mass ratio of 1:1 to 1.5; the grinding time is 6-8h;
in the color paste, the mass ratio of the pigment, the succinic acid, the mixed dispersing agent, the mixture and the deionized water is 4.8-5.0:0.8-1.1:5.0-5.2:7.8-8.0:15-16;
the preparation method of the modified chitosan comprises the following steps:
(1) Adjusting the pH value of the chitosan solution, adding 3, 4-dihydroxybenzene propionic acid, and stirring and mixing to obtain a mixed solution;
(2) Adding curcumin, EDC and NHS water solution into the mixed solution, uniformly mixing, adjusting the pH value, and stirring for reaction to obtain a prefabricated chitosan solution;
(3) And (3) dialyzing the prefabricated chitosan solution, and freeze-drying to obtain the modified chitosan.
2. The aqueous UV inkjet ink according to claim 1 wherein: in the step (1), the concentration of the chitosan solution is 0.65-0.80mol/mL, and the pH value is 4.8-5.0; the stirring and mixing conditions are that stirring is carried out for 30-60min at the rotating speed of 300-350 r/min; the dosage ratio of the chitosan solution, the NHS aqueous solution, the curcumin, the 3, 4-dihydroxybenzene propionic acid and the EDC in the steps (1) - (3) is 45-48mL:5mL:0.03-0.12g:0.11-0.48g:0.2-0.3g.
3. The aqueous UV inkjet ink according to claim 1 wherein: in the step (2), the concentration of the NHS aqueous solution is 1.8-2.2mmol/mL; the stirring reaction condition is that the rotation speed is 450-500r/min, and the stirring reaction time is 10-12h; the pH value is adjusted to 5.0-5.2.
4. The aqueous UV inkjet ink according to claim 1 wherein: in the step (3), the dialysis treatment is to dialyze in hydrochloric acid buffer solution with pH value of 4.8-5.0 for 48-50h, and then to dialyze in PBS buffer solution and deionized water for 2-3h respectively.
5. A method of preparing an aqueous UV inkjet ink according to any one of claims 1 to 4 wherein the method of preparation comprises the steps of:
s1, stirring and mixing aqueous polyurethane resin and deionized water to obtain a solution A;
s2, adding modified chitosan and an auxiliary agent into the solution A, and uniformly dispersing to obtain solution B;
s3, adding color paste into the solution B, and uniformly stirring to obtain solution C;
and S4, adding a photoinitiator into the solution C and stirring at a high speed to obtain the water-based UV inkjet ink.
6. The method for preparing the aqueous UV ink-jet ink according to claim 5, wherein:
in the step S1, stirring and mixing conditions are that stirring is carried out for 10-15min under the rotation speed of 480-500 r/min;
in the step S2, the uniform dispersion condition is that stirring is carried out for 10-15min under the condition that the rotating speed is 500-550 r/min;
in the step S3, stirring for 20-25min under the condition that the rotation speed is 500-550 r/min;
in the step S4, the high-speed stirring condition is that stirring is carried out for 30-35min under the rotating speed of 800-1000 r/min.
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| CN102988999A (en) * | 2012-05-09 | 2013-03-27 | 中国药科大学 | Curcumin-polysaccharide conjugate as well as preparation method and application thereof |
| CN105860653A (en) * | 2016-05-06 | 2016-08-17 | 安徽雅美油墨有限公司 | Modified-chitosan-containing high-waterproofness modified waterborne polyurethane printing ink and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102988999A (en) * | 2012-05-09 | 2013-03-27 | 中国药科大学 | Curcumin-polysaccharide conjugate as well as preparation method and application thereof |
| CN105860653A (en) * | 2016-05-06 | 2016-08-17 | 安徽雅美油墨有限公司 | Modified-chitosan-containing high-waterproofness modified waterborne polyurethane printing ink and preparation method thereof |
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| Title |
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| Evonik Operations GmbH.《润湿分散剂 TEGO® Dispers 760 W》.2023,第1页. * |
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