CN116445035B - Flexible plate water-based ink and preparation method thereof - Google Patents
Flexible plate water-based ink and preparation method thereof Download PDFInfo
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- CN116445035B CN116445035B CN202310455863.7A CN202310455863A CN116445035B CN 116445035 B CN116445035 B CN 116445035B CN 202310455863 A CN202310455863 A CN 202310455863A CN 116445035 B CN116445035 B CN 116445035B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 polysiloxane Polymers 0.000 claims abstract description 37
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 35
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 35
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 55
- 239000002808 molecular sieve Substances 0.000 claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 229920001661 Chitosan Polymers 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000976 ink Substances 0.000 description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 238000004383 yellowing Methods 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The application relates to the field of ink, and particularly discloses flexographic water-based ink and a preparation method thereof. The flexible plate water-based ink comprises the following raw materials in parts by weight: 60-70 parts of epoxy modified acrylic resin, 5-7 parts of hydroxyl-terminated polysiloxane, 8-10 parts of inorganic nano particles, 1-2 parts of defoamer, 1-2 parts of dispersant, 5-10 parts of pigment, 10-20 parts of propylene glycol, 10-15 parts of ethanol and 30-40 parts of water. The water-based ink prepared by the application has the advantages of good adhesiveness and good stability.
Description
Technical Field
The application relates to the field of ink, in particular to flexographic water-based ink and a preparation method thereof.
Background
The flexible plate water ink is also called liquid ink, and is mainly prepared by carrying out compound grinding processing on water-soluble resin, organic pigment, solvent and related auxiliary agents. The water-based ink is particularly suitable for packaging printed products with strict sanitary requirements such as cigarettes, wines, foods, beverages, medicines, children toys and the like.
The water-based printing ink is prepared by mixing water-based polymer emulsion, organic pigment, resin, surfactant and related additives physically through a chemical process, and the ink does not contain volatile organic solvents, so that the water-based printing ink has no adverse effect on the health of workers in the printing process, has no pollution to the atmosphere, eliminates the hidden danger of inflammability and explosiveness of workplaces, and improves the safety. Meanwhile, compared with the solvent-based ink, the use cost of the water-based ink is saved by about 30 percent. This unique advantage of ink meets increasingly stringent environmental regulations, is becoming increasingly popular with the packaging and printing community worldwide, and is gradually expanding rapidly to the journal printing industry.
However, the existing water-based ink has the problems of poor stability and poor adhesive force, and obviously cannot meet the requirements of the packaging printing industry.
Disclosure of Invention
In order to improve the adhesiveness and stability of the water-based ink, the application provides a flexible plate water-based ink and a preparation method thereof.
In a first aspect, the present application provides a flexographic water-based ink, which adopts the following technical scheme:
the flexible plate water-based ink comprises the following raw materials in parts by weight: 60-70 parts of epoxy modified acrylic resin, 5-7 parts of hydroxyl-terminated polysiloxane, 8-10 parts of inorganic nano particles, 1-2 parts of defoamer, 1-2 parts of dispersant, 5-10 parts of pigment, 10-20 parts of propylene glycol, 10-15 parts of ethanol and 30-40 parts of water.
By adopting the technical scheme, the acrylic resin is one of important binder resins in the water-based ink, and has the advantages of cleanness, inertness, light resistance, baking resistance (no yellowing), good luster, high stability, good rheological property and the like. However, the traditional acrylic resin for the ink has the defects of poor water resistance, poor adhesive force and the like, the epoxy resin has good bonding function, and the water resistance, stability and adhesiveness can be effectively improved by introducing the epoxy resin component into the acrylic molecular structure, so that the comprehensive performance of the water-based ink is greatly improved;
the hydroxyl-terminated polysiloxane has high adhesive property due to the fact that the hydroxyl-terminated polysiloxane is of a linear structure and contains hydroxyl at two ends, and the hydroxyl-terminated polysiloxane and epoxy groups in the epoxy modified acrylic resin are subjected to crosslinking curing reaction, so that the adhesive property of the ink is greatly improved; the inorganic nano particles have high surface energy, extremely strong adsorption capacity and extremely easy adsorption on the surface of a matrix, the combination capacity of an ink layer and the matrix is improved, the film formed by adding the inorganic nano particles into the epoxy modified acrylic emulsion has the advantages of water resistance, wear resistance and high tinting strength, the particle size of the inorganic nano particles is small, the inorganic nano particles can be effectively dispersed into the acrylic emulsion, and meanwhile, after the inorganic nano particles are combined with hydroxyl-terminated polysiloxane, an organic-silane coupling agent-inorganic interface layer is formed, so that the epoxy modified acrylic resin, the hydroxyl-terminated polysiloxane and the inorganic nano particles are matched for use, and the adhesive force between the ink layer and a printed matter is further improved.
Preferably, the epoxy modified acrylic resin comprises the following steps:
s1: uniformly mixing 10-20 parts of acrylic acid, 10-20 parts of methyl methacrylate, 5-8 parts of butyl methacrylate and 1-2 parts of vinyl triethoxysilane to obtain a mixed solution, and dividing the mixed solution into two parts by equal volume; 3-5 parts of benzoyl peroxide is dropwise added into one part of the mixed solution, and the mixture is stirred and mixed to obtain a mixed solution A, and the other part of the mixed solution B;
s2: mixing 1-2 parts of dimethylbenzene and 15-22 parts of epoxy resin, heating up to 70-80 ℃ while stirring, then dripping the mixed solution B into the mixed solution of dimethylbenzene and epoxy resin, reacting for 10-15 minutes, dripping the mixed solution A, and reacting for 2 hours under heat preservation to obtain a mixed solution C;
s3: and cooling the mixed solution C to 50-55 ℃, stirring and dropwise adding ammonia water to neutralize the mixed solution C until the pH of the system is 7-8, and carrying out heat preservation and stirring for 10-30 minutes to obtain the epoxy modified acrylic resin.
By adopting the technical scheme, the epoxy acrylic resin prepared by the method is used as a resin binder for water-based ink, and the prepared ink has good adhesive force, good water resistance, film forming property and pigment wetting dispersibility, and is environment-friendly and safe.
Preferably, the inorganic nanoparticles include nano 5A molecular sieves and nano titania.
By adopting the technical scheme, the nano titanium dioxide can play a better role in preventing sedimentation and aging in an ink system, the polarity of the silicon hydroxyl on the wall of the nano 5A molecular sieve can enable the 5A molecular sieve to have good compatibility with the binder with polar groups, so that the molecular sieve can be connected with the binder through chemical bonds, and the nano titanium dioxide and the nano 5A molecular sieve can be matched for use to enable the network chain structure of the binder to be more perfect, and the stability and adhesiveness of the ink are improved.
Preferably, the mass ratio of the nano 5A molecular sieve to the nano titanium dioxide is 1: (3-5).
By adopting the technical scheme, the mass ratio of the nano 5A molecular sieve to the nano titanium dioxide is 1: (3-5) can exert the compounding effect well, and further improve the stability and the adhesiveness of the ink.
Preferably, 1-3 parts of polydimethylsiloxane are also added.
By adopting the technical scheme, the hydroxyl-terminated polysiloxane has poor stability in the use process, is easy to bleach, and has good surface state control capability, and the stability and adhesiveness of the ink can be further improved by matching the hydroxyl-terminated polysiloxane with the polydimethylsiloxane.
Preferably, 5-6 parts of chitosan is also added.
By adopting the technical scheme, the chitosan is added into the ink system, so that the antibacterial capability, elasticity, water resistance and compatibility of the ink can be improved, the bonding strength of the chitosan and the epoxy modified acrylic emulsion can be improved due to the matched use of hydroxyl-terminated polysiloxane and polydimethylsiloxane, the adhesive force of the ink layer and a matrix can be improved, the inorganic nanoparticles absorb water due to the existence of the inorganic nanoparticles, the drying speed of the ink layer can be improved, if the drying speed of the ink layer is too high, the ink layer can be cracked, the chitosan has certain water retention, the drying problem brought by the inorganic nanoparticles can be solved, the cracking caused by the too high drying speed of the ink layer can be effectively prevented, and the adhesive force, the water resistance and the stability of the ink layer can be enhanced.
Preferably, the dispersant is oleamide.
By adopting the technical scheme, the oleamide can be used as a dispersing agent to reduce the viscosity of an ink system, effectively disperse solid and liquid particles such as nano inorganic particles and pigments, prevent sedimentation and agglomeration of the particles, improve the fluidity and simultaneously have the function of a slip agent, and can reduce the friction coefficient of the surface of the ink.
In a second aspect, the present application provides a method for preparing a flexographic water-based ink, which adopts the following technical scheme: a preparation method of a flexible plate water-based ink comprises the following steps:
s1: uniformly mixing epoxy modified acrylic resin, propylene glycol, ethanol and water to form emulsion;
s2: and uniformly mixing the emulsion, hydroxyl-terminated polysiloxane, inorganic nano particles, a defoaming agent, a dispersing agent and pigment to obtain the flexible plate water-based ink.
In summary, the present application has the following beneficial effects:
1. the epoxy resin component is introduced into the acrylic acid molecular structure, so that the water resistance, the stability and the adhesiveness can be effectively improved, the comprehensive performance of the water-based ink can be greatly improved, the hydroxyl-terminated polysiloxane and the epoxy group in the epoxy modified acrylic resin are subjected to a crosslinking curing reaction, the adhesiveness of the ink is greatly improved, the surface energy of inorganic nano particles is high, the inorganic nano particles have extremely strong adsorption capacity and are extremely easy to adsorb on the surface of a matrix, the bonding capacity of an ink layer and the matrix is improved, the film formed by adding the inorganic nano particles into the epoxy modified acrylic emulsion also has the advantages of water resistance, wear resistance and high tinting strength, the particle size of the inorganic nano particles is small, the inorganic nano particles can be effectively dispersed into the acrylic emulsion, and meanwhile, after the inorganic nano particles are combined with the hydroxyl-terminated polysiloxane, an organic-silane coupling agent-inorganic interface layer is formed, and the adhesive force between the ink layer and a printed matter is further improved.
2. The nano titanium dioxide can play a good role in preventing sedimentation and aging in an ink system, the polarity of the silicon hydroxyl on the wall of the nano 5A molecular sieve can enable the 5A molecular sieve to have good compatibility with a connecting material with a polar group, so that the molecular sieve can be connected with the connecting material through a chemical bond, and the nano titanium dioxide and the nano 5A molecular sieve can enable the network chain structure of the connecting material to be more perfect by matching.
3. The chitosan is added into an ink system, so that the antibacterial capability, elasticity, water resistance and compatibility of the ink can be improved, the bonding strength of the chitosan and the epoxy modified acrylic emulsion can be improved due to the matched use of hydroxyl-terminated polysiloxane and polydimethylsiloxane, the adhesive force of an ink layer and a matrix can be improved, the inorganic nano particles absorb water due to the existence of the inorganic nano particles, the drying speed of the ink layer can be improved, if the drying speed of the ink layer is too high, the ink layer can be cracked, the chitosan has certain water retention, the drying problem caused by the inorganic nano particles can be solved, the cracking caused by the too high drying speed of the ink layer can be effectively prevented, and the adhesive force, the water resistance and the stability of the ink layer can be enhanced.
Detailed Description
The raw material sources are as follows:
acrylic acid was from the new material technology limited company of zilu, hunan;
methyl methacrylate is from Shandong Ying chemical Co., ltd;
butyl methacrylate is from Shandong Hao chemical Co., ltd;
vinyl triethoxysilane is available from Qingdao Hengda New Material technologies Co., ltd;
the epoxy resin is from Baling petrochemical, E-20;
hydroxyl-terminated polysiloxanes are from Shenzhen Haisan biotechnology Co., ltd;
nano 5A molecular sieve and nano zeolite molecular sieve are from zhengzhou superlong nanomaterial limited;
polydimethylsiloxane was from Shanghai Seiyaka Biotechnology Co., ltd;
chitosan is from the company of volley biotechnology, langasite;
oleamide was from Shandong polymer chemistry Co., ltd;
the polyether modified silicon defoamer is from Shenzhen Ji Peng silicon fluorine materials Co., ltd;
hydroxypropyl methylcellulose was from the county of civilian sciences, inc.
The present application is further described in detail below in connection with the preparation examples and examples.
Preparation example
Preparation example 1
The epoxy modified acrylic resin comprises the following steps:
s1: uniformly mixing 10kg of acrylic acid, 10kg of methyl methacrylate, 5kg of butyl methacrylate and 1kg of vinyltriethoxysilane to obtain a mixed solution, and dividing the mixed solution into two parts by equal volume; 3kg of benzoyl peroxide is dropwise added into one part of the mixed solution, and the mixture is stirred and mixed to obtain a mixed solution A, and the other part of the mixed solution B;
s2: mixing 1kg of dimethylbenzene and 15kg of epoxy resin, heating to 70 ℃ while stirring, dripping the mixed solution B into the mixed solution of dimethylbenzene and epoxy resin, reacting for 10 minutes, dripping the mixed solution A, and reacting for 2 hours while maintaining the temperature to obtain a mixed solution C;
s3: and cooling the mixed solution C to 50 ℃, stirring and dropwise adding ammonia water to neutralize the mixed solution C until the pH of the system is 7, and carrying out heat preservation and stirring for 10 minutes to obtain the epoxy modified acrylic resin.
Preparation example 2
The epoxy modified acrylic resin comprises the following steps:
s1: uniformly mixing 15kg of acrylic acid, 15kg of methyl methacrylate, 6.5kg of butyl methacrylate and 1.5kg of vinyltriethoxysilane to obtain a mixed solution, and dividing the mixed solution into two parts by equal volume; adding 4kg of benzoyl peroxide into one part of the mixed solution dropwise, stirring and mixing to obtain a mixed solution A, and adding the other part of the mixed solution B;
s2: mixing 1.5kg of dimethylbenzene and 18kg of epoxy resin, heating up to 75 ℃ while stirring, then dropwise adding the mixed solution B into the mixed solution of dimethylbenzene and epoxy resin, reacting for 12 minutes, then dropwise adding the mixed solution A, and reacting for 2 hours under heat preservation to obtain a mixed solution C;
s3: and cooling the mixed solution C to 52 ℃, stirring and dropwise adding ammonia water to neutralize the mixed solution to the pH of 7, and carrying out heat preservation and stirring for 20 minutes to obtain the epoxy modified acrylic resin.
Preparation example 3
The epoxy modified acrylic resin comprises the following steps:
s1: uniformly mixing 20kg of acrylic acid, 20kg of methyl methacrylate, 8kg of butyl methacrylate and 2kg of vinyltriethoxysilane to obtain a mixed solution, and dividing the mixed solution into two parts by equal volume; dropwise adding 5kg of benzoyl peroxide into one part of the mixed solution, stirring and mixing to obtain a mixed solution A, and adding the other part of the mixed solution B;
s2: mixing 2kg of dimethylbenzene and 22kg of epoxy resin, heating up to 80 ℃ while stirring, dripping the mixed solution B into the mixed solution of dimethylbenzene and epoxy resin, reacting for 15 minutes, dripping the mixed solution A, and reacting for 2 hours while maintaining the temperature to obtain a mixed solution C;
s3: and cooling the mixed solution C to 55 ℃, stirring and dropwise adding ammonia water to neutralize the mixed solution C until the pH of the system is 8, and carrying out heat preservation and stirring for 30 minutes to obtain the epoxy modified acrylic resin.
Preparation example 4
The epoxy modified acrylic resin is prepared by the following steps:
50kg of acrylic resin, 10kg of ethanol, 2kg of vinyltriethoxysilane and 22kg of epoxy resin were uniformly mixed to obtain an epoxy-modified acrylic resin.
Examples
Example 1
A preparation method of a flexible plate water-based ink comprises the following steps:
s1: uniformly mixing 60kg of epoxy modified acrylic resin, 10kg of propylene glycol, 10kg of ethanol and 30kg of water to form emulsion;
s2: uniformly mixing the emulsion, 5kg of hydroxyl-terminated polysiloxane, 1kg of polydimethylsiloxane, 5kg of chitosan, 8kg of inorganic nano particles (4 kg of nano 5A molecular sieve and 4kg of nano titanium dioxide), 1kg of polyether modified silicon defoamer, 1kg of dispersing agent (oleamide) and pigment to obtain flexible plate water-based ink; wherein the epoxy-modified acrylic resin was derived from preparation example 1.
Example 2
A preparation method of a flexible plate water-based ink comprises the following steps:
s1: uniformly mixing 65kg of epoxy modified acrylic resin, 15kg of propylene glycol, 12kg of ethanol and 35kg of water to form emulsion;
s2: uniformly mixing the emulsion, 7kg of hydroxyl-terminated polysiloxane, 2kg of polydimethylsiloxane, 5.5kg of chitosan, 9kg of inorganic nano particles (4 kg of nano 5A molecular sieve and 5kg of nano titanium dioxide), 1.5kg of polyether modified silicon defoamer, 1.5kg of dispersing agent (oleamide) and pigment to obtain flexible plate water-based ink; wherein the epoxy-modified acrylic resin was derived from preparation example 1.
Example 3
A preparation method of a flexible plate water-based ink comprises the following steps:
s1: uniformly mixing 70kg of epoxy modified acrylic resin, 20kg of propylene glycol, 15kg of ethanol and 40kg of water to form emulsion;
s2: uniformly mixing the emulsion, 6kg of hydroxyl-terminated polysiloxane, 3kg of polydimethylsiloxane, 6kg of chitosan, 10kg of inorganic nano particles (4 kg of nano 5A molecular sieve and 6kg of nano titanium dioxide), 2kg of polyether modified silicon defoamer, 2kg of dispersing agent (oleamide) and pigment to obtain flexible plate water-based ink; wherein the epoxy-modified acrylic resin was derived from preparation example 1.
Examples 4 to 6
Examples 4 to 6 are different from example 2 in that the preparation method of the epoxy-modified acrylic resin is sequentially from preparation examples 2 to 4, and the remaining steps are the same as example 2.
Example 7
Example 7 differs from example 2 in that no nano 5A molecular sieve was added, the nano titania was 9kg, and the rest of the steps were the same as in example 2.
Example 8
Example 8 differs from example 2 in that no nano titanium dioxide was added, the nano 5A molecular sieve was 9kg, and the rest of the procedure was the same as in example 2.
Example 9
Example 9 differs from example 2 in that the nano titania was replaced with an equivalent amount of nano silica, and the rest of the procedure was the same as in example 2.
Example 10
Example 10 differs from example 2 in that the nano 5A molecular sieve was replaced with an equivalent amount of nano zeolite molecular sieve, and the rest of the procedure was the same as in example 2.
Examples 11 to 15
Examples 11 to 15 are different from example 2 in the mass and mass ratio of the nano 5A molecular sieve and the nano titania are different, and the mass and mass ratio of the nano 5A molecular sieve and the nano titania in examples 11 to 15 are shown in the following table:
TABLE 1 mass and mass ratio of nano 5A molecular sieves and nano titania in examples 11-15
| Nanometer 5A molecular sieve/kg | Nanometer titanium dioxide/kg | The mass ratio of the two | |
| Example 11 | 2.25 | 6.75 | 1：3 |
| Example 12 | 1.8 | 7.2 | 1：4 |
| Example 13 | 1.5 | 7.5 | 1：5 |
| Example 14 | 2.5 | 6.5 | 1：2.6 |
| Example 15 | 1.4 | 7.6 | 1：5.4 |
Example 16
Example 16 differs from example 12 in that the hydroxyl-terminated polysiloxane was replaced with an equivalent amount of polydimethylsiloxane, and the rest of the procedure was the same as in example 12.
Example 17
Example 17 differs from example 12 in that the polydimethylsiloxane was replaced with an equivalent amount of hydroxyl-terminated polysiloxane, and the rest of the procedure was the same as in example 12.
Example 18
Example 18 differs from example 12 in that no chitosan was added and the rest of the procedure was the same as example 12.
Example 19
Example 19 differs from example 12 in that the same amount of chitosan was replaced with the same amount of hydroxypropyl methylcellulose, and the rest of the procedure was the same as in example 12.
Example 20
Example 20 differs from example 12 in that oleamide was replaced with an equivalent amount of sodium lignin sulfonate, and the rest of the procedure was the same as example 12.
Comparative example
Comparative example 1
Comparative example 1 was different from example 12 in that the epoxy-modified acrylic resin was replaced with an equivalent amount of acrylic resin, and the rest of the procedure was the same as in example 12.
Comparative example 2
Comparative example 2 was different from example 12 in that no inorganic nanoparticles were added, and the rest of the procedure was the same as example 12.
Comparative example 3
Comparative example 3 differs from example 12 in that no hydroxyl-terminated polysiloxane was added, and the rest of the procedure was the same as in example 12.
Performance test
Detection method
The adhesion fastness of the aqueous inks prepared in examples 1 to 20 and comparative examples 1 to 3 was measured according to the national standard GB/T13217.7-2009 method for detecting adhesion fastness of liquid ink.
And (3) ink stability detection: the stability of the aqueous inks prepared in examples 1 to 20 and comparative examples 1 to 3 was measured with reference to standard QB 567-1983, and the presence or absence of the thickening and gelation phenomena of the ink layer was observed.
The ink layers prepared in examples 1 to 20 and comparative examples 1 to 3 were subjected to water resistance test according to the principle of the water resistance test of 5.7 in GB/T17121-1997, and the degree of scratch discoloration was classified into grades: 1. severe discoloration; 2. obvious discoloration; 3. slightly discoloring; 4. substantially free of discoloration; 5. does not change color.
TABLE 2 ink Performance test Table prepared in examples 1-20 and comparative examples 1-3
As can be seen by combining the data of examples 1-3 and table 2, the ink layers prepared in examples 1-3 of the present application have good adhesion properties, the adhesion fastness is basically over 93%, the phenomena of reverse thickening and gelation do not basically occur in the stability experiment, the stability is good, and the water resistance grade reaches grade 4;
as can be seen from the data of examples 2, 4-6, and table 2, the inks formulated by the acrylic resin modification method in this application have good adhesion and good water resistance, film forming properties, and stability;
as can be seen by combining the data of the embodiment 2 and the embodiment 7-10 and combining the data of the table 2, the adhesion of the ink can be effectively improved by the combination of the nano titanium dioxide and the nano 5A molecular sieve, mainly because the network structure of the binder can be more perfect by the combination of the nano titanium dioxide and the nano 5A molecular sieve, and the stability and the adhesion of the ink are improved;
as can be seen in combination with example 2, examples 11-15 and the data in table 2, the mass ratio of 5A molecular sieve to nano titania is 1: (3-5) can better play a role in matching, and further improve the water resistance and the adhesiveness of the ink;
it can be seen from the data of examples 12, 16-17, and Table 2 that the combination of hydroxyl-terminated polysiloxane and polydimethylsiloxane further improves the stability and adhesion of the ink;
as can be seen by combining examples 12, examples 18-19 and the data in table 2, the addition of chitosan to the ink system can improve the adhesion of the ink;
as can be seen from the data of example 12 and example 20 in combination with table 2, oleamide as a dispersant can significantly improve the adhesion of the ink;
as can be seen from the data of examples 12, 16 and comparative examples 1 to 3, the combination of the epoxy-modified acrylic resin, the hydroxyl-terminated polysiloxane and the inorganic nanoparticles can further improve the adhesion, water resistance and stability of the ink layer.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (4)
1. A flexographic aqueous ink, characterized in that: the material comprises the following raw materials in parts by weight: 60-70 parts of epoxy modified acrylic resin, 5-7 parts of hydroxyl-terminated polysiloxane, 8-10 parts of inorganic nano particles, 1-2 parts of defoamer, 1-2 parts of dispersant, 5-10 parts of pigment, 10-20 parts of propylene glycol, 10-15 parts of ethanol and 30-40 parts of water;
5-6 parts of chitosan is also added;
1-3 parts of polydimethylsiloxane is also added;
the inorganic nano particles comprise nano 5A molecular sieve and nano titanium dioxide; the mass ratio of the nano 5A molecular sieve to the nano titanium dioxide is 1:4.
2. the flexographic aqueous ink according to claim 1, wherein: the epoxy modified acrylic resin comprises the following steps:
s1: uniformly mixing 10-20 parts of acrylic acid, 10-20 parts of methyl methacrylate, 5-8 parts of butyl methacrylate and 1-2 parts of vinyl triethoxysilane to obtain a mixed solution, and dividing the mixed solution into two parts by equal volume; 3-5 parts of benzoyl peroxide is dropwise added into one part of the mixed solution, and the mixture is stirred and mixed to obtain a mixed solution A, and the other part of the mixed solution B;
s2: mixing 1-2 parts of dimethylbenzene and 15-22 parts of epoxy resin, heating up to 70-80 ℃ while stirring, then dripping the mixed solution B into the mixed solution of dimethylbenzene and epoxy resin, reacting for 10-15 minutes, dripping the mixed solution A, and reacting for 2 hours under heat preservation to obtain a mixed solution C;
s3: and cooling the mixed solution C to 50-55 ℃, stirring and dropwise adding ammonia water to neutralize the mixed solution C until the pH of the system is 7-8, and carrying out heat preservation and stirring for 10-30 minutes to obtain the epoxy modified acrylic resin.
3. The flexographic aqueous ink according to claim 1, wherein: the dispersing agent is oleamide.
4. A method for preparing the flexographic water-based ink according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
s1: uniformly mixing epoxy modified acrylic resin, propylene glycol, ethanol and water to form emulsion;
s2: and uniformly mixing the emulsion, hydroxyl-terminated polysiloxane, inorganic nano particles, a defoaming agent, a dispersing agent and pigment to obtain the flexible plate water-based ink.
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