CN114369391A - Environment-friendly degradable printing ink and preparation method thereof - Google Patents
Environment-friendly degradable printing ink and preparation method thereof Download PDFInfo
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- CN114369391A CN114369391A CN202210156022.1A CN202210156022A CN114369391A CN 114369391 A CN114369391 A CN 114369391A CN 202210156022 A CN202210156022 A CN 202210156022A CN 114369391 A CN114369391 A CN 114369391A
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 43
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000004321 preservation Methods 0.000 claims description 23
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 10
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 5
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 acrylic ester Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 125000003916 ethylene diamine group Chemical group 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
Abstract
The invention discloses an environment-friendly degradable printing ink and a preparation method thereof, wherein the printing ink consists of modified water-based acrylate, modified nano titanium dioxide, a defoaming agent, a dispersing agent and water; the preparation method comprises the following steps: adding the modified water-based acrylate, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800r/min to obtain the environment-friendly degradable printing ink. The invention has the beneficial effects that: the degradable environment-friendly printing ink prepared by the method can effectively meet the current printing requirements. Compared with the traditional printing ink, the alkaline solution can be used for degrading the printing ink, and the raw materials of the printed product can be effectively recycled, so that the energy can be saved, the consumption can be reduced, the pollution can be reduced, and the cost can be reduced.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to environment-friendly degradable printing ink and a preparation method thereof.
Background
The solvent-based ink is composed of four main components, namely colored dye, binder resin (high molecular resin or natural resin), organic solvent and related auxiliary agents, and the binder resin is usually dispersed in the organic solvent, so the binder component generally contains the organic solvent which accounts for about half of the total weight of the binder, if the binder component is contacted for a long time, the skin of operators and users is corroded to a certain extent, and the Volatile Organic Compounds (VOCs) contained in the binder component can be mixed in the air and passively absorbed into the human body in the production process, so the health of the human body is greatly threatened. The organic solvent component in the solvent-based ink accounts for about half of the total amount of the solvent, and the solvent is extremely easy to volatilize, the solvent is volatilized in the air in the production and use processes, part of the solvent which is volatilized into the air is mixed with oxygen, and even the solvent and the oxygen generate chemical reaction to generate new harmful substances, so that the air environment of human living and activities is greatly damaged, the ecological balance is disturbed under the severe condition, and the water-based ink is produced under the severe condition.
The water-based ink is called water ink for short and consists of pigment, relevant assistant, water-dispersible or water-soluble polymer resin binder and solvent. Therefore, the water-based ink has the greatest characteristic of being different from solvent-based ink, and the water-based ink has the most obvious characteristic of being very low in organic solvent content or completely free of organic solvent, so that the water-based ink has the advantages of being very low in VOCs content, non-toxic or low in toxicity, free of combustion, free of corrosion and the like, and water resources are very abundant on the earth, so that the water-based ink is popular under the current theme of green environmental protection, and is rapidly developed in the printing industry and related industries as a core green environment-friendly printing material.
However, the existing ink is not degradable, and the ink cannot be separated from the printed product, so that most of the printed products after use can only be subjected to waste treatment, and larger resource waste is caused.
Disclosure of Invention
Aiming at the problems, the invention provides the environment-friendly degradable printing ink and the preparation method thereof, the printing product adopting the degradable printing ink can degrade the printing ink on the surface of the product by using an alkaline solution (such as NaOH solution), the printed printing ink is degraded into extremely fine suspended matters, and the suspended matters are separated from the printing product and completely enter the alkaline solution, so that the product material can be repeatedly utilized.
On one hand, the invention provides environment-friendly degradable printing ink which comprises the following components in parts by weight:
20-35 parts of modified water-based acrylic ester,
20-25 parts of modified nano titanium dioxide,
2-4 parts of a defoaming agent,
0.75 to 2 portions of dispersant,
45-50 parts of water.
In some embodiments, the modified aqueous acrylate is prepared by the steps of:
step A: mixing diglycol laurate, stearyl alcohol and 1, 4-dihydroxy butane-2-sodium sulfonate, then carrying out vacuum dehydration, adding tris (2-hydroxyethyl) isocyanurate, hexamethylene diisocyanate and stannous oxide, and carrying out heat preservation reaction in a nitrogen atmosphere to obtain a prepolymer 1;
and B: adding a chain extender into the prepolymer 1, and carrying out heat preservation reaction in a nitrogen atmosphere to obtain a prepolymer 2;
and C: adding an end-capping reagent and polyethylene glycol methacrylate into the prepolymer 2, carrying out heat preservation reaction in a nitrogen atmosphere, and then adding water for emulsification to obtain an intermediate emulsion;
step D: adding methyl methacrylate and butyl acrylate into the emulsion, uniformly stirring, adding an initiator, and carrying out free radical polymerization reaction in a nitrogen protection atmosphere to obtain the modified water-based acrylate.
In some embodiments, in step A, the reaction temperature is maintained at 65-70 ℃ for 1.5-2.5 h.
In some embodiments, in step B, the reaction temperature is maintained at 20-25 ℃ for 0.5-1 h.
In some embodiments, in step C, the reaction temperature is maintained at 20-35 ℃ for 0.5-1 h.
In some embodiments, in step D, the reaction temperature is maintained at 70-80 ℃ for 1.5-3 h.
In some embodiments, the modified nano titania is prepared by:
adding the nano titanium dioxide into the ethanol-water mixed solution, uniformly mixing, stirring and heating, dropwise adding a coating agent, carrying out centrifugal separation after reaction, washing and drying after precipitation to obtain the modified nano titanium dioxide.
In some embodiments, the modified nano titania is prepared by:
adding nano titanium dioxide into an ethanol-water mixed solution, uniformly mixing in an ultrasonic crusher, stirring and heating to 80 ℃, dropwise adding a coating agent into the mixed solution, reacting for 3-5h, carrying out centrifugal separation, precipitating, washing with absolute ethanol and distilled water, and drying at 100 ℃ for 24h to obtain the modified nano titanium dioxide.
In some embodiments, the capping agent is methacryloxypropyltrimethoxysilane.
In another aspect, the invention provides a method for preparing an environment-friendly degradable printing ink, which comprises the following steps: adding the modified water-based acrylate, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800r/min to obtain the environment-friendly degradable printing ink.
The invention has the beneficial effects that:
the degradable environment-friendly printing ink prepared by the method can effectively meet the current printing requirements. Compared with the traditional printing ink, the alkaline solution can be used for degrading the printing ink, and the raw materials of the printed product can be effectively recycled, so that the energy can be saved, the consumption can be reduced, the pollution can be reduced, and the cost can be reduced.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1
The preparation method of the modified water-based acrylate comprises the following steps:
step A: sequentially adding 50mL of diglycol laurate, 200g of stearyl alcohol and 3.48g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at 90 ℃, then adding 63g of tris (2-hydroxyethyl) isocyanurate, 12.6g of hexamethylene diisocyanate and 0.35g of stannous oxide, and carrying out heat preservation reaction for 1.5h at 65 ℃ in a nitrogen atmosphere to obtain a prepolymer 1;
and B: reducing the temperature of the reaction system in the step A to 15 ℃, adding 8.4g of ethylenediamine chain extender into the prepolymer 1, and carrying out heat preservation reaction for 0.5h at 20 ℃ in a nitrogen atmosphere to obtain a prepolymer 2;
and C: adding 2.41g of di-n-butylamine end-capping reagent and 1.76g of polyethylene glycol methacrylate into the prepolymer 2, carrying out heat preservation reaction for 0.5h at 20 ℃ in a nitrogen atmosphere, and then adding deionized water for emulsification to obtain an intermediate emulsion;
step D: and adding 70g of methyl methacrylate and 32g of butyl acrylate into the intermediate emulsion, uniformly stirring, adding 0.85g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 1.5h at 70 ℃ in a nitrogen atmosphere to obtain the modified water-based acrylate.
The preparation steps of the modified nano titanium dioxide are as follows:
preparing ethanol-water mixed solution by absolute ethanol and deionized water according to the volume ratio of 6:1, adding 100g of nano titanium dioxide into 500mL of ethanol-water mixed solution, uniformly mixing the solution in an ultrasonic crusher, stirring and heating the mixture to 80 ℃, dropwise adding methacryloxypropyl trimethoxy silane into the mixture, wherein the weight ratio of the methacryloxypropyl trimethoxy silane to the nano titanium dioxide is 3:10, carrying out centrifugal separation after reacting for 3h, washing the precipitate with absolute ethanol and distilled water, and drying the precipitate at 100 ℃ for 24h to obtain the modified nano titanium dioxide.
And (2) adding 20 parts of modified water-based acrylate, 2 parts of JY-801 type organic silicon defoaming agent and 45 parts of deionized water into a stirring kettle, stirring for 30min at a stirring speed of 400r/min, then adding 20 parts of modified nano titanium dioxide and 0.75 part of EBS dispersing agent, and stirring for 20min at a stirring speed of 600r/min to obtain the environment-friendly degradable printing ink sample 1.
Example 2
The preparation method of the modified water-based acrylate comprises the following steps:
step A: sequentially adding 50mL of diglycol laurate, 200g of stearyl alcohol and 3.48g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at 90 ℃, then adding 63g of tris (2-hydroxyethyl) isocyanurate, 12.6g of hexamethylene diisocyanate and 0.35g of stannous oxide, and carrying out heat preservation reaction for 2.5h at 70 ℃ in a nitrogen atmosphere to obtain a prepolymer 1;
and B: reducing the temperature of the reaction system in the step A to 15 ℃, adding 8.4g of ethylenediamine chain extender into the prepolymer 1, and carrying out heat preservation reaction for 1h at 25 ℃ in a nitrogen atmosphere to obtain a prepolymer 2;
and C: adding 2.41g of di-n-butylamine end-capping reagent and 1.76g of polyethylene glycol methacrylate into the prepolymer 2, carrying out heat preservation reaction for 1h at 35 ℃ in a nitrogen atmosphere, and then adding deionized water for emulsification to obtain an intermediate emulsion;
step D: and adding 70g of methyl methacrylate and 32g of butyl acrylate into the intermediate emulsion, uniformly stirring, adding 0.85g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 3h at 80 ℃ in a nitrogen atmosphere to obtain the modified water-based acrylate.
The preparation steps of the modified nano titanium dioxide are as follows:
preparing ethanol-water mixed solution by absolute ethanol and deionized water according to the volume ratio of 6:1, adding 100g of nano titanium dioxide into 500mL of ethanol-water mixed solution, uniformly mixing the solution in an ultrasonic crusher, stirring and heating the mixture to 80 ℃, dropwise adding methacryloxypropyl trimethoxy silane into the mixture, wherein the weight ratio of the methacryloxypropyl trimethoxy silane to the nano titanium dioxide is 3:10, carrying out centrifugal separation after 5h of reaction, washing the precipitate with absolute ethanol and distilled water, and drying the precipitate at 100 ℃ for 24h to obtain the modified nano titanium dioxide.
And adding 35 parts of modified water-based acrylate, 4 parts of JY-801 type organic silicon defoaming agent and 50 parts of deionized water into a stirring kettle, stirring for 50min at a stirring speed of 500r/min, then adding 25 parts of modified nano titanium dioxide and 2 parts of EBS dispersing agent, and stirring for 30min at a stirring speed of 800r/min to obtain an environment-friendly degradable printing ink sample 2.
Example 3
The preparation method of the modified water-based acrylate comprises the following steps:
step A: sequentially adding 50mL of diglycol laurate, 200g of stearyl alcohol and 3.48g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at 90 ℃, then adding 63g of tris (2-hydroxyethyl) isocyanurate, 12.6g of hexamethylene diisocyanate and 0.35g of stannous oxide, and carrying out heat preservation reaction for 2.5h at 65 ℃ in a nitrogen atmosphere to obtain a prepolymer 1;
and B: reducing the temperature of the reaction system in the step A to 15 ℃, adding 8.4g of ethylenediamine chain extender into the prepolymer 1, and carrying out heat preservation reaction for 1h at 20 ℃ in a nitrogen atmosphere to obtain a prepolymer 2;
and C: adding 2.41g of di-n-butylamine end-capping reagent and 1.76g of polyethylene glycol methacrylate into the prepolymer 2, carrying out heat preservation reaction for 1h at 30 ℃ in a nitrogen atmosphere, and then adding deionized water for emulsification to obtain an intermediate emulsion;
step D: and adding 70g of methyl methacrylate and 32g of butyl acrylate into the intermediate emulsion, uniformly stirring, adding 0.85g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 2h at 75 ℃ in a nitrogen atmosphere to obtain the modified water-based acrylate.
The preparation steps of the modified nano titanium dioxide are as follows:
preparing ethanol-water mixed solution by absolute ethanol and deionized water according to the volume ratio of 6:1, adding 100g of nano titanium dioxide into 500mL of ethanol-water mixed solution, uniformly mixing the solution in an ultrasonic crusher, stirring and heating the mixture to 80 ℃, dropwise adding methacryloxypropyl trimethoxy silane into the mixture, wherein the weight ratio of the methacryloxypropyl trimethoxy silane to the nano titanium dioxide is 3:10, carrying out centrifugal separation after reacting for 3h, washing the precipitate with absolute ethanol and distilled water, and drying the precipitate at 100 ℃ for 24h to obtain the modified nano titanium dioxide.
And adding 28 parts of modified water-based acrylate, 3 parts of JY-801 type organic silicon defoaming agent and 50 parts of deionized water into a stirring kettle, stirring for 45min at the stirring speed of 450r/min, then adding 22 parts of modified nano titanium dioxide and 1 part of EBS dispersing agent, and stirring for 25min at the stirring speed of 700r/min to obtain the environment-friendly degradable printing ink sample 3.
Comparative example 1
Comparative sample 1 was prepared in substantially the same manner as in example 1 except that the modified nano titanium dioxide was replaced with the ordinary nano titanium dioxide.
Comparative example 2
Comparative sample 2 was prepared in substantially the same manner as in example 1 except that the modified nano-titania was prepared in a different manner.
The modified nano titanium dioxide of comparative example 2 was prepared as follows:
preparing ethanol-water mixed solution by absolute ethanol and deionized water according to the volume ratio of 6:1, adding 100g of nano titanium dioxide into 500mL of ethanol-water mixed solution, uniformly mixing the ethanol-water mixed solution in an ultrasonic pulverizer, stirring and heating the mixture to 80 ℃, dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0%, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the nano titanium dioxide is 1:1, carrying out centrifugal separation after reacting for 3h, washing the precipitate with absolute ethanol and distilled water, and drying for 24h at 100 ℃ to obtain the modified nano titanium dioxide.
Ink Performance testing
Adhesion force: the surface of the coating film is tested by a Baige method according to the national standard GB 9286-1988.
The three-dimensional effect is as follows: the gravure ink is observed, and if the protrusions can be seen visually, the three-dimensional effect is strong; if the protrusion can be touched by hands, the three-dimensional effect is strong.
Viscosity: and tested with a rotational viscometer.
Gloss: tested according to GB/T13217.2-2009.
Bending: the test is carried out according to the paint film flexibility test method in GB/T1731-1993.
Water resistance: the test is carried out according to the method A of measuring the water resistance of a paint film in GB/T1733 + 1993.
Solid content: tested according to the national standard GB/T1725-2007.
Degradability: dipping 35% NaOH solution by using linen according to 500g/cm2And (3) wiping the ink printing position back and forth by force, wherein the stroke of each time is 2-3 cm, and the reciprocating is carried out for 20 times.
The test results are shown in the following table.
It will be apparent to those skilled in the art that various modifications may be made to the above embodiments without departing from the general spirit and concept of the invention. All falling within the scope of protection of the present invention. The protection scheme of the invention is subject to the appended claims.
Claims (10)
1. The environment-friendly degradable printing ink is characterized by comprising the following components in parts by weight:
20-35 parts of modified water-based acrylic ester,
20-25 parts of modified nano titanium dioxide,
2-4 parts of a defoaming agent,
0.75 to 2 portions of dispersant,
45-50 parts of water.
2. The environmentally degradable printing ink according to claim 1, wherein the modified aqueous acrylate is prepared by the following steps:
step A: mixing diglycol laurate, stearyl alcohol and 1, 4-dihydroxy butane-2-sodium sulfonate, then carrying out vacuum dehydration, adding tris (2-hydroxyethyl) isocyanurate, hexamethylene diisocyanate and stannous oxide, and carrying out heat preservation reaction in a nitrogen atmosphere to obtain a prepolymer 1;
and B: adding a chain extender into the prepolymer 1, and carrying out heat preservation reaction in a nitrogen atmosphere to obtain a prepolymer 2;
and C: adding an end-capping reagent and polyethylene glycol methacrylate into the prepolymer 2, carrying out heat preservation reaction in a nitrogen atmosphere, and then adding water for emulsification to obtain an intermediate emulsion;
step D: adding methyl methacrylate and butyl acrylate into the emulsion, uniformly stirring, adding an initiator, and carrying out free radical polymerization reaction in a nitrogen protection atmosphere to obtain the modified water-based acrylate.
3. The environment-friendly degradable printing ink according to claim 2, wherein in the step A, the temperature of the heat preservation reaction is 65-70 ℃, and the time of the heat preservation reaction is 1.5-2.5 h.
4. The environment-friendly degradable printing ink according to claim 2, wherein in the step B, the temperature of the heat preservation reaction is 20-25 ℃, and the time of the heat preservation reaction is 0.5-1 h.
5. The environment-friendly degradable printing ink according to claim 2, wherein in the step C, the temperature of the heat preservation reaction is 20-35 ℃, and the time of the heat preservation reaction is 0.5-1 h.
6. The environment-friendly degradable printing ink according to claim 2, wherein in the step D, the temperature of the heat preservation reaction is 70-80 ℃, and the time of the heat preservation reaction is 1.5-3 h.
7. The environmentally degradable printing ink according to claim 1, wherein the modified nano titanium dioxide is prepared by the following steps:
adding the nano titanium dioxide into the ethanol-water mixed solution, uniformly mixing, stirring and heating, dropwise adding a coating agent, carrying out centrifugal separation after reaction, washing and drying after precipitation to obtain the modified nano titanium dioxide.
8. The environmentally degradable printing ink according to claim 7, wherein the modified nano titanium dioxide is prepared by the following steps:
adding nano titanium dioxide into an ethanol-water mixed solution, uniformly mixing in an ultrasonic crusher, stirring and heating to 80 ℃, dropwise adding a coating agent into the mixed solution, reacting for 3-5h, carrying out centrifugal separation, precipitating, washing with absolute ethanol and distilled water, and drying at 100 ℃ for 24h to obtain the modified nano titanium dioxide.
9. The environmentally degradable printing ink according to claim 7 or 8, wherein the capping agent is methacryloxypropyltrimethoxysilane.
10. The method for preparing the environmentally degradable printing ink according to any one of claims 1 to 9, comprising the steps of: adding the modified water-based acrylate, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800r/min to obtain the environment-friendly degradable printing ink.
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