CN111423765A - Preparation process of environment-friendly water-based ink - Google Patents
Preparation process of environment-friendly water-based ink Download PDFInfo
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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
- C09D11/02—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
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/00—Processes of polymerisation
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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Abstract
The invention discloses a preparation process of environment-friendly water-based ink, which comprises the following steps: firstly, weighing raw materials; secondly, adding deionized water into a dispersion cylinder, adding pigment, carrying out normal temperature ultrasound for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, and carrying out high-speed dispersion and grinding to obtain color paste; and thirdly, mixing the color paste with the polyacrylate emulsion, and adding the modified filler, the dispersant and the defoaming agent to obtain the environment-friendly water-based ink. The water-based polyacrylate emulsion is used as a film forming substance of the ink, the emulsion has high film forming property and adhesive force, and the addition of the modified filler can effectively prevent the ink aging phenomenon caused by ultraviolet rays, reduce the damage caused by the ultraviolet rays and the organic resin substrate, and ensure that the water-based ink has both water resistance and ultraviolet resistance stability; the raw materials are all green and environment-friendly, and the water-based ink which is environment-friendly, excellent in comprehensive performance and capable of effectively defending ultraviolet rays is obtained.
Description
Technical Field
The invention belongs to the technical field of ink preparation, and particularly relates to a preparation process of environment-friendly water-based ink.
Background
Ink is an important material for printing packaging materials, and represents patterns and characters on a printing material through printing. Chlorinated polypropylene ink, polyurethane ink and polyacrylate oil ink are used in the largest amount in printing and packaging, and the solvent-based ink contains a large amount of organic solvents such as benzene, toluene, butanone, ethyl acetate and the like, so that the volatile solvents pollute the air and harm the health of operators in the using process of the solvent-based ink, and the residual solvents in the packaged products seriously pollute food in the packages, so the water-based ink is increasingly important.
The water-based ink is prepared by compounding and grinding a water-based connecting material, an organic pigment, a solvent and related auxiliary agents, and is particularly suitable for packaging and printing products with strict requirements on sanitary conditions, such as cigarettes, wines, foods, beverages, medicines, toys for children and the like. The water-based ink uses water to replace 30-70% of toxic organic solvents in the traditional ink, so that the water-based ink has small influence on the health of workers in the printing process, has small pollution to the atmospheric environment, eliminates the hidden danger of flammability and explosiveness of workplaces, improves the safety, and is a recognized environment-friendly ink.
The invention patent with application number 201710512557.7 discloses a water-based printing ink and a preparation method thereof, wherein the ink is prepared from the following raw materials in parts by weight: 15-10 parts of alcohol/water type acrylic resin, 10-15 parts of polyurethane resin, 2-10 parts of acrylic resin, 10-20 parts of lignin modified phenolic resin, 15-20 parts of saturated polyester resin, 5-10 parts of isopropanol, 10-15 parts of dipropylene glycol dimethyl ether, 5-10 parts of isopropyl acetate, 2-10 parts of black pigment, 20-30 parts of water-based pigment, 1-2 parts of magnet, 2-5 parts of hydrotalcite, 1-5 parts of ethylene bis stearamide, 2-3 parts of polypropylene wax, 1-2 parts of hydroxylamine hydrochloride, 1.5-2 parts of antioxidant, 20-30 parts of calcium chloride, 5-10 parts of activated alumina, 2-5 parts of calcium carbonate and 2-3 parts of light stabilizer. By the mode, the printing ink is non-toxic, harmless, green and environment-friendly, and is high in surface glossiness and good in colorability. The ink is water-based environment-friendly ink, but the adhesive property and the dispersion property of the ink need to be further improved, the adhesion to various substrate materials is not high, and the ink cannot effectively protect ultraviolet rays, so that the application of the ink is limited.
Disclosure of Invention
The invention aims to provide a preparation process of environment-friendly water-based ink, which adopts water-based polyacrylate emulsion as a film forming substance of the ink, wherein the water-based polyacrylate emulsion has higher film forming property and adhesive force, and can effectively prevent the ink aging phenomenon caused by ultraviolet rays, reduce the damage caused by the ultraviolet rays and the organic resin substrate material, and avoid the decomposition of low-surface-energy substances by adding a modified filler, so that the water-based ink has both water resistance and ultraviolet resistance stability; according to the invention, the water-based polyacrylate emulsion is used as a film forming substance, the deionized water is used as a solvent, the raw materials are all green and environment-friendly, the use of a volatile organic solvent is avoided, and the water-based ink which is environment-friendly, excellent in comprehensive performance and capable of effectively defending ultraviolet rays is obtained.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of environment-friendly water-based ink comprises the following steps:
firstly, the following components in parts by weight: 60-70 parts of polyacrylate emulsion, 6-7 parts of modified filler, 4-5 parts of pigment, 0.5-0.7 part of wetting agent, 0.8-1 part of dispersing agent, 0.5-0.7 part of defoaming agent and 10-12 parts of deionized water;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
and thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 80-90min, adding the defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink.
Further, the modified filler is prepared by the following method:
(1) weighing 1.6g of nano ZnO powder, dispersing in 150m L of absolute ethyl alcohol, carrying out ultrasonic treatment at normal temperature for 30min, adding 3.3g of ethylene carbonate, continuing to carry out ultrasonic dispersion for 30min, placing the system in a 35 ℃ constant temperature water bath, keeping the constant temperature of 35 ℃ for ultrasonic dispersion, slowly dripping a mixture of 8.3g of ethyl orthosilicate and 100m L of absolute ethyl alcohol, controlling the dripping time to be 3h, adding ammonia water to adjust the pH value of the system to be 8-9, continuing to carry out ultrasonic dispersion for 2h after the reaction is finished, carrying out centrifugal washing, carrying out vacuum drying on the product for 24h, and grinding the product through a 200-mesh sieve to obtain a composite filler;
(2) weighing 0.5g of composite filler, adding the composite filler into DMF (dimethyl formamide) of 200m L, stirring at 200r/min for 10min, and performing ultrasonic dispersion for 30min to obtain a composite filler dispersion liquid;
(3) 5.3g of isophorone diisocyanate were weighed into the dispersion, stirred continuously, and N was added at 82 ℃2Reacting for 20 hours under protection, centrifuging the obtained product, washing and precipitating for 3 times by using n-butyl acetate to remove excessive isophorone diisocyanate, and drying to obtain the modified filler.
Further, the polyacrylate emulsion is prepared by the following method:
(1) dissolving 0.08g of ammonium persulfate in 10g of water completely to obtain an initiator aqueous solution for later use; weighing 7.4g of methyl methacrylate, 10.2g of isooctyl acrylate, 0.12g of n-dodecyl mercaptan, 0.2g of methacrylic acid and 0.4g of diacetone acrylamide, and uniformly mixing to obtain a monomer mixture for later use;
(2) 0.6g of composite emulsifier and 0.1g of NaHCO are added into a flask316.4g of deionized water, 0.6g of methyl methacrylate and 1.8g of isooctyl acrylate, N2Emulsifying at 40 deg.C and 400r/min for 30min under atmosphere, and then reducing stirring speed to 300 r/min;
(3) heating the system to 78 ℃, keeping stirring at a constant speed of 300r/min, adding 30% of the total mass of the initiator aqueous solution until no reflux exists in a condensation pipe, then dropwise adding the rest monomer mixture and the rest initiator aqueous solution, finishing dropping in 80min, heating to 90 ℃, and keeping the temperature for 2 h;
(4) then cooling to below 40 ℃, adding ammonia water to adjust the pH value to 8-9, stirring for 15min, adding 0.2g of adipic dihydrazide, stirring for 15min, and sieving by a 200-mesh sieve to obtain a polyacrylate emulsion;
further, the compound emulsifier in the step (2) is formed by compounding sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether according to the mass ratio of 1: 5.
The invention has the beneficial effects that:
the invention takes water-based acrylate emulsion as a film forming substance of the printing ink, and diacetone acrylamide is introduced in the polymerization process and has two reactivitiesRadical (I): n-substituted amides and ketones, especially with acrylic acidsSheet BodyCopolymerization to introduce ketones into the polymerCarbonyl radical(-CO-); adding adipic acid dihydrazide into the emulsion, and then adding-NHNH in the adipic acid dihydrazide2The group and-CO-in the polymer have ketone hydrazine cross-linking reaction to generate hydrazone, and the formed C ═ N (hydrazone) has higher bond energy and needs higher temperature for breaking the C ═ N (hydrazone), so that the thermal stability of the emulsion is improved; meanwhile, as n-dodecyl mercaptan (chain transfer agent) is added into the emulsion polymerization system, most of high molecular chains are subjected to chain transfer reaction, the polymerization degree of the polymer is reduced, a copolymer with lower molecular weight is generated, the molecular weight distribution is narrower, and the emulsion has better wetting property and film-forming property; moreover, the diacetone acrylamide is added to generate a ketone hydrazine crosslinking reaction, a polyacrylate coating film is changed into thermosetting molecules from thermoplasticity, the crosslinking degree of the coating film is increased, the density is increased, the water absorption is reduced, and the cohesive force of the emulsion film is higher, so that the adhesive force of the ink is improved;
according to the invention, the modified filler is doped in the ink, the surface of the prepared composite filler contains a large number of hydroxyl functional groups, isophorone diisocyanate can be grafted to the surface of the composite filler through the reaction with hydroxyl, and the compatibility of the filler and polyacrylate emulsion can be improved by the isophorone diisocyanate grafted on the composite filler, so that the modified filler can be uniformly dispersed in the ink; due to the prepared composite fillerCoating nano SiO on the surface of nano ZnO2The formed zinc oxide has stronger photocatalysis performance and ultraviolet shielding capability, and the nano SiO is coated on the surface of the nano ZnO2Can inhibit the strong photocatalysis capability of zinc oxide, can prevent the direct contact of nano ZnO and a resin substrate, reduce the photocatalysis performance and protect the resin substrate from being degraded, and simultaneously, the nano SiO2The modified filler has certain ultraviolet absorption performance, so that the ultraviolet shielding capacity of the filler is enhanced, and the photocatalytic performance of the modified filler is inhibited while the modified filler has the ultraviolet absorption performance; when the modified filler is added into the ink, the aging phenomenon of the ink caused by ultraviolet rays can be effectively prevented, the damage caused by the ultraviolet rays to an organic resin substrate is reduced, and the decomposition of a low-surface-energy substance can be avoided, so that the water-based ink has both water resistance and ultraviolet resistance stability;
the water-based polyacrylate emulsion is used as a film forming substance of the ink, has high film forming performance and adhesive force, can effectively prevent the ink aging phenomenon caused by ultraviolet rays by adding the modified filler, reduces the damage caused by the ultraviolet rays and the organic resin substrate, and can avoid the decomposition of low surface energy substances, so that the water-based ink has both water resistance and ultraviolet resistance stability; according to the invention, the water-based polyacrylate emulsion is used as a film forming substance, the deionized water is used as a solvent, the raw materials are all green and environment-friendly, the use of a volatile organic solvent is avoided, and the water-based ink which is environment-friendly, excellent in comprehensive performance and capable of effectively defending ultraviolet rays is obtained.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation process of environment-friendly water-based ink comprises the following steps:
firstly, the following components in parts by weight: 60-70 parts of polyacrylate emulsion, 6-7 parts of modified filler, 4-5 parts of pigment, 0.5-0.7 part of wetting agent, 0.8-1 part of dispersing agent, 0.5-0.7 part of defoaming agent and 10-12 parts of deionized water;
specifically, the wetting agent is wetting agent 101A, institute of chemical engineering, Dalian and lightweight industries; the dispersing agent is polyethylene glycol; the defoaming agent is an organic silicon defoaming agent;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
the color paste is prepared firstly, so that the compatibility of the color paste and a polymer matrix can be improved, the performance of the ink is further improved, and the color paste has good stability, proper rheological property and higher ink coating adhesive force and glossiness due to the addition of the wetting agent and the dispersing agent in proper amounts;
thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 80-90min, adding the defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink;
the modified filler is prepared by the following method:
(1) weighing 1.6g of nano ZnO powder, dispersing in 150m L of absolute ethyl alcohol, carrying out ultrasonic treatment at normal temperature for 30min, adding 3.3g of ethylene carbonate, continuing to carry out ultrasonic dispersion for 30min, placing the system in a 35 ℃ constant temperature water bath, keeping the constant temperature of 35 ℃ for ultrasonic dispersion, slowly dripping a mixture of 8.3g of ethyl orthosilicate and 100m L of absolute ethyl alcohol, controlling the dripping time to be 3h, adding ammonia water to adjust the pH value of the system to be 8-9, continuing to carry out ultrasonic dispersion for 2h after the reaction is finished, carrying out centrifugal washing, carrying out vacuum drying on the product for 24h, and grinding the product through a 200-mesh sieve to obtain a composite filler;
on one hand, tetraethoxysilane is hydrolyzed to form nano SiO with a Si-O-Si three-dimensional network structure2On the other hand, carbonyl on the ethylene carbonate is combined with-Si-OH formed after the hydrolysis condensation of TEOS to form hydrogen bonds to be adsorbed on the surface of nano ZnO, and then-OH on the surface of ZnO can be bonded and reacted with Si-OH groups adsorbed on the surface of ZnO to generate Zn-O-Si bonds, thereby realizing the nano SiO with a Si-O-Si three-dimensional network structure2Coating nano ZnO, wherein the coating form is not simple physical coating, but bonding is carried out through chemical bond Zn-O-Si bond to finally form nano SiO2A composite filler coated with ZnO;
(2) weighing 0.5g of composite filler, adding the composite filler into DMF (dimethyl formamide) of 200m L, stirring at 200r/min for 10min, and performing ultrasonic dispersion for 30min to obtain a composite filler dispersion liquid;
(3) 5.3g of isophorone diisocyanate were weighed into the dispersion, stirred continuously, and N was added at 82 ℃2Reacting for 20 hours under protection, centrifuging the obtained product, washing and precipitating for 3 times by using n-butyl acetate to remove excessive isophorone diisocyanate, and drying to obtain a modified filler;
the prepared composite filler surface contains a large amount of hydroxyl functional groups, isophorone diisocyanate can be grafted to the composite filler surface through the reaction with hydroxyl, and the compatibility of the filler and polyacrylate emulsion can be improved by the isophorone diisocyanate grafted on the composite filler, so that the modified filler can be uniformly dispersed in the ink; because the prepared composite filler is prepared by coating nano SiO on the surface of nano ZnO2The formed zinc oxide has stronger photocatalysis performance and ultraviolet shielding capability, and the nano SiO is coated on the surface of the nano ZnO2Can inhibit the strong photocatalysis capability of zinc oxide, can prevent the direct contact of nano ZnO and a resin substrate, reduce the photocatalysis performance and protect the resin substrate from being degraded, and simultaneously, the nano SiO2The modified filler has certain ultraviolet absorption performance, so that the ultraviolet shielding capacity of the filler is enhanced, and the photocatalytic performance of the modified filler is inhibited while the modified filler has the ultraviolet absorption performance; when the modified filler is added into the ink, the aging phenomenon of the ink caused by ultraviolet rays can be effectively prevented, the damage caused by the ultraviolet rays and the organic resin base material can be reduced, and the low-temperature-resistant ink can be preventedThe decomposition of surface energy substances enables the water-based ink to have both water resistance and ultraviolet stability;
the polyacrylate emulsion is prepared by the following method:
(1) dissolving 0.08g of ammonium persulfate in 10g of water completely to obtain an initiator aqueous solution for later use; weighing 7.4g of methyl methacrylate, 10.2g of isooctyl acrylate, 0.12g of n-dodecyl mercaptan, 0.2g of methacrylic acid and 0.4g of diacetone acrylamide, and uniformly mixing to obtain a monomer mixture for later use;
(2) 0.6g of compound emulsifier (the compound emulsifier is formed by compounding sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether according to the mass ratio of 1: 5) and 0.1g of NaHCO are added into a flask316.4g of deionized water, 0.6g of methyl methacrylate and 1.8g of isooctyl acrylate, N2Emulsifying at 40 deg.C and 400r/min for 30min under atmosphere, and then reducing stirring speed to 300 r/min;
(3) heating the system to 78 ℃, keeping stirring at a constant speed of 300r/min, adding 30% of the total mass of the initiator aqueous solution until no reflux exists in a condensation pipe, then dropwise adding the rest monomer mixture and the rest initiator aqueous solution, finishing dropping in 80min, heating to 90 ℃, and keeping the temperature for 2 h;
(4) then cooling to below 40 ℃, adding ammonia water to adjust the pH value to 8-9, stirring for 15min, adding 0.2g of adipic dihydrazide, stirring for 15min, and sieving by a 200-mesh sieve to obtain a polyacrylate emulsion;
the diacetone acrylamide has two reactivitiesRadical (I): n-substituted amides and ketones, especially with acrylic acidsSheet BodyCopolymerization to introduce ketones into the polymerCarbonyl radical(-CO-); adding adipic acid dihydrazide into the emulsion, and then adding-NHNH in the adipic acid dihydrazide2The group and-CO-in the polymer have ketone hydrazine cross-linking reaction to generate hydrazone, and the formed C ═ N (hydrazone) has higher bond energy and needs higher temperature for breaking the C ═ N (hydrazone), so that the thermal stability of the emulsion is improved; meanwhile, as n-dodecyl mercaptan (chain transfer agent) is added into the emulsion polymerization system, most of high molecular chains are subjected to chain transfer reaction, the polymerization degree of the polymer is reduced, a copolymer with lower molecular weight is generated, the molecular weight distribution is narrower, and the emulsion is subjected to chain transfer reactionHas better wetting property and film forming property; moreover, the diacetone acrylamide is added to generate a ketone hydrazine crosslinking reaction, a polyacrylate coating film is changed into thermosetting molecules from thermoplastic, the crosslinking degree of the coating film is increased, the density is increased, the water absorption is reduced, the cohesive force of the emulsion film is higher, and the adhesive force of the ink is improved.
Example 1
A preparation process of environment-friendly water-based ink comprises the following steps:
firstly, the following components in parts by weight: 60 parts of polyacrylate emulsion, 6 parts of modified filler, 4-5 parts of pigment, 0.5 part of wetting agent, 0.8 part of dispersing agent, 0.5 part of defoaming agent and 10 parts of deionized water;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
and thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 80min, adding a defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink.
Example 2
A preparation process of environment-friendly water-based ink comprises the following steps:
firstly, the following components in parts by weight: weighing 65 parts of polyacrylate emulsion, 6.5 parts of modified filler, 4.5 parts of pigment, 0.6 part of wetting agent, 0.9 part of dispersing agent, 0.6 part of defoaming agent and 11 parts of deionized water;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
and thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 85min, adding a defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink.
Example 3
A preparation process of environment-friendly water-based ink comprises the following steps:
firstly, the following components in parts by weight: 70 parts of polyacrylate emulsion, 7 parts of modified filler, 4-5 parts of pigment, 0.7 part of wetting agent, 1 part of dispersing agent, 0.7 part of defoaming agent and 12 parts of deionized water;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
and thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 90min, adding a defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink.
Comparative example 1
The polyacrylate emulsion of example 1 was changed to a conventional polyacrylate emulsion.
Comparative example 2
The modified filler of example 1 was removed.
Comparative example 3
Water-based inks are commonly commercially available.
The following performance tests were performed on the aqueous inks obtained in examples 1 to 3 and comparative examples 1 to 3:
(1) the ink viscosity is measured by GB/T13217.4-2008, the initial drying of the ink is tested by referring to the national standard GB/T13217.5-2008, the adhesive force of the ink coating is measured by GB/T9286-1998, the water resistance of the ink coating is tested by selecting a 2cm × 2cm film with the thickness of 2mm and soaking the film in distilled water for 24 hours, and the water absorption is tested, wherein the test results are shown in the following table 1:
TABLE 1
It can be seen that the viscosity of the ink prepared in examples 1-3 is 2270-;
(2) the ultraviolet resistance of the ink coating is that the water-based ink is dried on a glass dish to form a film, the film with the size of 2cm × 2cm and the thickness of 2mm is selected, an ultraviolet spectrophotometer is used for measuring the absorbance value at the position of 200-800nm, and the test result is as the following table 2:
TABLE 2
The ink films prepared in examples 1-3 have high absorbance values up to 3.8-4.0 in the wavelength range of 200-300nm, and have high absorption in the UVB band of 280-320nm, i.e., low transmittance; higher ultraviolet light absorbance (2.1-3.8) appears in the UVA wave band of 300-400nm, and the ultraviolet light absorbance has the absorption on the UVA wave band, wherein UVA is the most common ultraviolet light wave band in daily life, and the addition of the modified filler can effectively improve the ultraviolet light absorption capacity of the ink.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. A preparation process of environment-friendly water-based ink is characterized by comprising the following steps:
firstly, the following components in parts by weight: 60-70 parts of polyacrylate emulsion, 6-7 parts of modified filler, 4-5 parts of pigment, 0.5-0.7 part of wetting agent, 0.8-1 part of dispersing agent, 0.5-0.7 part of defoaming agent and 10-12 parts of deionized water;
step two, color paste preparation:
adding deionized water into a dispersion cylinder, adding pigment, performing normal-temperature ultrasonic treatment for 10min to prepare a pigment water dispersion, adding a wetting agent and a half of dispersing agent, dispersing in a high-speed dispersion machine at 6000r/min for 60min, adding into a sand mill, and grinding until the particle size is less than 10 μm to obtain color paste;
and thirdly, mixing the color paste with the polyacrylate emulsion, adding the modified filler and the rest half of the dispersant, performing ultrasonic dispersion treatment at normal temperature for 80-90min, adding the defoaming agent, and mechanically stirring at 200r/min for 10min to obtain the environment-friendly water-based ink.
2. The process for preparing the environment-friendly aqueous ink according to claim 1, wherein the modified filler is prepared by the following method:
(1) weighing 1.6g of nano ZnO powder, dispersing in 150m L of absolute ethyl alcohol, carrying out ultrasonic treatment at normal temperature for 30min, adding 3.3g of ethylene carbonate, continuing to carry out ultrasonic dispersion for 30min, placing the system in a 35 ℃ constant temperature water bath, keeping the constant temperature of 35 ℃ for ultrasonic dispersion, slowly dripping a mixture of 8.3g of ethyl orthosilicate and 100m L of absolute ethyl alcohol, controlling the dripping time to be 3h, adding ammonia water to adjust the pH value of the system to be 8-9, continuing to carry out ultrasonic dispersion for 2h after the reaction is finished, carrying out centrifugal washing, carrying out vacuum drying on the product for 24h, and grinding the product through a 200-mesh sieve to obtain a composite filler;
(2) weighing 0.5g of composite filler, adding the composite filler into DMF (dimethyl formamide) of 200m L, stirring at 200r/min for 10min, and performing ultrasonic dispersion for 30min to obtain a composite filler dispersion liquid;
(3) 5.3g of isophorone diisocyanate were weighed into the dispersion, stirred continuously, and N was added at 82 ℃2Reacting for 20 hours under protection, centrifuging the obtained product, washing and precipitating for 3 times by using n-butyl acetate to remove excessive isophorone diisocyanate, and drying to obtain the modified filler.
3. The process for preparing the environment-friendly aqueous ink according to claim 1, wherein the polyacrylate emulsion is prepared by the following method:
(1) dissolving 0.08g of ammonium persulfate in 10g of water completely to obtain an initiator aqueous solution for later use; weighing 7.4g of methyl methacrylate, 10.2g of isooctyl acrylate, 0.12g of n-dodecyl mercaptan, 0.2g of methacrylic acid and 0.4g of diacetone acrylamide, and uniformly mixing to obtain a monomer mixture for later use;
(2) 0.6g of composite emulsifier and 0.1g of NaHCO are added into a flask316.4g of deionized water, 0.6g of methyl methacrylate and 1.8g of isooctyl acrylate, N2Emulsifying at 40 deg.C and 400r/min for 30min under atmosphere, and then reducing stirring speed to 300 r/min;
(3) heating the system to 78 ℃, keeping stirring at a constant speed of 300r/min, adding 30% of the total mass of the initiator aqueous solution until no reflux exists in a condensation pipe, then dropwise adding the rest monomer mixture and the rest initiator aqueous solution, finishing dropping in 80min, heating to 90 ℃, and keeping the temperature for 2 h;
(4) then cooling to below 40 ℃, adding ammonia water to adjust the pH value to 8-9, stirring for 15min, adding 0.2g of adipic dihydrazide, stirring for 15min, and sieving by a 200-mesh sieve to obtain the polyacrylate emulsion.
4. The preparation process of the environment-friendly water-based ink as claimed in claim 3, wherein the compound emulsifier in the step (2) is prepared by compounding sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether according to the mass ratio of 1: 5.
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