CN112662227A - Carbon-free environment-friendly offset printing black ink and preparation method thereof - Google Patents
Carbon-free environment-friendly offset printing black ink and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of printing ink, and particularly discloses carbon-free environment-friendly offset printing black ink and a preparation method thereof. The carbon-free environment-friendly offset printing black ink is prepared by mixing the following raw materials in parts by weight: 1200 portions and 1400 portions of blue ink; 900 portions of red ink and 1100 portions; 900 portions of yellow ink and 1100 portions; the blue ink is prepared by mixing the following raw materials: blue pigment, vehicle, filler, water, surfactant and photoinitiator; the red ink is prepared by mixing the following raw materials: red pigment, binder, filler, water, surfactant and photoinitiator; the yellow ink is prepared by mixing the following raw materials: yellow pigment, binder, filler, water, surfactant and photoinitiator. The carbon-free environment-friendly offset printing black ink has the advantages of no carbon black, environmental protection, no adverse effect on human health, good antibacterial property and lasting air purifying effect.
Description
Technical Field
The application relates to the technical field of printing ink, in particular to carbon-free environment-friendly printing black ink and a preparation method thereof
Background
With the rapid development of the packaging and printing industry, the ink industry is also rapidly growing correspondingly, wherein the UV offset printing ink has incomparable advantages compared with the traditional ink, and is widely applied to various fields such as cigarette and wine packaging, cosmetic packaging, medicine packaging or printed matters such as newspapers, magazines, books and the like.
The UV offset printing ink is dried and cured by ultraviolet radiation and by means of free radicals or cations formed after a photoinitiator absorbs radiation energy to initiate polymerization, crosslinking and grafting reactions of monomers and oligomers to form a high molecular polymer with a crosslinked three-dimensional network structure; most UV offset inks consist of unsaturated resins, acrylate monomers, photoinitiators, fillers, pigments.
In the prior art, chinese patent application No. CN201310621757.8 discloses a quick-drying offset printing ink, which comprises the following substances in parts by weight: 15-25 parts of carbon black, 4-8 parts of propylene glycol, 25-35 parts of rosin modified phenolic resin, 15-25 parts of cottonseed oil, 4-6 parts of linseed oil, 2-4 parts of tung oil, 3-5 parts of polyethylene wax, 0.5-2 parts of cobalt naphthenate, 1-3 parts of manganese naphthenate styrene solution with the mass percentage concentration of 4%, 4-8 parts of dimethyl, 0.5-2 parts of methyl paraben and 1-3 parts of absolute ethyl alcohol.
The existing offset printing ink has high curing speed and long quality guarantee period, but contains a large amount of carbon black, the carbon black mostly contains substances such as cyclic aromatic hydrocarbon series, dimethyl ammonium nitrate and the like, and the substances are volatilized due to heating of the printing ink during printing and are absorbed by human bodies through breathing, so that the harm is caused to the health of the human bodies.
Aiming at the related technologies, the inventor considers that the existing offset printing ink containing carbon black is volatile and harmful substances are harmful to human bodies during printing, and the offset printing ink is poor in environmental protection and health.
Disclosure of Invention
In order to avoid adverse effects of offset printing ink on the health of human bodies in the printing process, the application provides carbon-free environment-friendly offset printing black ink and a preparation method thereof.
In a first aspect, the application provides a carbon-free environment-friendly offset black ink, which adopts the following technical scheme:
the carbon-free environment-friendly offset printing black ink is prepared by mixing the following raw materials in parts by weight:
1200 portions and 1400 portions of blue ink;
900 portions of red ink and 1100 portions;
900 portions of yellow ink and 1100 portions;
the blue ink is prepared by mixing the following raw materials in parts by weight: 13-18 parts of blue pigment, 40-60 parts of binder, 6-10 parts of filler, 40-60 parts of water, 2-2.8 parts of surfactant and 3-8 parts of photoinitiator;
the red ink is prepared by mixing the following raw materials in parts by weight: 15-20 parts of red pigment, 38-57 parts of binder, 8-12 parts of filler, 45-65 parts of water, 1.8-2.4 parts of surfactant and 4-9 parts of photoinitiator;
the yellow ink is prepared by mixing the following raw materials in parts by weight: 18-24 parts of yellow pigment, 42-65 parts of binder, 7-15 parts of filler, 35-55 parts of water, 2.2-2.6 parts of surfactant and 5-10 parts of photoinitiator.
By adopting the technical scheme, the black ink prepared by using the three pigments of the red ink, the yellow ink and the blue ink meets the requirement of no carbon black, solves the problem that the carbon black is easy to be heated and volatilize harmful substances in the printing process of the black ink containing the carbon black in the prior art to the maximum extent, has the advantages of no carbon black and no adverse effect on human health, and has small color difference with the standard black ink and good printing quality.
Preferably, the raw materials comprise the following components in parts by weight: 1300 parts of blue ink, 1000 parts of red ink and 1000 parts of yellow ink.
By adopting the technical scheme, the using amounts of the three primary color inks are accurately controlled, so that the prepared black offset ink has good color and luster, good blackness and high printing quality, is not broken during printing, does not contain carbon black, and has no adverse effect on human health.
Preferably, the vehicle in the blue ink, the red ink and the yellow ink is prepared from the following raw materials in percentage by weight: 10-20% of rosin modified phenolic resin, 1-5% of epoxy resin emulsion and 75-85% of polyurethane emulsion; the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer according to the mass ratio of 2: 1-1.5.
By adopting the technical scheme, the rosin modified phenolic resin, the epoxy resin and the polyurethane emulsion are used as the connecting material, no organic solvent is used, the VOC emission is low, the environment can be effectively protected, the flexibility and the weather resistance of the black ink can be improved after the three substances are matched to prepare the connecting material, the ethyl acrylate modified polyurethane and the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer can be tightly combined with pigment molecules, the adhesive property of the black ink is improved, and the definition of the ink is improved.
Preferably, the fillers in the blue ink, the red ink and the yellow ink are prepared by mixing and calcining kaolin, cerium oxide and germanite powder in a mass ratio of 1:1: 2-3.
By adopting the technical scheme, the kaolin and the germanite powder have negative ion release capacity, the kaolin is calcined to form the negative ion release glass ceramics, and the doped cerium oxide can reduce quartz crystals in the glass ceramics to generate silicon, so that the crystal size and microstructure of the negative ion glass ceramics are improved to a certain extent, the release amount of negative ions is increased, and the effect of purifying air is achieved.
Preferably, the blue ink is costwood VC-S350B, the red ink is costwood VC-350R, and the yellow ink is costwood VC-350Y.
By adopting the technical scheme, the Cosmith VC-S350 series tri-primary color inks have excellent adhesive force, can be printed on the surfaces of PP, PET and other materials, particularly soft PVC, has excellent adhesive force, good fluidity, transferability and dot reproducibility, can be used for high-quality prints, has excellent curing performance, can improve the production efficiency, has no carbon black, is relatively environment-friendly, and has no adverse effect on human health.
Preferably, the raw material also comprises a silver ion antibacterial agent, and the dosage of the silver ion antibacterial agent is 80-100 parts by weight.
By adopting the technical scheme, the offset black ink is possibly polluted by production raw materials and production equipment in the production and storage processes, or external microorganisms are introduced due to improper storage, and the finished product of the printed matter is polluted by the microorganisms introduced from the outside, the microorganisms are easy to breed and reproduce, the ink is damaged, the printed matter is seriously polluted, and the silver ion antibacterial agent is added into the offset black ink, so that the black ink has antibacterial performance, and is prevented from being polluted by the microorganisms after production, storage or printing.
Preferably, the raw material also comprises anion powder, and the dosage of the anion powder is 110-150 parts by weight.
By adopting the technical scheme, the office is an office place with dense staff, the air circulation is not smooth, the spirit of the staff is easy to be caused, the negative ion powder is added into the offset black ink, when the offset black ink is printed into printed matters such as newspaper, impurities, books and the like, the negative ions can kill germs, purify air, increase the oxygen content in blood, improve the mental state of a human body, and improve the regional air quality, so that the air quality of the office is higher.
In a second aspect, the application provides a method for preparing carbon-free environment-friendly offset black ink, which adopts the following technical scheme:
a preparation method of carbon-free environment-friendly offset printing black ink comprises the following steps: and uniformly mixing the red ink, the yellow ink and the blue ink to form an ink mixture, grinding the ink mixture for 1-2.5h at the grinding temperature of 40-60 ℃, standing and cooling to room temperature, and filtering to obtain the carbon-free environment-friendly offset printing black ink.
By adopting the technical scheme, the three colors of printing ink are mixed and ground, so that the printing ink has the characteristics of small fineness, uniform particles, simple preparation method and suitability for large-specification production.
Preferably, the ink mixture is added with anion powder before grinding, the weight part of the anion powder is 110-150 parts, and the preparation method of the anion powder is as follows: (1) grinding and sieving the coffee grounds by weight parts to obtain 3000-mesh coffee grounds with the particle size of 1500-; (2) uniformly mixing 30-50 parts of coffee grounds, 30-50 parts of tourmaline, 20-30 parts of titanium oxide and 10-20 parts of lanthanum sulfate; (3) dissolving 100-150 parts of sodium alginate in water, adding 40-80 parts of calcium chloride, performing ultrasonic dispersion, uniformly mixing with the product obtained in the step (2), and performing spray drying to obtain the anion powder.
By adopting the technical scheme, after coffee grounds are soaked in alkali liquor and ethanol, impurities on the surfaces of the coffee grounds can be removed, oil on the surfaces of the coffee grounds is removed after vacuum drying, then the coffee grounds, tourmaline and the like are mixed, sodium alginate has good film forming property, the gel strength of the sodium alginate is high under the action of calcium ions in calcium chloride, sodium alginate gel can be coated on the surfaces of raw materials such as the coffee grounds, the tourmaline and the like which are not coated can release negative ions, purify air and adsorb peculiar smell of the air, and the sodium alginate gel is degraded gradually along with the lapse of time as the sodium alginate gel is degraded, and the coated tourmaline, the coffee grounds and the like are released, so that the negative ions are released, the air is purified, the release time of the negative ions is prolonged, and the air purification effect is prolonged.
Preferably, the silver ion antibacterial agent is added into the ink mixture before grinding, and the weight part of the silver ion antibacterial agent is 80-100 parts; the preparation method of the silver ion antibacterial agent comprises the following steps: distilling cashew nut shell oil under reduced pressure to obtain a distillate, adding acetone, ethyl vanillin and salt into the distillate, adding alkali liquor to adjust the pH to 7.5-11, heating to 80-95 ℃, reacting for 2-4h at a constant temperature, adding 10-undecylenic acid, stirring, adding 1, 4-hydroquinone and chloroplatinic acid, reacting for 30-40min at 70-90 ℃, adding nano silver powder, and performing ultrasonic dispersion to prepare the silver ion antibacterial agent, wherein the mass ratio of the distillate, the ethyl vanillin, the undecylenic acid and the nano silver ions is 1:0.3-0.5:0.1-0.3: 1-2.
By adopting the technical scheme, the silver ion antibacterial agent is added into the ink mixture, so that the ink has an antibacterial effect, the ink is prevented from being polluted by microorganisms after being stored or printed, the antibacterial agent is prepared by using cashew nut shell oil, 10-undecylenic acid, ethyl vanillin and the like, the distilled fraction of the cashew nut shell oil mainly contains cardanol, the benzene ring of the cardanol contains a hydroxyl group, so that the ortho-position hydrogen atom and the para-position hydrogen atom of the cardanol are more active, the cardanol can perform polycondensation reaction with the ethyl vanillin under the catalysis of salt, the ethyl vanillin has the antibacterial and bactericidal effects, the cardanol after polycondensation is esterified with the 10-undecylenic acid, the hydroxyl group on the cardanol and the carboxyl group on the 10-undecylenic acid can be esterified to form 10-undecylenic acid glucose ester, and the 10-undecylenic acid glucose ester has good inhibitory effects on fungi, gram-negative bacteria and gram-positive bacteria, and the nano silver powder added subsequently can be uniformly coated in a polymer formed by cardanol, ethyl vanillin and undecylenic acid through spray drying, so that the antibacterial performance of the black ink is enhanced.
In summary, the present application has the following beneficial effects:
1. the black ink is prepared by adopting the three primary color inks, no carbon black is added, the environment is protected, no adverse effect is caused to human health, the requirements of certain presswork for the carbon-free ink are met, for example, some infant readings require the carbon-free ink for printing, the formula is simple, the black ink is suitable for large-scale production, the printing quality is high, and the concentration requirement and the blackness effect requirement of the existing black ink can be met.
2. According to the application, the filler is prepared by preferably mixing three raw materials, namely germanite powder, kaolin and cerium oxide, wherein the kaolin is calcined to generate negative ions to release the glass ceramics, the doped cerium oxide can enhance the negative ion release amount of the glass ceramics, and the negative ion release amount can be increased by cooperating with the germanite powder, so that the indoor environment is changed, and the air is purified.
3. According to the application, cashew nut shell oil is preferably subjected to reduced pressure distillation to extract cardanol, then ethyl vanillin is mixed with 10-undecylenic acid to react with cardanol, finally cardanol is mixed with silver micro powder to prepare a silver ion antibacterial agent with strong antibacterial property, and the silver ion antibacterial agent is mixed into offset black ink, so that the offset black ink can be prevented from being polluted by microorganisms in the production and storage processes, and the printed matter can be prevented from being polluted by microorganisms after the offset black ink is printed into the printed matter.
4. In the application, tourmaline, lanthanum sulfate, sodium alginate, coffee grounds and other components are preferably adopted to prepare the anion powder, the coffee grounds are pretreated to remove impurities and oil, then sodium alginate and calcium chloride are used to form gel to coat on the surfaces of the coffee grounds, the tourmaline and other substances, the coffee grounds, the tourmaline and the like which are not coated release anions, the coated coffee grounds and the like are gradually exposed along with the degradation of the sodium alginate gel to release the anions, so that the anion release effect of the offset black ink is prolonged, and the air purification effect is relatively durable.
Detailed Description
Preparation examples 1 to 5 of silver ion antibacterial agent
Preparation examples 1-5 Ethyl vanillin was selected from Henzhou Sensen Biotech Inc. model number YS 065; 10-undecenoic acid having a purity of 99% and selected from Alfa Aesar (Tianjin) chemical company, ltd; the chloroplatinic acid is selected from Shaanxi Rui Ke New Material Co., Ltd, and the nano silver powder is selected from Qinghe county Peak light metallic Material Co., Ltd, with a cargo number of 4215.
Preparation example 1: distilling cashew nut shell oil under reduced pressure to obtain a distillate, taking 1kg of the distillate, adding 0.1kg of acetone, 0.3kg of ethyl vanillin and 0.03kg of salt into the distillate, adding alkali liquor to adjust the pH value to 7.5, heating to 80 ℃, reacting for 4h at constant temperature, adding 0.1kg of 10-undecylenic acid, stirring for 10min, adding 0.03kg of 1, 4-benzenediol and 0.05kg of chloroplatinic acid, reacting for 40min at 70 ℃, adding 1kg of nano silver powder, performing ultrasonic dispersion to prepare the silver ion antibacterial agent, wherein the vacuum degree of the reduced pressure distillation is 0.5MPa, the reduced pressure distillation time is 4h, the salt is calcium carbonate, the alkali liquor is sodium hydroxide, the ultrasonic power is 100w, and the ultrasonic time is 40 min.
Preparation example 2: distilling cashew nut shell oil under reduced pressure to obtain a distillate, taking 1kg of the distillate, adding 0.2kg of acetone, 0.4kg of ethyl vanillin and 0.04kg of salt into the distillate, adding alkali liquor to adjust the pH value to 9, heating to 90 ℃, reacting for 3 hours at constant temperature, adding 0.2kg of 10-undecylenic acid, stirring for 20 minutes, adding 0.04kg of 1, 4-benzenediol and 0.05kg of chloroplatinic acid, reacting for 35 minutes at 80 ℃, adding 1.5kg of nano silver powder, and performing ultrasonic dispersion to prepare the silver ion antibacterial agent, wherein the vacuum degree of the reduced pressure distillation is 0.3MPa, the reduced pressure distillation time is 5 hours, the salt is sodium carbonate, the alkali liquor is barium hydroxide, the ultrasonic power is 150w, and the ultrasonic time is 20 minutes.
Preparation example 3: distilling cashew nut shell oil under reduced pressure to obtain a distillate, taking 1kg of the distillate, adding 0.3kg of acetone, 0.5kg of ethyl vanillin and 0.05kg of salt into the distillate, adding alkali liquor to adjust the pH value to 11, heating to 95 ℃, reacting for 2h at constant temperature, adding 0.3kg of 10-undecylenic acid, stirring for 30min, adding 0.05kg of 1, 4-benzenediol and 0.06kg of chloroplatinic acid, reacting for 30min at 90 ℃, adding 2kg of nano silver powder, performing ultrasonic dispersion to prepare the silver ion antibacterial agent, wherein the vacuum degree of the reduced pressure distillation is 0.2MPa, the reduced pressure distillation time is 6h, the salt is calcium carbonate, the alkali liquor is triethylamine, the ultrasonic power is 200w, and the ultrasonic time is 10 min.
Preparation example 4: the difference from preparation example 1 is that ethyl vanillin was not added.
Preparation example 5: the difference from preparation example 1 is that 10-undecenoic acid was not added.
Preparation examples 1 to 5 of anion powders
Preparation examples 1-5 sodium alginate was selected from Guangzhou Chang flatcar chemical Co., Ltd, model number HG 80; the water-soluble epoxy resin emulsion is selected from Hengyang Tuofan New Polymer Co, Inc., model number of 6520; the titanium oxide is selected from Jiangsu Tianxing New Material Co., Ltd, and the model is A12; the lanthanum sulfate is selected from Shandong Xiangguan New Material Co., Ltd, and has a model number of SDXG-000254.
Preparation example 1: (1) grinding and sieving coffee grounds to obtain coffee grounds with the particle size of 1500 meshes, soaking the ground coffee grounds in a 5moL/L sodium hydroxide solution for 20min, adding the coffee grounds into an ethanol solution, soaking for 20min, filtering, washing to be neutral, and drying in vacuum until the vacuum degree is 0.05MPa and the water content of the coffee grounds is less than or equal to 2 percent, wherein the mass ratio of the coffee grounds to the sodium hydroxide to the ethanol solution is 1:2: 2; (2) uniformly mixing 30g of coffee grounds with 30g of tourmaline, 20g of titanium oxide and 10g of lanthanum sulfate, and grinding until the particle size is 10 um; (3) dissolving 100g of sodium alginate in 500g of water, adding 40g of calcium chloride, and performing ultrasonic dispersion with ultrasonic power of 140w for 10 min; and (3) uniformly mixing the solution and the product obtained in the step (2), and performing spray drying to obtain the anion powder, wherein the spray drying pressure is 40MPa, the air inlet temperature is 135 ℃, the air outlet temperature is 65 ℃, and the sample injection flow rate is 500 mL/h.
Preparation example 2: (1) grinding and sieving coffee grounds to obtain coffee grounds with the particle size of 2000 meshes, soaking the ground coffee grounds in 8moL/L sodium hydroxide solution for 25min, adding the coffee grounds into ethanol solution, soaking for 25min, filtering, washing to be neutral, and drying in vacuum until the vacuum degree is 0.05MPa and the water content of the coffee grounds is less than or equal to 2 percent, wherein the mass ratio of the coffee grounds to the sodium hydroxide to the ethanol solution is 1:2: 2; (2) uniformly mixing 40g of coffee grounds with 40g of tourmaline, 25g of titanium oxide and 15g of lanthanum sulfate, and grinding until the particle size is 10 um; (3) dissolving 130g of sodium alginate in 600g of water, adding 60g of calcium chloride, and performing ultrasonic dispersion with the ultrasonic power of 120w for 20 min; and (3) uniformly mixing the solution and the product obtained in the step (2), and performing spray drying to obtain the anion powder, wherein the spray drying pressure is 50MPa, the air inlet temperature is 165 ℃, the air outlet temperature is 75 ℃, and the sample injection flow rate is 600 mL/h.
Preparation example 3: (1) grinding and sieving coffee grounds to obtain coffee grounds with particle sizes of 3000 meshes, soaking the ground coffee grounds in 10moL/L sodium hydroxide solution for 30min, adding the coffee grounds into ethanol solution, soaking for 30min, filtering, washing to be neutral, and drying in vacuum until the vacuum degree is 0.08MPa and the water content of the coffee grounds is less than or equal to 2 percent and the mass ratio of the coffee grounds to the sodium hydroxide to the ethanol solution is 1:2: 2; (2) uniformly mixing 50g of coffee grounds with 50g of tourmaline, 30g of titanium oxide and 20g of lanthanum sulfate, and grinding until the particle size is 10 um; (3) dissolving 150g of sodium alginate in 700g of water, adding 80g of calcium chloride, and performing ultrasonic dispersion with ultrasonic power of 100w for 30 min; and (3) uniformly mixing the solution and the product obtained in the step (2), and performing spray drying to obtain the anion powder, wherein the spray drying pressure is 60MPa, the air inlet temperature is 175 ℃, the air outlet temperature is 85 ℃, and the sample injection flow rate is 800 mL/h.
Preparation example 4: the difference from preparation example 1 is that no coffee grounds were added.
Preparation example 5: the difference from the preparation example 1 is that sodium alginate and calcium chloride are replaced by water-soluble epoxy resin emulsion.
Preparation example 1 of Ethyl acrylate-modified polyurethane
The polyurethane emulsion in preparation example 1 was selected from Guangdong Yuebeautification industries, Inc. with the model number DC 191; the ethyl acrylate is selected from Shenyang chemical industries, Ltd.
Preparation example 1: adding 10g of polyurethane emulsion and 3g of ethyl acrylate into a four-neck flask provided with a thermometer, a stirrer and a reflux condenser, stirring at the speed of 2000r/min for 20min, heating to 80 ℃, dropwise adding 0.7g of potassium sulfate, completing dropwise adding for 2h, continuing heat preservation reaction, measuring the monomer conversion rate until the monomer conversion rate is unchanged, finishing the reaction, cooling and discharging, and filtering to obtain filtrate, namely the ethyl acrylate modified polyurethane.
Examples
The magenta pigment in the following examples and comparative examples was selected from Shanghai pigment Chemicals, Inc. model number BASF 4535K/5B-K; the blue pigment is selected from Guanghong plastic pigment Limited in Shenzhen, and the model is K7090; yellow is selected from Seff New Material Co, of Fushan city, model number is Basff L2060; the rosin modified phenolic resin is selected from Shanghai North China chemical technology Co., Ltd, type 1303; the epoxy resin emulsion is selected from Shandong Liang New Material Co., Ltd, and has a model of LA-88S; the ethyl acrylate-modified polyurethane was selected from preparation example 1 of ethyl acrylate-modified polyurethane; the carboxyl modified ternary chloride-vinyl acetate resin is selected from Shandong Apol chemical engineering Co., Ltd, and has the model of TP-400M; the polysorbate is selected from the Federal fine chemical industry Co., Ltd in Guangdong, and has a model of S-80; and nonylphenol polyoxyethylene ether is selected from Guangzhou Juland chemical technology Co., Ltd, model number NPE-10; the 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide is selected from the group consisting of environmental protection science and technology limited of Jinbang, and the model is TPO; the 4-methylbenzophenone is selected from Shanghai Linggui chemical Co., Ltd, Cat No. 16522; the germanite powder is selected from ZSF-BW2 sold by ZSF product processing factories in Lingshou county; the cerium oxide is selected from Captain chemical products, Inc. of Henan, with a product number of 652.
Example 1: the raw material formula of the carbon-free environment-friendly offset printing black ink is shown in Table 1, and the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps:
uniformly mixing the red ink, the yellow ink and the blue ink to form an ink mixture, grinding the ink mixture for 1h at the grinding temperature of 60 ℃, standing and cooling to room temperature, and filtering to obtain the carbon-free environment-friendly offset printing black ink;
the blue ink is selected from the group consisting of Coomassie VC-S350B, and VC-S350B type blue ink is prepared by the following method: uniformly stirring 60g of binder, 2.8g of surfactant, 8g of photoinitiator and 60g of water at the rotating speed of 3000r/min, adding 18g of blue pigment and 10g of filler, uniformly stirring at the rotating speed of 2500r/min, and grinding until the particle size is 100um to obtain blue ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 10% of rosin modified phenolic resin, 5% of epoxy resin emulsion and 85% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1, the photoinitiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2 and calcining at 1800 ℃ for 4 hours;
the red ink is selected from Kesiwood VC-350R, and the preparation method of the VC-350R type red ink is as follows: stirring 57g of vehicle, 2.4g of surfactant, 9g of photoinitiator and 65g of water uniformly at the rotating speed of 3000r/min, adding 20g of red pigment and 12g of filler, stirring uniformly at the rotating speed of 2500r/min, and grinding until the particle size is 100um to obtain red ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 10% of rosin modified phenolic resin, 5% of epoxy resin emulsion and 85% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1, the photoinitiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2 and calcining at 1800 ℃ for 4 hours;
the yellow ink is selected from Kesiwood VC-350Y, and the VC-350Y type yellow ink is prepared by the following method: uniformly stirring 65g of vehicle, 2.6g of surfactant, 10g of photoinitiator and 55g of water at the rotating speed of 3000r/min, adding 24g of yellow pigment and 15g of filler, uniformly stirring at the rotating speed of 2500r/min, and grinding until the particle size is 100um to obtain yellow ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 10% of rosin modified phenolic resin, 5% of epoxy resin emulsion and 85% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1, the photoinitiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2 and calcining at 1800 ℃ for 4 hours.
TABLE 1 consumption of raw materials for carbon-free environmental offset black ink in examples 1-6
Example 2: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps:
uniformly mixing the red ink, the yellow ink and the blue ink to form an ink mixture, grinding the ink mixture for 2 hours at the grinding temperature of 50 ℃, standing and cooling to room temperature, and filtering to obtain the carbon-free environment-friendly offset printing black ink;
the blue ink is prepared by the following method: uniformly stirring 50g of bonding material, 2.4g of surfactant, 5g of photoinitiator and 50g of water at the rotating speed of 3500r/min, adding 15g of blue pigment and 8g of filler, uniformly stirring at the rotating speed of 3000r/min, and grinding until the particle size is 150um to obtain blue ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 15% of rosin modified phenolic resin, 3% of epoxy resin emulsion and 82% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.3; the surface active agent is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1.5, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2.5 and calcining at 1900 ℃ for 3 hours;
the preparation method of the red ink comprises the following steps: uniformly stirring 48g of bonding material, 2.1g of surfactant, 7g of photoinitiator and 55g of water at the rotating speed of 3200r/min, adding 18g of red pigment and 10g of filler, uniformly stirring at the rotating speed of 2800r/min, and grinding until the particle size is 150um to obtain red ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 15% of rosin modified phenolic resin, 3% of epoxy resin emulsion and 82% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.3; the surface active agent is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1.5, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2.5 and calcining at 1900 ℃ for 3 hours;
the yellow ink is prepared by the following method: uniformly stirring 56g of bonding material, 2.4g of surfactant, 8g of photoinitiator and 45g of water at the rotating speed of 3500r/min, adding 21g of yellow pigment and 12g of filler, uniformly stirring at the rotating speed of 2800r/min, and grinding to obtain yellow ink with the particle size of 150 um; the bonding material is prepared by mixing the following raw materials in percentage by weight; 15% of rosin modified phenolic resin, 3% of epoxy resin emulsion and 82% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.3; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1.5, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:2.5 and calcining at 1900 ℃ for 3 hours.
Example 3: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps:
uniformly mixing the red ink, the yellow ink and the blue ink to form an ink mixture, grinding the ink mixture for 2.5 hours at the grinding temperature of 40 ℃, standing and cooling to room temperature, and filtering to obtain the carbon-free environment-friendly offset printing black ink;
the blue ink is prepared by the following method: uniformly stirring 40g of bonding material, 2g of surfactant, 3g of photoinitiator and 54g of water at the rotating speed of 4000r/min, adding 13g of blue pigment and 6g of filler, uniformly stirring at the rotating speed of 3500r/min, and grinding until the particle size is 100um to obtain blue ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 20% of rosin modified phenolic resin, 1% of epoxy resin emulsion and 75% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.5; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:2, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:3 and calcining for 2 hours at 2000 ℃;
the preparation method of the red ink comprises the following steps: uniformly stirring 38g of bonding material, 1.8g of surfactant, 9g of photoinitiator and 45g of water at the rotating speed of 3500r/min, adding 15g of red pigment and 8g of filler, uniformly stirring at the rotating speed of 3000r/min, and grinding until the particle size is 100um to obtain red ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 20% of rosin modified phenolic resin, 1% of epoxy resin emulsion and 75% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.5; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:2, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:3 and calcining for 2 hours at 2000 ℃;
the yellow ink is prepared by the following method: uniformly stirring 42g of vehicle, 2.2g of surfactant, 5g of photoinitiator and 35g of water at the rotating speed of 3500r/min, adding 18g of yellow pigment and 7g of filler, uniformly stirring at the rotating speed of 3000r/min, and grinding until the particle size is 100um to obtain yellow ink; the bonding material is prepared by mixing the following raw materials in percentage by weight; 20% of rosin modified phenolic resin, 1% of epoxy resin emulsion and 75% of polyurethane emulsion, wherein the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin according to the mass ratio of 2: 1.5; the surfactant is prepared by mixing polysorbate and nonylphenol polyoxyethylene ether in a mass ratio of 1:2, the photoinitiator is 4-methylbenzophenone, and the filler is prepared by mixing kaolin, cerium oxide and germanite powder in a mass ratio of 1:1:3 and calcining for 2 hours at 2000 ℃.
Examples 4 to 8: the carbon-free environment-friendly offset black ink is different from the offset black ink in example 1 in that the raw material formula is shown in Table 1.
Example 9: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder is added into the ink mixture, the using amount of the negative ion powder is 110g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept stand and cooled to room temperature and then filtered to prepare the carbon-free environment-friendly offset printing black ink, and the negative ion powder is selected from a Hengxin mineral processing plant in Lingshou county, the model is 1905, and the mesh number is 800.
Example 10: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, a silver ion antibacterial agent is added into the ink mixture, the dosage of the silver ion antibacterial agent is 80g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept stand and cooled to room temperature and then filtered to prepare the carbon-free environment-friendly offset printing black ink, and the silver ion antibacterial agent is selected from Nanjing Tianshi blue Shield Biotech limited, the model of which is LD 904.
Example 11: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder and a silver ion antibacterial agent are added into the ink mixture, the using amount of the negative ion powder is 110g, the using amount of the silver ion antibacterial agent is 80g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept still and cooled to room temperature, and then the mixture is filtered to prepare the carbon-free environment-friendly offset black ink, wherein the negative ion powder is selected from a Gangxin mineral product processing factory in Lingshu county, the model is 1905, the mesh number is 800 meshes, and the silver ion antibacterial agent is selected from Nanjing Tianshi Landun Biotech limited, the model is LD 904.
Example 12: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder is added into the ink mixture, the using amount of the negative ion powder is 110g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept stand and cooled to room temperature, and then filtration is carried out, so that the carbon-free environment-friendly offset printing black ink is prepared, wherein the negative ion powder is selected from preparation example 1 of the negative ion powder.
Example 13: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder is added into the ink mixture, the using amount of the negative ion powder is 130g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept stand and cooled to room temperature, and then filtration is carried out, so that the carbon-free environment-friendly offset printing black ink is prepared, wherein the negative ion powder is selected from preparation example 2 of the negative ion powder.
Example 14: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder is added into the ink mixture, the amount of the negative ion powder is 150g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept stand and cooled to room temperature, and then filtration is carried out, so that the carbon-free environment-friendly offset printing black ink is prepared, wherein the negative ion powder is selected from preparation example 3 of the negative ion powder.
Example 15: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that anion powder is selected from the preparation example 4 of the anion powder.
Example 16: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that anion powder is selected from preparation example 5 of the anion powder.
Example 17: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, a silver ion antibacterial agent is added into the ink mixture, the silver ion antibacterial agent accounts for 80g, the ink mixture is ground for 1h at the grinding temperature of 60 ℃, and is kept stand and cooled to room temperature, and then the mixture is filtered to obtain the carbon-free environment-friendly offset printing black ink, wherein the silver ion antibacterial agent is selected from preparation example 1 of the silver ion antibacterial agent.
Example 18: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, 90g of silver ion antibacterial agent is added into the ink mixture, the ink mixture is ground for 1h at the grinding temperature of 60 ℃, and is kept stand and cooled to room temperature, and then is filtered to obtain the carbon-free environment-friendly offset black ink, wherein the silver ion antibacterial agent is selected from preparation example 2 of the silver ion antibacterial agent.
Example 19: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, 100g of silver ion antibacterial agent is added into the ink mixture, the ink mixture is ground for 1h at the grinding temperature of 60 ℃, and is kept stand and cooled to room temperature, and then is filtered to obtain the carbon-free environment-friendly offset black ink, wherein the silver ion antibacterial agent is selected from preparation example 3 of the silver ion antibacterial agent.
Example 20: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that a silver ion antibacterial agent is selected from preparation example 4 of the silver ion antibacterial agent.
Example 21: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that a silver ion antibacterial agent is selected from preparation example 5 of the silver ion antibacterial agent.
Example 22: the carbon-free environment-friendly offset printing black ink is different from the embodiment 1 in that the preparation method of the carbon-free environment-friendly offset printing black ink comprises the following steps: 1100g of red ink, 900g of yellow ink and 1300g of blue ink are mixed uniformly to form an ink mixture, negative ion powder and a silver ion antibacterial agent are added into the ink mixture, the using amount of the negative ion powder is 110g, the using amount of the silver ion antibacterial agent is 80g, the ink mixture is ground for 1h, the grinding temperature is 60 ℃, the mixture is kept still and cooled to room temperature, and then the mixture is filtered to obtain the carbon-free environment-friendly offset black ink, wherein the negative ion powder is selected from preparation example 1 of the negative ion powder, and the silver ion antibacterial agent is selected from preparation example 1 of the silver ion antibacterial agent.
Example 23: the carbon-free environment-friendly offset black ink is different from the black ink in example 1 in that cerium oxide is not added into a filler.
Comparative example
Comparative example 1: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that the amount of the blue ink is 1500 g.
Comparative example 2: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that the amount of the blue ink is 1000 g.
Comparative example 3: a carbon-free environment-friendly offset black ink is different from the black ink in example 1 in that the red ink is used in an amount of 800 g.
Comparative example 4: a carbon-free environment-friendly offset black ink, which is different from the black ink in example 1 in that the amount of the red ink is 1200 g.
Comparative example 5: a carbon-free environment-friendly offset black ink is different from the black ink in example 1 in that the yellow ink is used in an amount of 800 g.
Comparative example 6: a carbon-free environment-friendly offset black ink is different from the black ink in example 1 in that the yellow ink is used in an amount of 1200 g.
Comparative example 7: a quick-drying offset printing ink is prepared by the following method: then, putting 30g of rosin modified phenolic resin, 20g of cottonseed oil, 5g of linseed oil and 3g of tung oil into a stainless steel pot, heating to 285 ℃, continuously stirring for 50 minutes, then cooling to 205 ℃, adding 20g of carbon black, uniformly stirring, and taking out to obtain a mixture A; then mixing 6g of propylene glycol, 4g of polyethylene wax, 1g of cobalt naphthenate, 2g of manganese naphthenate styrene solution with the mass percentage concentration of 4%, 6g of xylene and 1g of methyl paraben, adding the mixture into a stainless steel reaction pot, heating to 80 ℃, continuously stirring for 20 minutes, and taking out the mixture after cooling to 50 ℃ to obtain a mixture B; and putting the mixture A, the mixture B and 2g of absolute ethyl alcohol into a stainless steel reaction pot, uniformly stirring for 20 minutes, taking out, putting into a stainless steel container or an iron container, and sealing to obtain the quick-drying offset printing ink.
Comparative example 8: the preparation method of the offset rotary black ink comprises the following steps: (1) preparing a binder: putting 22kg of rosin modified phenolic resin, 23kg of petroleum resin (103#), 45kg of kerosene with the boiling point of 260 ℃ of ink oil and 10kg of soybean oil into a reaction kettle, heating the materials to 160 ℃, stirring the materials until the resins are completely resinified, heating the materials to 180 ℃, keeping the temperature for 30 minutes, adding 0.5kg of liquid gelling agent, stirring the materials, keeping the temperature for 30 minutes, and detecting the viscosity of 15000-; filtering according to a conventional method after the product is qualified for later use; (2) preparation of the composition: 22kg of modified resin (ER125), 73kg of mineral oil adopting 7# engine oil or 32# engine oil and 5kg of soybean oil are put into a reaction kettle, stirred and heated to 150 ℃, the temperature is kept for 30 minutes, and the viscosity is detected to be 4000-6000mpas/25 ℃; filtering according to a conventional method after the product is qualified for later use; (3) preparing ink: 20kg of carbon black, 10kg of composition, 2kg of Hualan, 37kg of bonding material, 29kg of kerosene with boiling point of 260 ℃, 1.5kg of drying inhibitor and 0.5kg of bentonite are put into a dispersion tank for dispersion for 30 minutes, then put into a storage tank, put into a bead mill for grinding, put into an adjusting tank when the fineness is 7.5 mu m and adjusted to be qualified, filtered according to the conventional method and packaged.
Performance test
First, offset inks were prepared in the same manner as in examples 1 to 23 and comparative examples 1 to 8, and the properties of the offset inks were measured in the following manner, and the measurement results are shown in Table 2, wherein the black ink standards for measurement were compared with the standard black ink in appendix A of GB/T14624.2-93 "ink tinting strength test method", and the standard black ink was composed of the following substances in mass percent: 8 percent of carbon black, 72 percent of resin oil with the viscosity of 16000-.
1. Chroma: detecting according to 5.1 in QB/T2730.1-2005 printing ink;
2. surface tension: detecting according to 5.2 in QB/T2730.1-2005 printing ink;
3. viscosity; GB/T13217.4-2009 viscosity test method for liquid ink;
4. tinting strength: detecting according to GB/T14624.2-2008 'offset printing ink tinting strength test method';
5. printing effect; the offset inks prepared in the examples and comparative examples were printed on plain a4 paper at a high web press speed of 200m/min, in chinese and numeric characters in a chinese font size eight, and the print quality was evaluated as its legibility: a-clear and smooth lines; b-is clearer and the lines are thicker; c-has burrs and is fuzzy.
TABLE 2 measurement results of the properties of offset black inks in examples and comparative examples
As can be seen from the data in Table 2, the offset inks prepared in examples 1-8 have a low chroma, high surface tension and viscosity, high color impact and good printing results.
When the commercially available anion powder or the commercially available silver ion antibacterial agent or the anion powder or the antibacterial agent prepared in the application is added, the chroma of the offset black ink is not greatly changed compared with the chroma of the offset black ink in examples 1-8, and the printing effect is good, which shows that the addition of the commercially available anion powder and the silver ion antibacterial agent or the addition of the anion powder and the silver ion antibacterial agent prepared in the application has no great influence on the chroma, the surface tension, the printing quality and other properties of the offset ink.
In example 23, when cerium oxide was not added to the filler, the offset ink had no significant effect on the printing effect, color press force, and other properties.
In comparative examples 1 to 2, since the amount of the blue ink was changed, it was found from the results of the test that as the amount of the blue ink was increased, the chroma value was increased, and the color difference from the standard black ink was increased, and the printing effect was deteriorated.
In comparative examples 3 to 4, the amount of red ink was changed, and after printing, the font definition was decreased, the lines were thickened, and the chroma was increased.
In comparative examples 5 to 6, when the amount of the yellow ink was changed, the color of the ink became large and the quality of the impression was deteriorated, as is clear from the data in Table 2.
Comparative example 7 and comparative example 8 are offset inks prepared by the prior art, have small color difference with standard black ink and good printing quality, and have similar performance to the offset ink of the application, which shows that the application can form a black ink with small color difference and good printing quality of the standard ink by adjusting the using amount of the three inks.
Secondly, detecting antibacterial property and negative ion release amount performance of offset printing ink
1. And (3) antibacterial property: the culture medium is nutrient agar, the strains are colibacillus and staphylococcus aureus, and the concentration of the suspension prepared respectively is 2.0 multiplied by 106mL, adding 0.5g of black ink into the bacterial suspension, culturing at 37 ℃ for 24 hours, and detecting the size of a bacteriostatic circle;
2. the release amount of negative ions is as follows: the amount of released negative ions was measured by using a COM-3010PRO type ion detector produced in Japan, and the inks prepared in examples and comparative examples were set at 1m3In the test box (length, width and height are all 1m), the concentration of negative ions in the air is measured (24h and 30 days)
TABLE 3 detection of antibacterial property and anion release amount of offset black ink
As can be seen by combining examples 1-8 and examples 9-12, the negative ion powder and the silver ion antibacterial agent are not added in examples 1-8, the offset black ink prepared in examples 1-8 does not generate inhibition zones in nutrient agar, which indicates that the offset black ink prepared in examples 1-8 has no inhibition effect on Escherichia coli and Staphylococcus aureus, i.e. no antibacterial effect, but the filler made of kaolin, germanite powder and cerium oxide is added in examples 1-8, the offset black ink can release negative ions and purify air, and the release amount of the negative ions after 24 hours is 1580-3The negative ion release amount of the offset black ink after 30 days is 1012-1044/cm3The release amount of negative ions gradually decreases with the time, and the purification effect is weakened.
In contrast, in example 9, which was added with commercially available anion powder, the amount of anion released was reduced from that released in 24 hours at 30 days, as compared with examples 1 to 8, indicating that the cleaning effect was not sustained.
In the example 10, the commercially available silver ion antibacterial agent is added, so that the size of the inhibition zone for escherichia coli and staphylococcus aureus is increased and the inhibition effect is obviously enhanced compared with the examples 1-8.
In example 11, the commercial anion powder and the commercial silver ion antibacterial agent are used together, and the negative ion release amount and the inhibition zone size of the offset black ink are not much different from those of examples 9-10, which shows that the commercial anion powder and the silver ion antibacterial agent can enable the offset black ink to have the antibacterial effect and the negative ion release function.
In examples 12 to 14, the negative ion powder prepared in the present application was used, and as can be seen from the test results, the negative ion release amount was significantly increased at 30 days as compared to 24 hours, and the negative ion release amount was higher, indicating that the offset black ink prepared in examples 12 to 14 had a better antibacterial effect and a longer lasting air purification effect.
In example 15, since coffee grounds were not added when the negative ion powder was prepared, it was found from the detection results that, compared to example 15, the antibacterial effect of the offset black ink was not greatly changed, but the negative ion release amount at 24 hours was significantly decreased, but after the release was continued for 30 days, the offset black ink still had a high negative ion release amount and the air purification effect was durable.
In example 16, as the epoxy resin emulsion was used instead of the gel formed by degradable sodium alginate and calcium chloride, it is understood from the results in table 3 that the amount of negative ions released at 24 hours did not change much from example 12, but the amount of negative ions released after 30 days was decreased compared to the amount of negative ions released at 24 hours, indicating that the negative ion release ability of the offset black ink was not durable.
In examples 17 to 19, when the silver ion antibacterial agent prepared in the present application was added, the negative ion release amount was not changed much at 24 hours and 30 days, but the inhibition zone size of the offset black ink was significantly increased, which indicates that the silver ion antibacterial agent prepared in the present application has a strong antibacterial effect, as compared with examples 1 to 9.
In example 20, since ethyl vanillin is not added, the detection result shows that the inhibition zone of the offset black ink to escherichia coli and staphylococcus aureus is obviously reduced, and the antibacterial effect is weakened.
Example 21 the negative ion release amount of the offset black ink is not much different from that of example 12 because 10-undecylenic acid is not added, but the bacteriostatic effect on escherichia coli and staphylococcus aureus is weakened.
In example 22, because the silver ion antibacterial agent and the negative ion powder prepared in the present application are added to the offset black ink at the same time, as can be seen from the data in table 3, the size of the inhibition zone of the offset black ink to escherichia coli and staphylococcus aureus is significantly increased compared to examples 1 to 9, and the release amount of negative ions is not significantly different from 24 hours at 30 days, which indicates that the offset black ink prepared in the present application has a higher antibacterial property and a lasting air purification effect.
Example 23 shows that the negative ion release amount at 24h and 30 days is reduced compared to example 1 because cerium oxide is not added to the filler, and the negative ion release amount at 30 days is significantly reduced compared to the negative ion release amount at 24h in the offset black ink prepared in example 17, indicating that cerium oxide can increase the volatilization of the negative ion release amount, but cannot prolong the durability of the cleaning effect.
In comparative examples 1 to 6, the amounts of the red ink, the blue ink and the yellow ink were changed, and the results in table 3 show that the inhibition zones for escherichia coli and staphylococcus aureus were 0, and no antibacterial effect was exhibited, but the amount of negative ion released was not much different from that in example 1, and the air-purifying effect was exhibited, and the amount of negative ion released was reduced after 30 days, and the purifying effect was not lasting.
Comparative examples 7 and 8 are offset inks prepared according to the prior art, and it can be seen from the data in table 3 that the offset inks prepared according to comparative examples 7 to 8 have no inhibitory effect on escherichia coli and staphylococcus aureus, and the negative ion release amounts of the inks prepared according to comparative examples 7 to 8 are 0, so that the offset inks prepared according to comparative examples 7 to 8 have no antibacterial effect and no effect of purifying air.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The carbon-free environment-friendly offset printing black ink is characterized by being prepared by mixing the following raw materials in parts by weight:
1200 portions and 1400 portions of blue ink;
900 portions of red ink and 1100 portions;
900 portions of yellow ink and 1100 portions;
the blue ink is prepared by mixing the following raw materials in parts by weight: 13-18 parts of blue pigment, 40-60 parts of binder, 6-10 parts of filler, 40-60 parts of water, 2-2.8 parts of surfactant and 3-8 parts of photoinitiator;
the red ink is prepared by mixing the following raw materials in parts by weight: 15-20 parts of red pigment, 38-57 parts of binder, 8-12 parts of filler, 45-65 parts of water, 1.8-2.4 parts of surfactant and 4-9 parts of photoinitiator;
the yellow ink is prepared by mixing the following raw materials in parts by weight: 18-24 parts of yellow pigment, 42-65 parts of binder, 7-15 parts of filler, 35-55 parts of water, 2.2-2.6 parts of surfactant and 5-10 parts of photoinitiator.
2. The carbon-free environment-friendly offset black ink as claimed in claim 1, wherein: the weight parts of the raw materials are as follows: 1300 parts of blue ink, 1000 parts of red ink and 1000 parts of yellow ink.
3. The carbon-free environment-friendly offset printing black ink as claimed in claim 1, wherein the vehicle in the blue ink, the red ink and the yellow ink is prepared from the following raw materials in percentage by weight: 10-20% of rosin modified phenolic resin, 1-5% of epoxy resin emulsion and 75-85% of polyurethane emulsion; the polyurethane emulsion is formed by mixing ethyl acrylate modified polyurethane and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer according to the mass ratio of 2: 1-1.5.
4. The carbon-free environment-friendly offset black ink as claimed in claim 1, wherein the filler in the blue ink, the red ink and the yellow ink is prepared by mixing and calcining kaolin, cerium oxide and germanite powder in a mass ratio of 1:1: 2-3.
5. The carbon-free environment-friendly offset printing black ink as claimed in claim 1, wherein the blue ink is costwood VC-S350B, the red ink is costwood VC-350R, and the yellow ink is costwood VC-350Y.
6. The carbon-free environment-friendly offset black ink as claimed in claim 1, wherein the raw material further comprises a silver ion antibacterial agent, and the amount of the silver ion antibacterial agent is 80-100 parts by weight.
7. The carbon-free environment-friendly offset black ink as claimed in claim 1, wherein the raw material further comprises anion powder, and the amount of the anion powder is 110-150 parts by weight.
8. The method for preparing the carbon-free environment-friendly offset black ink as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: and uniformly mixing the red ink, the yellow ink and the blue ink to form an ink mixture, grinding the ink mixture for 1-2.5h at the grinding temperature of 40-60 ℃, standing and cooling to room temperature, and filtering to obtain the carbon-free environment-friendly offset printing black ink.
9. The method for preparing carbon-free environment-friendly offset black ink as claimed in claim 8, wherein the ink mixture is added with anion powder in an amount of 110-150 parts by weight before grinding, and the method for preparing the anion powder comprises the following steps: (1) grinding and sieving the coffee grounds by weight parts to obtain 3000-mesh coffee grounds with the particle size of 1500-; (2) uniformly mixing 30-50 parts of coffee grounds, 30-50 parts of tourmaline, 20-30 parts of titanium oxide and 10-20 parts of lanthanum sulfate; (3) dissolving 100-150 parts of sodium alginate in water, adding 40-80 parts of calcium chloride, performing ultrasonic dispersion, uniformly mixing with the product obtained in the step (2), and performing spray drying to obtain the anion powder.
10. The method for preparing the carbon-free environment-friendly offset black ink as claimed in claim 8, wherein before grinding, the ink mixture is added with silver ion antibacterial agent, and the weight part of the silver ion antibacterial agent is 80-100 parts; the preparation method of the silver ion antibacterial agent comprises the following steps: distilling cashew nut shell oil under reduced pressure to obtain a fraction, adding acetone, ethyl vanillin and salt into the fraction, adding alkali liquor to adjust the pH to 7.5-11, heating to 80-95 ℃, reacting for 2-4h at a constant temperature, adding 10-undecylenic acid, stirring, adding 1, 4-benzenediol and chloroplatinic acid, reacting for 30-40min at 70-90 ℃, adding nano silver powder, and performing ultrasonic dispersion to prepare the silver ion antibacterial agent, wherein the mass ratio of the fraction, the ethyl vanillin, the 10-undecylenic acid and the nano silver powder is 1:0.3-0.5:0.1-0.3: 1-2.
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| CN113683918A (en) * | 2021-08-23 | 2021-11-23 | 杭华油墨股份有限公司 | Carbon-free black ink based on point-reading printing and preparation method thereof |
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