CN111995907A - Printing ink capable of being quickly colored and preparation method thereof - Google Patents

Printing ink capable of being quickly colored and preparation method thereof Download PDF

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Publication number
CN111995907A
CN111995907A CN202010909643.3A CN202010909643A CN111995907A CN 111995907 A CN111995907 A CN 111995907A CN 202010909643 A CN202010909643 A CN 202010909643A CN 111995907 A CN111995907 A CN 111995907A
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stirring
temperature
printing ink
rotation speed
parts
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黄少荣
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses printing ink capable of being rapidly colored and a preparation method thereof, wherein the printing ink comprises the following raw materials in parts by weight: 50-80 parts of epoxy styrene-acrylic resin, 30-60 parts of nano titanium dioxide sol, 1-3 parts of defoaming agent, 3-5 parts of dispersing agent, 10-15 parts of pigment and 5-8 parts of high-temperature resistant filler; ethylene glycol methyl ether, styrene, acrylic acid and n-butyl acrylate are used as raw materials to be polymerized to prepare the epoxy styrene-acrylic resin, the epoxy styrene-acrylic resin has the advantages of high solid content, low viscosity and low molecular weight, the surface gloss of the ink can be high, the ink is suitable for dispersing pigments, nano titanium dioxide sol is prepared by using n-butyl titanate as a raw material, the raw materials are mixed to prepare the ink, the light resistance of the ink is improved, a high-temperature-resistant filler is prepared, graphene also has good heat resistance, the heat resistance of the printing ink is improved, and the organic silicon has good water resistance, so that the water resistance of the ink is improved.

Description

Printing ink capable of being quickly colored and preparation method thereof
Technical Field
The invention belongs to the technical field of ink preparation, and relates to printing ink capable of being quickly colored and a preparation method thereof.
Background
With the continuous development of modern industry, the status of printing industry in production and life is becoming more and more important. The development degree of the printing industry is one of important marks for measuring the national industrialization and modernization degrees, the water-based ink takes water as a main solvent, and is a novel printing ink which is formed by designing, blending and grinding a water-based high molecular polymer as a connecting material and auxiliaries such as pigment, surfactant and the like, the water-based ink has the advantages of nonflammability in the printing process, no harm to the health of ink manufacturers and printing operators, no pollution to the atmospheric environment and the like, and is environment-friendly and safe, and the water-based ink is used as a novel printing ink, has no residues of certain toxic and harmful substances in solvent-based ink in printed matters, and cannot pollute packaged goods; meanwhile, the water-based ink has the advantage of easy cleaning on a printing machine, thereby improving the productivity.
The existing printing ink can be scraped after film formation to enable the printing ink to fall off, so that the using effect of the printing ink is influenced, part of the printing ink needs to be used in a high-temperature environment after film formation, and the high-temperature environment enables the printing ink to have a fading phenomenon, so that the use is influenced.
Disclosure of Invention
The invention aims to provide printing ink capable of being quickly colored and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the existing printing ink can be scraped after film formation to enable the printing ink to fall off, so that the using effect of the printing ink is influenced, part of the printing ink needs to be used in a high-temperature environment after film formation, and the high-temperature environment enables the printing ink to have a fading phenomenon, so that the use is influenced.
The purpose of the invention can be realized by the following technical scheme:
a printing ink capable of being rapidly colored comprises the following raw materials in parts by weight: 50-80 parts of epoxy styrene-acrylic resin, 30-60 parts of nano titanium dioxide sol, 1-3 parts of defoaming agent, 3-5 parts of dispersing agent, 10-15 parts of pigment and 5-8 parts of high-temperature resistant filler;
the printing ink is prepared by the following steps:
step S1: mixing ethylene glycol monomethyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 120 plus materials/min and the temperature is 80-90 ℃, reacting for 1-2h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1-1.5h, adding the rest of the mixed solution, continuing to react for 3-5h, cooling under the condition that the temperature is 30-35 ℃, adjusting the pH value of the reaction solution to 8-9, and preparing the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120-plus 150r/min, stirring for 20-30min under the condition that the temperature is 25-30 ℃, then continuously stirring for 10-15min under the condition that the temperature is 60-70 ℃, adjusting the pH value to be 1-2, and continuously stirring for 4-6h to prepare nano titanium dioxide sol;
step S3: adding deionized water, a defoaming agent, a dispersing agent, a pigment and a high-temperature-resistant filler into a stirring kettle, stirring for 10-15min at the rotation speed of 500-4000 r/min, stirring for 1-1.5h at the rotation speed of 3000-4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 2000-3000r/min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1-1.5h at the rotation speed of 3000-4000r/min, and grinding through a 15-20 mu m screen to obtain the printing ink.
Further, the mixed solution in the step S1 contains ethylene glycol monomethyl ether, styrene, acrylic acid, N-butyl acrylate, and N-methylol acrylamide in an amount of 6g by mass: 3.5-3.8g:2.05-2.1g:3.5g:3.5-4mL, the using amount of ammonium persulfate is 3-5% of the mass of ethylene glycol monomethyl ether, and the using amount ratio of sodium hydroxide to deionized water in the dropping liquid in the step S2 is 8-10g:100mL, the volume ratio of the dosage of the n-butyl titanate, the ethanol and the dropping liquid is 3:20:80-100, the dosage of the deionized water in the step S3 is 20-30% of the mass sum of the epoxy styrene-acrylic resin and the nano titanium dioxide sol, the defoaming agent is one or more of GP type glyceryl polyether, GPE type polyoxyethylene ether and PPG type polypropylene glycol which are mixed in any proportion, and the dispersing agent is one or two of liquid paraffin and microcrystalline paraffin which are mixed in any proportion.
Further, the high-temperature-resistant filler is prepared by the following steps:
step A1: adding chromium oxide and phosphoric acid solution into a reaction kettle, stirring for 20-30min under the conditions that the rotation speed is 200-80 ℃ and the temperature is 70-80 ℃, adding aluminum hydroxide, heating to 95-98 ℃, stirring for 1-1.5h, cooling to 80-85 ℃, adding paraformaldehyde and tributyl phosphate, continuing stirring for 5-10min, heating to 110-120 ℃, preserving heat for 20-30min, cooling to 60-70 ℃, adding gamma-aminopropyltriethoxysilane and ethanol solution, and performing ultrasonic treatment for 10-15min under the condition that the frequency is 3-5MHz to prepare aluminum chromium phosphate peptization;
step A2: adding octamethylcyclotetrasiloxane and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, reacting for 5-8h under the conditions that the rotating speed is 100-150 ℃ and the temperature is 130-150 ℃ to obtain alkali glue, adding 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and dimethyl sulfoxide into the reaction kettle, introducing nitrogen for protection, reacting for 10-15h under the conditions that the rotating speed is 60-80r/min and the temperature is 70-75 ℃, filtering to remove filtrate, and distilling the filtrate under the conditions that the pressure is-0.095 MPa and the temperature is 100-110 ℃ to obtain silicone oil base liquid;
step A3: adding a sulfuric acid solution into a reaction kettle, adding graphite, sodium nitrate and potassium permanganate at the rotation speed of 120-5 ℃ at the temperature of 3-5 ℃, continuously stirring for 1-1.5h, heating to 30-40 ℃, continuously stirring for 20-40min, heating to 80-90 ℃, continuously stirring for 5-10min, adding hydrogen peroxide, continuously stirring for 20-30min, filtering to remove filtrate, dispersing filter cakes in deionized water, adding sodium hydroxide and monochloroacetic acid, stirring at the rotation speed of 300-500r/min at the temperature of 50-60 ℃ for 20-30min, filtering to remove filtrate, and drying the filter cakes to obtain a carrier;
step A4: and B, adding the aluminum chromium phosphate peptization prepared in the step A1, the silicone oil base liquid prepared in the step A2, the carrier prepared in the step A3 and deionized water into a reaction kettle, stirring for 5-10 hours at the rotation speed of 150-200r/min and at the temperature of 25-30 ℃, adding dicyclohexylcarbodiimide, continuously stirring for 20-30 minutes, performing ultrasonic treatment for 5-10 minutes at the frequency of 5-10MHz, filtering to remove filtrate, and drying a filter cake to obtain the high-temperature-resistant filler.
Further, the dosage ratio of the chromic oxide, the phosphoric acid solution and the aluminum hydroxide in the step A1 is 1g:15mL:4g, the dosage of the paraformaldehyde is 10-15% of the mass of the aluminum hydroxide, the dosage of the tributyl phosphate is 3-5% of the mass of the aluminum hydroxide, the dosage of the gamma-aminopropyltriethoxysilane is 3-5% of the mass of the aluminum hydroxide, and the mass fraction of the ethanol solution is 30-50%.
Further, in the alkali glue described in the step a2, the amount of sodium hydroxide is 0.015-0.02% of the mass of octamethylcyclotetrasiloxane, the amount of 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane are in a mass ratio of 1:20:15, and the amount of dimethyl sulfoxide is 0.05-0.06% of the mass of octamethylcyclotetrasiloxane.
Further, the amount ratio of the graphite, the sodium nitrate, the potassium permanganate and the hydrogen peroxide in the step A3 is 1g to 0.5g to 3g to 2-3mL, the mass fraction of the hydrogen peroxide is 5-8%, and the amount ratio of the filter cake, the sodium hydroxide and the monochloroacetic acid is 1-1.5 to 5 to 6.
Further, in the step A4, the dosage of the aluminum chromium phosphate peptization, the silicone oil base solution and the carrier is 2mL:2mL:3-4g, and the dosage of the dicyclohexylcarbodiimide is 50-60% of the mass of the carrier.
A manufacturing method of printing ink capable of being rapidly colored comprises the following steps:
step S1: mixing ethylene glycol monomethyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 120 plus materials/min and the temperature is 80-90 ℃, reacting for 1-2h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1-1.5h, adding the rest of the mixed solution, continuing to react for 3-5h, cooling under the condition that the temperature is 30-35 ℃, adjusting the pH value of the reaction solution to 8-9, and preparing the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120-plus 150r/min, stirring for 20-30min under the condition that the temperature is 25-30 ℃, then continuously stirring for 10-15min under the condition that the temperature is 60-70 ℃, adjusting the pH value to be 1-2, and continuously stirring for 4-6h to prepare nano titanium dioxide sol;
step S3: adding deionized water, a defoaming agent, a dispersing agent, a pigment and a high-temperature-resistant filler into a stirring kettle, stirring for 10-15min at the rotation speed of 500-4000 r/min, stirring for 1-1.5h at the rotation speed of 3000-4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 2000-3000r/min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1-1.5h at the rotation speed of 3000-4000r/min, and grinding through a 15-20 mu m screen to obtain the printing ink.
The invention has the beneficial effects that: in the process of preparing the printing ink capable of being quickly colored, firstly, ethylene glycol methyl ether, styrene, acrylic acid and n-butyl acrylate are used as raw materials to be polymerized to prepare epoxy styrene-acrylic resin, the epoxy styrene-acrylic resin has the advantages of high solid, low viscosity and low molecular weight, can ensure that the surface gloss of the printing ink is high, and is suitable for pigment dispersion, then, n-butyl titanate is used as a raw material to prepare nano titanium dioxide sol, and the raw materials are mixed to prepare the printing ink, so that the light resistance of the printing ink is improved, the printing suitability of the printing ink is improved, and a high-temperature resistant filler is prepared, wherein the high-temperature resistant filler is prepared by reacting cadmium oxide, a phosphoric acid solution and aluminum hydroxide as raw materials to prepare aluminum chromium phosphate, gamma-aminopropyltriethoxysilane is used for modification, so that a large amount of amino groups are contained on the surface of the aluminum chromium phosphate, and then, 1, 3-bis (3-aminopropyl) -, Polymerizing tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane, attacking silicon in 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane by hydroxyl to break Si-O-Si bonds to form silanol, attacking the silicon of tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane by the hydroxyl to break the Si-O-Si bonds to generate ring opening, combining the tetramethylcyclotetrasiloxane and the octamethylcyclotetrasiloxane after the ring opening to increase the chain length, further reacting with the silanol, finishing the reaction to enable two ends of a long chain to contain amino groups to prepare silicone oil base liquid, oxidizing graphene for carboxylation to enable the surface of the graphene to contain a large amount of active carboxyl groups, further mixing aluminum chromium phosphate peptization, the silicone oil base liquid and a carrier, and under the catalysis of dicyclohexylcarbodiimide, the amino and the carboxyl are condensed, so that aluminum chromium phosphate and silicone oil molecules are fixed on the surface of the graphene to prepare the high-temperature-resistant filler, the aluminum chromium phosphate serving as the high-temperature-resistant filler has good heat resistance, the graphene also has good heat resistance, the heat resistance of the printing ink is further increased, the organic silicon has good water resistance, and the water resistance of the printing ink is further increased.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
A printing ink capable of being rapidly colored comprises the following raw materials in parts by weight: 50 parts of epoxy styrene-acrylic resin, 30 parts of nano titanium dioxide sol, 1 part of GP type glycerol polyether, 3 parts of liquid paraffin, 10 parts of pigment and 5 parts of high temperature resistant filler;
the printing ink is prepared by the following steps:
step S1: mixing ethylene glycol methyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 120r/min and the temperature is 80 ℃, reacting for 1h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1h, adding the rest of the mixed solution, continuing to react for 3h, cooling to the temperature of 30 ℃, adjusting the pH value of the reaction solution to 8, and preparing the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120r/min, stirring for 20min at the temperature of 25 ℃, then continuously stirring for 10min at the temperature of 60 ℃, adjusting the pH value to 1, and continuously stirring for 4h to prepare nano titanium dioxide sol;
step S3: adding deionized water, GP type glyceryl polyether, liquid paraffin, pigment and high temperature resistant filler into a stirring kettle, stirring for 10min at the rotation speed of 500r/min, then stirring for 1h at the rotation speed of 3000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 for 30min at the rotation speed of 2000r/min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1h at the rotation speed of 3000r/min, and then grinding through a 15-micron screen mesh to obtain the printing ink.
The high-temperature resistant filler is prepared by the following steps:
step A1: adding chromium oxide and phosphoric acid solution into a reaction kettle, stirring for 20min at the rotation speed of 200r/min and the temperature of 70 ℃, adding aluminum hydroxide, heating to 95 ℃, stirring for 1h, cooling to 80 ℃, adding paraformaldehyde and tributyl phosphate, continuing stirring for 5min, heating to 110 ℃, keeping the temperature for 20min, cooling to 60 ℃, adding gamma-aminopropyltriethoxysilane and ethanol solution, and performing ultrasonic treatment for 10min at the frequency of 3MHz to obtain aluminum chromium phosphate peptization;
step A2: adding octamethylcyclotetrasiloxane and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, reacting for 5 hours at the rotation speed of 100r/min and the temperature of 130 ℃ to obtain alkali glue, adding 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and dimethyl sulfoxide into the reaction kettle, introducing nitrogen for protection, reacting for 10 hours at the rotation speed of 60r/min and the temperature of 70 ℃, filtering to remove a filtrate, and distilling the filtrate under the pressure of-0.095 MPa and the temperature of 100 ℃ to obtain a silicone oil base solution;
step A3: adding a sulfuric acid solution into a reaction kettle, adding graphite, sodium nitrate and potassium permanganate at the rotation speed of 120r/min and the temperature of 3 ℃, continuously stirring for 1h, heating to the temperature of 30 ℃, continuously stirring for 20min, heating to the temperature of 80 ℃, continuously stirring for 5min, adding hydrogen peroxide, continuously stirring for 20min, filtering to remove filtrate, dispersing a filter cake in deionized water, adding sodium hydroxide and monochloroacetic acid, stirring for 20min at the rotation speed of 300r/min and the temperature of 50 ℃, filtering to remove filtrate, and drying the filter cake to obtain a carrier;
step A4: and B, adding the aluminum chromium phosphate peptization prepared in the step A1, the silicone oil base solution prepared in the step A2, the carrier prepared in the step A3 and deionized water into a reaction kettle, stirring for 5 hours at the rotation speed of 150r/min and the temperature of 25 ℃, adding dicyclohexylcarbodiimide, continuously stirring for 20 minutes, performing ultrasonic treatment for 5 minutes at the frequency of 5MHz, filtering to remove filtrate, and drying a filter cake to obtain the high-temperature-resistant filler.
Example 2
A printing ink capable of being rapidly colored comprises the following raw materials in parts by weight: 60 parts of epoxy styrene-acrylic resin, 40 parts of nano titanium dioxide sol, 2 parts of GP type glycerol polyether, 4 parts of liquid paraffin, 13 parts of pigment and 6 parts of high temperature resistant filler;
the printing ink is prepared by the following steps:
step S1: mixing ethylene glycol methyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 150r/min and the temperature is 85 ℃, reacting for 1.5h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1.3h, adding the rest of the mixed solution, continuing to react for 4h, cooling to 35 ℃, and adjusting the pH value of the reaction solution to 9 to prepare the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120r/min, stirring for 25min at the temperature of 30 ℃, continuously stirring for 13min at the temperature of 65 ℃, adjusting the pH value to be 2, and continuously stirring for 5h to prepare nano titanium dioxide sol;
step S3: adding deionized water, a defoaming agent, a dispersing agent, a pigment and a high-temperature-resistant filler into a stirring kettle, stirring for 13min at the rotation speed of 600r/min, then stirring for 1.5h at the rotation speed of 4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 3000r/min for 35min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1.5h at the rotation speed of 4000r/min, and then grinding through a 20-micron screen to obtain the printing ink.
The high-temperature resistant filler is prepared by the following steps:
step A1: adding a chromic oxide solution and a phosphoric acid solution into a reaction kettle, stirring for 25min at the rotation speed of 300r/min and the temperature of 75 ℃, adding aluminum hydroxide, heating to 98 ℃, stirring for 1.5h, cooling to 85 ℃, adding paraformaldehyde and tributyl phosphate, continuously stirring for 8min, heating to 115 ℃, keeping the temperature for 25min, cooling to 65 ℃, adding gamma-aminopropyltriethoxysilane and an ethanol solution, and performing ultrasonic treatment for 13min at the frequency of 4MHz to obtain an aluminum chromium phosphate peptization;
step A2: adding octamethylcyclotetrasiloxane and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, reacting for 6 hours at the rotation speed of 120r/min and the temperature of 150 ℃ to obtain alkali glue, adding 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and dimethyl sulfoxide into the reaction kettle, introducing nitrogen for protection, reacting for 15 hours at the rotation speed of 80r/min and the temperature of 75 ℃, filtering to remove filtrate, and distilling the filtrate under the conditions that the pressure is-0.095 MPa and the temperature is 100-;
step A3: adding a sulfuric acid solution into a reaction kettle, adding graphite, sodium nitrate and potassium permanganate at the rotation speed of 150r/min and the temperature of 4 ℃, continuously stirring for 1.5h, heating to 440 ℃, continuously stirring for 30min, heating to 85 ℃, continuously stirring for 8min, adding hydrogen peroxide, continuously stirring for 25min, filtering to remove filtrate, dispersing a filter cake in deionized water, adding sodium hydroxide and monochloroacetic acid, stirring for 25min at the rotation speed of 400r/min and the temperature of 55 ℃, filtering to remove filtrate, and drying the filter cake to obtain a carrier;
step A4: and B, adding the aluminum chromium phosphate peptization prepared in the step A1, the silicone oil base solution prepared in the step A2, the carrier prepared in the step A3 and deionized water into a reaction kettle, stirring for 8 hours at the rotation speed of 200r/min and the temperature of 30 ℃, adding dicyclohexylcarbodiimide, continuously stirring for 25 minutes, performing ultrasonic treatment at the frequency of 8MHz for 8 minutes, filtering to remove filtrate, and drying a filter cake to obtain the high-temperature-resistant filler.
Example 3
A printing ink capable of being rapidly colored comprises the following raw materials in parts by weight: 80 parts of epoxy styrene-acrylic resin, 60 parts of nano titanium dioxide sol, 3 parts of GP type glycerol polyether, 5 parts of liquid paraffin, 15 parts of pigment and 8 parts of high temperature resistant filler;
the printing ink is prepared by the following steps:
step S1: mixing ethylene glycol methyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 150r/min and the temperature is 90 ℃, reacting for 2 hours, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1.5 hours, adding the rest of the mixed solution, continuing to react for 5 hours, cooling to 35 ℃, and adjusting the pH value of the reaction solution to 9 to prepare the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 150r/min, stirring for 30min at the temperature of 30 ℃, then continuously stirring for 15min at the temperature of 70 ℃, adjusting the pH value to be 2, and continuously stirring for 6h to prepare nano titanium dioxide sol;
step S3: adding deionized water, GP type glyceryl polyether, liquid paraffin, pigment and high temperature resistant filler into a stirring kettle, stirring for 15min at the rotation speed of 800r/min, then stirring for 1.5h at the rotation speed of 4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 3000r/min for 40min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1.5h at the rotation speed of 4000r/min, and then grinding through a 20-micron screen mesh to obtain the printing ink.
The high-temperature resistant filler is prepared by the following steps:
step A1: adding a chromic oxide solution and a phosphoric acid solution into a reaction kettle, stirring for 30min at the rotation speed of 300r/min and the temperature of 80 ℃, adding aluminum hydroxide, heating to 98 ℃, stirring for 1.5h, cooling to 85 ℃, adding paraformaldehyde and tributyl phosphate, continuously stirring for 10min, heating to 120 ℃, keeping the temperature for 30min, cooling to 70 ℃, adding gamma-aminopropyltriethoxysilane and an ethanol solution, and performing ultrasonic treatment for 15min at the frequency of 5MHz to obtain an aluminum chromium phosphate peptization;
step A2: adding octamethylcyclotetrasiloxane and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, reacting for 8 hours at the rotation speed of 120r/min and the temperature of 150 ℃ to obtain alkali glue, adding 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and dimethyl sulfoxide into the reaction kettle, introducing nitrogen for protection, reacting for 15 hours at the rotation speed of 80r/min and the temperature of 75 ℃, filtering to remove a filtrate, and distilling the filtrate under the pressure of-0.095 MPa and the temperature of 110 ℃ to obtain a silicone oil base solution;
step A3: adding a sulfuric acid solution into a reaction kettle, adding graphite, sodium nitrate and potassium permanganate at the rotation speed of 150r/min and the temperature of 5 ℃, continuously stirring for 1.5h, heating to 40 ℃, continuously stirring for 40min, heating to 90 ℃, continuously stirring for 10min, adding hydrogen peroxide, continuously stirring for 30min, filtering to remove filtrate, dispersing a filter cake in deionized water, adding sodium hydroxide and monochloroacetic acid, stirring for 30min at the rotation speed of 500r/min and the temperature of 60 ℃, filtering to remove filtrate, and drying the filter cake to obtain a carrier;
step A4: and B, adding the aluminum chromium phosphate peptization prepared in the step A1, the silicone oil base solution prepared in the step A2, the carrier prepared in the step A3 and deionized water into a reaction kettle, stirring for 10 hours at the rotation speed of 200r/min and the temperature of 30 ℃, adding dicyclohexylcarbodiimide, continuously stirring for 30 minutes, performing ultrasonic treatment for 10 minutes at the frequency of 10MHz, filtering to remove filtrate, and drying a filter cake to obtain the high-temperature-resistant filler.
Comparative example
This comparative example is a common printing ink on the market.
The results of performance test on the printing inks prepared in examples 1 to 3 and comparative example are shown in table 1 below;
scratch resistance: using an Elcometer equipped with a tungsten carbide tip of 0.75mm (0.03') diameterTM3092 durometer hardness tester measures the scratch resistance of the printing inks prepared in examples 1-3 and comparative examples, with A: no scraping at 8N; b: no scraping at 7N; c: no scraping at 5N; d: scraping under 5N;
TABLE 1
Figure BDA0002662770910000131
The printing inks obtained from examples 1-3 of Table 1 above all had a scratch resistance rating of A, and did not fade when incubated at 200 ℃ for 5 hours, while the printing inks obtained from comparative examples had a scratch resistance rating of C, and faded when incubated at 120 ℃ for 5 hours, showing good scratch resistance and heat resistance.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (8)

1. A printing ink capable of being rapidly colored, which is characterized in that: the feed comprises the following raw materials in parts by weight: 50-80 parts of epoxy styrene-acrylic resin, 30-60 parts of nano titanium dioxide sol, 1-3 parts of defoaming agent, 3-5 parts of dispersing agent, 10-15 parts of pigment and 5-8 parts of high-temperature resistant filler;
the printing ink is prepared by the following steps:
step S1: mixing ethylene glycol monomethyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 120 plus materials/min and the temperature is 80-90 ℃, reacting for 1-2h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1-1.5h, adding the rest of the mixed solution, continuing to react for 3-5h, cooling under the condition that the temperature is 30-35 ℃, adjusting the pH value of the reaction solution to 8-9, and preparing the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120-plus 150r/min, stirring for 20-30min under the condition that the temperature is 25-30 ℃, then continuously stirring for 10-15min under the condition that the temperature is 60-70 ℃, adjusting the pH value to be 1-2, and continuously stirring for 4-6h to prepare nano titanium dioxide sol;
step S3: adding deionized water, a defoaming agent, a dispersing agent, a pigment and a high-temperature-resistant filler into a stirring kettle, stirring for 10-15min at the rotation speed of 500-4000 r/min, stirring for 1-1.5h at the rotation speed of 3000-4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 2000-3000r/min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1-1.5h at the rotation speed of 3000-4000r/min, and grinding through a 15-20 mu m screen to obtain the printing ink.
2. A rapidly pigmentable printing ink as claimed in claim 1, wherein: the mass ratio of the ethylene glycol monomethyl ether, the styrene, the acrylic acid, the N-butyl acrylate and the N-hydroxymethyl acrylamide solution in the mixed solution in the step S1 is 6g:3.5-3.8g:2.05-2.1g:3.5g:3.5-4mL, the using amount of ammonium persulfate is 3-5% of the mass of ethylene glycol monomethyl ether, and the using amount ratio of sodium hydroxide to deionized water in the dropping liquid in the step S2 is 8-10g:100mL, the volume ratio of the dosage of the n-butyl titanate, the ethanol and the dropping liquid is 3:20:80-100, the dosage of the deionized water in the step S3 is 20-30% of the mass sum of the epoxy styrene-acrylic resin and the nano titanium dioxide sol, the defoaming agent is one or more of GP type glyceryl polyether, GPE type polyoxyethylene ether and PPG type polypropylene glycol which are mixed in any proportion, and the dispersing agent is one or two of liquid paraffin and microcrystalline paraffin which are mixed in any proportion.
3. A rapidly pigmentable printing ink as claimed in claim 1, wherein: the high-temperature resistant filler is prepared by the following steps:
step A1: adding chromium oxide and phosphoric acid solution into a reaction kettle, stirring for 20-30min under the conditions that the rotation speed is 200-80 ℃ and the temperature is 70-80 ℃, adding aluminum hydroxide, heating to 95-98 ℃, stirring for 1-1.5h, cooling to 80-85 ℃, adding paraformaldehyde and tributyl phosphate, continuing stirring for 5-10min, heating to 110-120 ℃, preserving heat for 20-30min, cooling to 60-70 ℃, adding gamma-aminopropyltriethoxysilane and ethanol solution, and performing ultrasonic treatment for 10-15min under the condition that the frequency is 3-5MHz to prepare aluminum chromium phosphate peptization;
step A2: adding octamethylcyclotetrasiloxane and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, reacting for 5-8h under the conditions that the rotating speed is 100-150 ℃ and the temperature is 130-150 ℃ to obtain alkali glue, adding 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and dimethyl sulfoxide into the reaction kettle, introducing nitrogen for protection, reacting for 10-15h under the conditions that the rotating speed is 60-80r/min and the temperature is 70-75 ℃, filtering to remove filtrate, and distilling the filtrate under the conditions that the pressure is-0.095 MPa and the temperature is 100-110 ℃ to obtain silicone oil base liquid;
step A3: adding a sulfuric acid solution into a reaction kettle, adding graphite, sodium nitrate and potassium permanganate at the rotation speed of 120-5 ℃ at the temperature of 3-5 ℃, continuously stirring for 1-1.5h, heating to 30-40 ℃, continuously stirring for 20-40min, heating to 80-90 ℃, continuously stirring for 5-10min, adding hydrogen peroxide, continuously stirring for 20-30min, filtering to remove filtrate, dispersing filter cakes in deionized water, adding sodium hydroxide and monochloroacetic acid, stirring at the rotation speed of 300-500r/min at the temperature of 50-60 ℃ for 20-30min, filtering to remove filtrate, and drying the filter cakes to obtain a carrier;
step A4: and B, adding the aluminum chromium phosphate peptization prepared in the step A1, the silicone oil base liquid prepared in the step A2, the carrier prepared in the step A3 and deionized water into a reaction kettle, stirring for 5-10 hours at the rotation speed of 150-200r/min and at the temperature of 25-30 ℃, adding dicyclohexylcarbodiimide, continuously stirring for 20-30 minutes, performing ultrasonic treatment for 5-10 minutes at the frequency of 5-10MHz, filtering to remove filtrate, and drying a filter cake to obtain the high-temperature-resistant filler.
4. A rapidly pigmentable printing ink as claimed in claim 3, wherein: the dosage ratio of the chromic oxide, the phosphoric acid solution and the aluminum hydroxide in the step A1 is 1g, 15mL and 4g, the dosage of the paraformaldehyde is 10-15% of the mass of the aluminum hydroxide, the dosage of the tributyl phosphate is 3-5% of the mass of the aluminum hydroxide, the dosage of the gamma-aminopropyltriethoxysilane is 3-5% of the mass of the aluminum hydroxide, and the mass fraction of the ethanol solution is 30-50%.
5. A rapidly pigmentable printing ink as claimed in claim 3, wherein: in the alkali glue described in the step A2, the amount of sodium hydroxide is 0.015-0.02% of the mass of octamethylcyclotetrasiloxane, the amount of 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane are in a mass ratio of 1:20:15, and the amount of dimethyl sulfoxide is 0.05-0.06% of the mass of octamethylcyclotetrasiloxane.
6. A rapidly pigmentable printing ink as claimed in claim 3, wherein: the amount ratio of the graphite, the sodium nitrate, the potassium permanganate and the hydrogen peroxide in the step A3 is 1g to 0.5g to 3g to 2-3mL, the mass fraction of the hydrogen peroxide is 5-8%, and the amount ratio of the filter cake, the sodium hydroxide and the monochloroacetic acid is 1-1.5 to 5 to 6.
7. A rapidly pigmentable printing ink as claimed in claim 3, wherein: step A4, the dosage of the aluminum phosphate chromium peptization, the silicone oil base solution and the carrier is 2mL:2mL:3-4g, and the dosage of the dicyclohexylcarbodiimide is 50-60% of the mass of the carrier.
8. A method of making a rapidly pigmenting printing ink as claimed in claim 1, wherein: the method comprises the following steps:
step S1: mixing ethylene glycol monomethyl ether, styrene, acrylic acid and N-butyl acrylate to prepare a mixed solution, adding the mixed solution with the volume of 1/3 into a reaction kettle, introducing nitrogen for protection, stirring and adding ammonium persulfate under the conditions that the rotating speed is 120 plus materials/min and the temperature is 80-90 ℃, reacting for 1-2h, adding an N-hydroxymethyl acrylamide solution, continuing to react for 1-1.5h, adding the rest of the mixed solution, continuing to react for 3-5h, cooling under the condition that the temperature is 30-35 ℃, adjusting the pH value of the reaction solution to 8-9, and preparing the epoxy styrene-acrylic resin;
step S2: dissolving sodium hydroxide in deionized water to prepare dropping liquid, adding n-butyl titanate and ethanol into a reaction kettle, stirring and adding the dropping liquid under the condition that the rotating speed is 120-plus 150r/min, stirring for 20-30min under the condition that the temperature is 25-30 ℃, then continuously stirring for 10-15min under the condition that the temperature is 60-70 ℃, adjusting the pH value to be 1-2, and continuously stirring for 4-6h to prepare nano titanium dioxide sol;
step S3: adding deionized water, a defoaming agent, a dispersing agent, a pigment and a high-temperature-resistant filler into a stirring kettle, stirring for 10-15min at the rotation speed of 500-4000 r/min, stirring for 1-1.5h at the rotation speed of 3000-4000r/min to obtain a first mixture, mixing the epoxy styrene-acrylic resin prepared in the step S1 and the nano titanium dioxide sol prepared in the step S2 at the rotation speed of 2000-3000r/min to obtain a second mixture, mixing the first mixture and the second mixture, stirring for 1-1.5h at the rotation speed of 3000-4000r/min, and grinding through a 15-20 mu m screen to obtain the printing ink.
CN202010909643.3A 2020-09-02 2020-09-02 Printing ink capable of being quickly colored and preparation method thereof Withdrawn CN111995907A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116042017A (en) * 2023-03-13 2023-05-02 湖南华庆科技有限公司 High-tensile high-temperature-resistant resin ink and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116042017A (en) * 2023-03-13 2023-05-02 湖南华庆科技有限公司 High-tensile high-temperature-resistant resin ink and preparation method thereof

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