CN112029341B - Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof - Google Patents
Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof Download PDFInfo
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- CN112029341B CN112029341B CN202010968383.7A CN202010968383A CN112029341B CN 112029341 B CN112029341 B CN 112029341B CN 202010968383 A CN202010968383 A CN 202010968383A CN 112029341 B CN112029341 B CN 112029341B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
Abstract
The invention relates to the technical field of printing ink, and discloses environment-friendly acrylate modified waterborne polyurethane printing ink and a preparation method thereof. Comprises the following components in parts by weight: acrylate modified waterborne polyurethane, modified nano titanium dioxide, a defoaming agent, a dispersing agent and water; firstly, adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800 r/min. The water-based ink prepared by the invention has the advantages of environmental protection, high solid content and excellent water resistance; in addition, the nano titanium dioxide pigment added into the ink can be uniformly dispersed in an aqueous medium, and the acrylate modified aqueous polyurethane binder cannot be degraded by photocatalysis, so that the service life of the ink is prolonged.
Description
Technical Field
The invention relates to the technical field of printing ink, in particular to environment-friendly acrylate modified waterborne polyurethane printing ink and a preparation method thereof.
Background
The solvent-based ink is composed of four main components, namely colored dye, binder resin (high molecular resin or natural resin), organic solvent and related auxiliary agents, and the binder resin is usually dispersed in the organic solvent, so the binder component generally contains the organic solvent which accounts for about half of the total weight of the binder, if the binder component is contacted for a long time, the skin of operators and users is corroded to a certain extent, and the Volatile Organic Compounds (VOCs) contained in the binder component can be mixed in the air and passively absorbed into the human body in the production process, so the health of the human body is greatly threatened. The organic solvent component in the solvent-based ink accounts for about half of the total amount of the solvent, and the solvent is extremely easy to volatilize, the solvent is volatilized in the air in the production and use processes, part of the solvent which is volatilized into the air is mixed with oxygen, and even the solvent and the oxygen generate chemical reaction to generate new harmful substances, so that the air environment of human living and activities is greatly damaged, the ecological balance is disturbed under the severe condition, and the water-based ink is produced under the severe condition. The water-based ink is called water ink for short and consists of pigment, relevant assistant, water-dispersible or water-soluble polymer resin binder and solvent. Therefore, the water-based ink has the greatest characteristic of being different from solvent-based ink, and the water-based ink has the most obvious characteristic of being very low in organic solvent content or completely free of organic solvent, so that the water-based ink has the advantages of being very low in VOCs content, non-toxic or low in toxicity, free of combustion, free of corrosion and the like, and water resources are very abundant on the earth, so that the water-based ink is popular under the current theme of green environmental protection, and is rapidly developed in the printing industry and related industries as a core green environment-friendly printing material.
Polyurethane is a kind of macromolecular compound connecting material containing urethane, and is produced by using polyisocyanate and polyalcohol through step-by-step polymerization reaction. Hydrophilic groups are connected in the molecular chain of the polyurethane to form the waterborne polyurethane, and the waterborne polyurethane has strong affinity with water. The most widespread approach to the synthesis of aqueous polyurethanes is structural modification, i.e., the modification of the hydrophobic polyurethane backbone with hydrophilic functional groups, the water added during the synthesis acting primarily as a pre-polymer for emulsification and dispersion. The aqueous polyurethane resin has good film forming property, excellent wear resistance and bonding property, good low temperature resistance, gloss retention, wide adjustability and other advantages, so people are constantly researching and developing the aqueous ink polyurethane resin. However, the aqueous polyurethane emulsion directly synthesized by the traditional diisocyanate and oligomer polyol still has the problems of low solid content, poor stability, poor self-thickening property, insufficient glossiness of emulsion film, unsatisfactory water resistance and the like. On the other hand, the related characteristics of the pigment in the ink are important factors influencing the production of the water-based ink, and the rutile type nano titanium dioxide is stable in structure, non-toxic, odorless, fine in particle, high in whiteness and good in shielding performance, so that the rutile type nano titanium dioxide is frequently used as the pigment of the water-based ink, but the rutile type nano titanium dioxide is easy to agglomerate in a water-based medium and has certain photocatalytic characteristics, so that the photocatalytic degradation of an ink binder is caused.
Chinese patent publication No. CN106554476 discloses a preparation method of polyurethane resin for flexible package gravure table printing ink, which comprises the steps of firstly putting polybasic acid and dihydric alcohol into a reaction container, heating and vacuumizing to prepare polyester polyol, and then adding a micromolecular polyol chain extender into a prepolymer to prepare the polyurethane resin. The polyurethane resin prepared in the technical scheme of the patent is solvent type resin, and the volatilization of the solvent easily causes air pollution and threatens human health.
Chinese patent publication No. CN106833116 discloses a waterborne polyurethane printing ink and a preparation process thereof, which comprises the following components in parts by weight: the paint comprises water-based polyurethane emulsion, deionized water, organic pigment or inorganic pigment, water-based wax emulsion, methyl alcohol amine neutralizer, thickener, defoamer and wetting agent. The aqueous polyurethane ink in the technical scheme of the patent has the problems of low solid content, poor stability, poor self-thickening property, insufficient glossiness of a latex film, insufficient water resistance and the like.
Chinese patent publication No. CN101003703 discloses a composite white ink for aqueous flexographic and gravure printing, which comprises the following components: the water-soluble polyurethane resin, the stabilizer, the titanium dioxide, the water-soluble acrylic resin, the water, the dispersant, the scratch-resistant agent, the defoaming agent and the ethanol. According to the technical scheme, titanium dioxide is used as a white pigment of the ink, but nano titanium dioxide is easy to agglomerate in an aqueous medium and has certain photocatalytic characteristics, so that photocatalytic degradation of the ink binder is caused.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides the environment-friendly acrylate modified waterborne polyurethane printing ink. The water-based ink prepared by the invention has the advantages of environmental protection, high solid content and excellent water resistance; in addition, the nano titanium dioxide pigment added into the ink can be uniformly dispersed in an aqueous medium, and the acrylate modified aqueous polyurethane binder cannot be degraded by photocatalysis, so that the service life of the ink is prolonged.
The invention also provides a preparation method of the environment-friendly acrylate modified waterborne polyurethane printing ink.
In order to achieve the purpose, the invention adopts the following technical scheme: an environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following components in parts by weight:
40-50 parts of acrylate modified waterborne polyurethane, 20-25 parts of modified nano titanium dioxide, 1-3 parts of defoaming agent, 0.5-1 part of dispersing agent and 30-40 parts of water.
Preferably, the preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) mixing polyethylene glycol adipate, polyoxypropylene glycol and 1, 4-dihydroxy butane-2-sodium sulfonate, then carrying out vacuum dehydration, adding isophorone diisocyanate, hexamethylene diisocyanate and a stannous octoate catalyst, and carrying out heat preservation reaction in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) adding a chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding an end-capping reagent and 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out a heat preservation reaction in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with a main chain introduced with active double bonds;
4) adding methyl methacrylate and butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding an initiator, and carrying out free radical polymerization reaction in a nitrogen protection atmosphere to obtain the acrylate modified waterborne polyurethane.
Preferably, the heat preservation reaction temperature in the step 1) is 75-85 ℃, and the heat preservation reaction time is 2-4 h.
Preferably, the temperature in the step 2) is kept between 30 and 40 ℃, and the reaction time is kept between 0.5 and 2 hours.
Preferably, the temperature in the step 3) is kept between 40 and 60 ℃, and the reaction time is kept between 0.5 and 2 hours.
Preferably, the temperature for the heat preservation reaction in the step 4) is 70-90 ℃, and the time for the free radical polymerization reaction is 2-4 h.
Preferably, the preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to obtain a dopamine solution, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 8-9, then adding nano titanium dioxide, stirring and reacting for 2-5h, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide, adding the dopamine-coated nano titanium dioxide into a sodium hexametaphosphate solution, stirring and dispersing uniformly to obtain a suspension, adjusting the pH value of the system to 8.5-10, heating to 70-80 ℃, slowly dropwise adding a sodium silicate solution and an aluminum sulfate solution into the suspension, standing and aging for 15-20h, and sequentially filtering, separating, washing, drying and grinding to obtain the modified nano titanium dioxide.
Preferably, the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1: 2-3.
A preparation method of environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following steps:
adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800 r/min.
Because polyester polyol as a soft polyurethane material generally has the characteristics of good mechanical property, excellent solvent resistance and abrasion resistance and the like, but the hydrolysis resistance and the low-temperature flexibility of the polyester polyol are poor; the polyurethane material with polyether glycol as the soft segment has good hydrolysis resistance, low temperature resistance and bending resistance, so that the invention selects polyester and polyether to synthesize the mixed waterborne polyurethane, thereby obtaining the waterborne polyurethane resin with the advantages of the polyester and the polyether. Because the molecular structure of the aromatic polyisocyanate contains benzene rings, the polyurethane material prepared from the aromatic polyisocyanate can turn yellow after being illuminated for a long time, and the appearance of the product is influenced; and the aromatic polyisocyanate has high activity, the reaction is difficult to control, and the reaction conditions are harsh, so the aliphatic polyisocyanate is selected to synthesize the waterborne polyurethane, so that the yellowing-resistant waterborne polyurethane resin is obtained, and the reaction conditions are easy to control. Most of anionic waterborne polyurethane produced inside and outside China in the prior art is carboxylic acid type, and the carboxylic acid type waterborne polyurethane still has the defects of low solid content, heavy amine smell, stability only in an alkaline environment and the like, so that the sulfonate type waterborne polyurethane is synthesized by using the sulfonate type hydrophilic monomer, and the sulfonate type waterborne polyurethane resin which has high solid content, no odor and better stability at lower pH is obtained. The invention selects the acrylate to chemically modify the waterborne polyurethane, so that the waterborne polyurethane not only keeps good weather resistance, water resistance and solvent resistance of the acrylate, but also combines the advantages of the polyurethane, simultaneously improves the adhesive force of the waterborne polyurethane on a nonpolar film, and is greatly beneficial to the improvement of the coating performance and the reduction of the cost of the waterborne polyurethane resin.
The relevant characteristics of the pigment in the ink are important factors influencing the production of the water-based ink, and the nano titanium dioxide has stable structure, no toxicity, no odor, fine particles, high whiteness and good shielding performance, so the nano titanium dioxide is selected as the pigment of the acrylate modified water-based polyurethane, but the nano titanium dioxide is easy to agglomerate in a water-based medium, has certain photocatalytic characteristics and is easy to cause photocatalytic degradation of ink binders. In the invention, the nano titanium dioxide is subjected to surface modification treatment, sodium silicate and aluminum sulfate are used as precursors to be hydrolyzed to generate Si (OH)4And Al (OH)3The silicon-aluminum film layer is deposited and coated on the surface of the titanium dioxide, and can shield the photocatalytic property of the nano titanium dioxide, so that the negative effect of the nano titanium dioxide on photocatalytic degradation of the acrylate modified waterborne polyurethane binder is avoided, and the service life of the ink is prolonged; in addition, the silicon-aluminum film layer has good wettability, so that the wetting and dispersing performance of the nano titanium dioxide in the water-based ink is improved, and the whiteness of the ink is further improvedValue, hiding power and gloss. In experiments of coating the silicon-aluminum film layer on the surface of the nano titanium dioxide, the team of the invention finds that the combination stability of the silicon-aluminum film layer and the nano titanium dioxide is poor, and the silicon-aluminum film layer is easy to fall off and separate from the surface of the nano titanium dioxide under the stirring action in the subsequent ink ingredient stirring process, so that the improvement effect of the silicon-aluminum film layer on the performance of the nano titanium dioxide is greatly reduced. Therefore, the invention further pretreats the nano titanium dioxide, firstly coats a polydopamine layer on the surface of the nano titanium dioxide through the auto-oxidation polymerization reaction of dopamine, then deposits and combines a silicon-aluminum film layer on the polydopamine layer, more hydroxyl groups are loaded on the polydopamine layer, and the hydroxyl groups loaded on the polydopamine layer and Si (OH) are utilized4And Al (OH)3The silicon-aluminum thin film layer is tightly combined on the surface of the nano titanium dioxide by the action of hydrogen bonds and the adhesion action of the polydopamine layer, so that the silicon-aluminum thin film layer is prevented from falling off from the surface of the nano titanium dioxide in the subsequent ink ingredient stirring and mixing process, and the wetting dispersion performance and the photocatalytic degradation resistance of the nano titanium dioxide coated by the silicon-aluminum thin film layer in the water-based ink are maintained.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. In the present invention, unless otherwise specified, raw materials, equipment, and the like used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) sequentially adding 100g of polyethylene glycol adipate with the molecular weight of 1000, 200g of polypropylene oxide glycol with the molecular weight of 2000 and 7.68 g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at the constant temperature of 90 ℃, then adding 71g of isophorone diisocyanate, 13.5g of hexamethylene diisocyanate and 0.04g of stannous octoate catalyst, and carrying out heat preservation reaction for 3h at the temperature of 80 ℃ in the nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) reducing the temperature of the reaction system in the step 1) to 30 ℃, adding 7.2g of ethylenediamine chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction for 1h at 35 ℃ in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding 5.16 g of di-n-butylamine end-capping agent and 4.64g of 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out heat preservation reaction for 1h at 55 ℃ in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with a main chain introduced with active double bonds;
4) and (3) reducing the temperature of the reaction system in the step 3) to 40 ℃, adding 80g of methyl methacrylate and 40g of butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding 0.96g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 2.5h at 85 ℃ in a nitrogen protection atmosphere to obtain the acrylate modified waterborne polyurethane.
The preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to prepare a dopamine solution with the mass concentration of 3.0%, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 9, then adding nano titanium dioxide, wherein the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1:2.5, stirring and reacting for 4 hours, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide; adding sodium hexametaphosphate into deionized water, stirring and dissolving to prepare a sodium hexametaphosphate solution with the mass concentration of 0.5%, adding dopamine-coated nano titanium dioxide into the sodium hexametaphosphate solution according to the mass volume ratio of 1g/20mL, stirring and dispersing uniformly to obtain a suspension, adjusting the pH of the system to 8.5, heating to 80 ℃, slowly dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0% into the suspension, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the dopamine-coated nano titanium dioxide is 1:1, standing and aging for 18h, and filtering, separating, washing, drying and grinding are sequentially carried out to obtain the modified nano titanium dioxide.
The environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following components in parts by weight:
42 parts of acrylate modified waterborne polyurethane binder, 23 parts of modified nano titanium dioxide pigment, 2 parts of dimethyl silicone oil defoamer, 0.8 part of polyacrylamide dispersant and 35 parts of water.
The preparation method of the environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following steps:
adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 30min at a stirring speed of 500r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20min at a stirring speed of 800r/min to obtain the acrylic modified waterborne polyurethane.
Example 2
The preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) sequentially adding 100g of polyethylene glycol adipate with the molecular weight of 1000, 200g of polypropylene oxide glycol with the molecular weight of 2000 and 7.68 g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at the constant temperature of 90 ℃, then adding 71g of isophorone diisocyanate, 13.5g of hexamethylene diisocyanate and 0.04g of stannous octoate catalyst, and carrying out heat preservation reaction for 3h at the temperature of 80 ℃ in the nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) reducing the temperature of the reaction system in the step 1) to 30 ℃, adding 7.2g of ethylenediamine chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction for 1h at 35 ℃ in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding 5.16 g of di-n-butylamine end-capping agent and 4.64g of 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out heat preservation reaction for 1.5h at 45 ℃ in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with active double bonds introduced into a main chain;
4) and (3) reducing the temperature of the reaction system in the step 3) to 40 ℃, adding 80g of methyl methacrylate and 40g of butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding 0.96g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 3.5h at 75 ℃ in a nitrogen protection atmosphere to obtain the acrylate modified waterborne polyurethane.
The preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to prepare a dopamine solution with the mass concentration of 3.0%, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 8, then adding nano titanium dioxide, wherein the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1:2.5, stirring and reacting for 3 hours, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide; adding sodium hexametaphosphate into deionized water, stirring and dissolving to prepare a sodium hexametaphosphate solution with the mass concentration of 0.5%, adding dopamine-coated nano titanium dioxide into the sodium hexametaphosphate solution according to the mass volume ratio of 1g/20mL, stirring and dispersing uniformly to obtain a suspension, adjusting the pH value of the system to 10, heating to 70 ℃, slowly dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0% into the suspension, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the dopamine-coated nano titanium dioxide is 1:1, standing and aging for 16h, and filtering, separating, washing, drying and grinding are sequentially carried out to obtain the modified nano titanium dioxide.
The environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following components in parts by weight:
45 parts of acrylate modified waterborne polyurethane connecting material, 22 parts of modified nano titanium dioxide pigment, 2 parts of dimethyl silicone oil defoaming agent, 0.6 part of polyacrylamide dispersant and 35 parts of water.
The preparation method of the environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following steps:
adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 50min at a stirring speed of 400r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 30min at a stirring speed of 600r/min to obtain the acrylic modified waterborne polyurethane.
Example 3
The preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) sequentially adding 100g of polyethylene glycol adipate with the molecular weight of 1000, 200g of polypropylene oxide glycol with the molecular weight of 2000 and 7.68 g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at the constant temperature of 90 ℃, then adding 71g of isophorone diisocyanate, 13.5g of hexamethylene diisocyanate and 0.04g of stannous octoate catalyst, and carrying out heat preservation reaction for 2h at the temperature of 85 ℃ in the nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) reducing the temperature of the reaction system in the step 1) to 30 ℃, adding 7.2g of ethylenediamine chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction for 0.5h at 40 ℃ in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding 5.16 g of di-n-butylamine end-capping agent and 4.64g of 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out heat preservation reaction for 0.5h at 60 ℃ in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with active double bonds introduced into a main chain;
4) and (3) reducing the temperature of the reaction system in the step 3) to 40 ℃, adding 80g of methyl methacrylate and 40g of butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding 0.96g of potassium persulfate initiator, and carrying out free radical polymerization reaction 2 at 90 ℃ in a nitrogen protection atmosphere to obtain the acrylate modified waterborne polyurethane.
The preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to prepare a dopamine solution with the mass concentration of 3.0%, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 8.5, then adding nano titanium dioxide, wherein the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1:3, stirring and reacting for 5 hours, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide; adding sodium hexametaphosphate into deionized water, stirring and dissolving to prepare a sodium hexametaphosphate solution with the mass concentration of 0.5%, adding dopamine-coated nano titanium dioxide into the sodium hexametaphosphate solution according to the mass volume ratio of 1g/20mL, stirring and dispersing uniformly to obtain a suspension, adjusting the pH value of the system to 9, heating to 75 ℃, slowly dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0% into the suspension, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the dopamine-coated nano titanium dioxide is 1:1, standing and aging for 20 hours, and sequentially filtering, separating, washing, drying and grinding to obtain the modified nano titanium dioxide.
The environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following components in parts by weight:
40 parts of acrylate modified waterborne polyurethane connecting material, 25 parts of modified nano titanium dioxide pigment, 3 parts of dimethyl silicone oil defoaming agent, 1 part of polyacrylamide dispersant and 40 parts of water.
The preparation method of the environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following steps:
adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 40min at the stirring speed of 450r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 25min at the stirring speed of 700r/min to obtain the acrylic modified waterborne polyurethane.
Example 4
The preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) sequentially adding 100g of polyethylene glycol adipate with the molecular weight of 1000, 200g of polypropylene oxide glycol with the molecular weight of 2000 and 7.68 g of 1, 4-dihydroxy butane-2-sodium sulfonate into a reaction kettle with a stirrer, carrying out vacuum dehydration for 1h at the constant temperature of 90 ℃, then adding 71g of isophorone diisocyanate, 13.5g of hexamethylene diisocyanate and 0.04g of stannous octoate catalyst, and carrying out heat preservation reaction for 4h at the temperature of 75 ℃ in the nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) reducing the temperature of the reaction system in the step 1) to 30 ℃, adding 7.2g of ethylenediamine chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction for 2 hours at 30 ℃ in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding 5.16 g of di-n-butylamine end-capping agent and 4.64g of 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out heat preservation reaction for 2h at 40 ℃ in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with a main chain introduced with active double bonds;
4) and (3) reducing the temperature of the reaction system in the step 3) to 40 ℃, adding 80g of methyl methacrylate and 40g of butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding 0.96g of potassium persulfate initiator, and carrying out free radical polymerization reaction for 4h at 70 ℃ in a nitrogen protection atmosphere to obtain the acrylate modified waterborne polyurethane.
The preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to prepare a dopamine solution with the mass concentration of 3.0%, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 8.5, then adding nano titanium dioxide, wherein the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1:2, stirring and reacting for 2 hours, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide; adding sodium hexametaphosphate into deionized water, stirring and dissolving to prepare a sodium hexametaphosphate solution with the mass concentration of 0.5%, adding dopamine-coated nano titanium dioxide into the sodium hexametaphosphate solution according to the mass volume ratio of 1g/20mL, stirring and dispersing uniformly to obtain a suspension, adjusting the pH value of the system to 9, heating to 75 ℃, slowly dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0% into the suspension, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the dopamine-coated nano titanium dioxide is 1:1, standing and aging for 15h, and filtering, separating, washing, drying and grinding are sequentially carried out to obtain the modified nano titanium dioxide.
The environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following components in parts by weight:
50 parts of acrylate modified waterborne polyurethane binder, 20 parts of modified nano titanium dioxide pigment, 1 part of dimethyl silicone oil defoamer, 0.5 part of polyacrylamide dispersant and 30 parts of water.
The preparation method of the environment-friendly acrylate modified waterborne polyurethane printing ink comprises the following steps:
adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 40min at the stirring speed of 450r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 25min at the stirring speed of 700r/min to obtain the acrylic modified waterborne polyurethane.
Comparative example 1
The comparative example 1 is different from the example 1 in that the modified nano titanium dioxide is replaced with the general nano titanium dioxide.
Comparative example 2
The comparative example 2 is different from the example 1 in that the preparation method of the modified nano titanium dioxide comprises the following steps:
the preparation method of the modified nano titanium dioxide comprises the following steps:
adding sodium hexametaphosphate into deionized water, stirring and dissolving to prepare a sodium hexametaphosphate solution with the mass concentration of 0.5%, adding nano titanium dioxide into the sodium hexametaphosphate solution according to the mass-volume ratio of 1g/20mL, stirring and dispersing uniformly to obtain a suspension, adjusting the pH of the system to 8.5, heating to 80 ℃, slowly dropwise adding a sodium silicate solution with the mass concentration of 5.0% and an aluminum sulfate solution with the mass concentration of 5.0% into the suspension, wherein the volume ratio of the sodium silicate solution to the aluminum sulfate solution is 1:0.5, the mass ratio of the sodium silicate to the nano titanium dioxide is 1:1, standing and aging for 18h, and filtering, separating, washing, drying and grinding are sequentially carried out to obtain the modified nano titanium dioxide.
And (3) detecting the performance of the ink:
and (3) testing the covering power: the covering power refers to the minimum amount of ink required by coating a substance to be measured on a substrate to cover a unit area, and the unit is g/m2The method comprises the steps of representing, testing the covering power of the water-based ink by using the GB.ISO.ASTM type covering power test paperboard, firstly weighing the quality of the covering power paperboard on a balance, then uniformly coating the ink on the paperboard according to GB1726-79, observing the inclined angle of the board surface by 30 degrees under proper light intensity, just covering the black and white grids on the paperboard by the ink so as to reach a coating end point, weighing the quality of the covering power paperboard after drying, and dividing the mass difference between the front and the rear of the paperboard by the coating area to obtain the size of the covering power.
And (3) whiteness testing: uniformly coating the water-based ink on a BOPP film by using a 10-micron wire rod, then putting the BOPP film into a 55-DEG C oven to dry ink marks of the water-based ink to obtain a water-based ink scratch sample, and storing the scratch sample in the 40-DEG C oven for subsequent testing. The ink films of the aqueous inks of examples 1 to 4 and comparative examples 1 to 2 were subjected to a whiteness test using a WD type fully automatic whiteness meter.
And (3) testing the glossiness: gloss is the ability of a material surface to reflect light numerically. Uniformly coating the water-based ink on a BOPP film by using a 10-micron wire rod, then putting the BOPP film into a 55-DEG C oven to dry ink marks of the water-based ink to obtain a water-based ink scratch sample, and storing the scratch sample in the 40-DEG C oven for subsequent testing. The aqueous ink scratch was measured for gloss in the 60 degree direction using an NHG268 type gloss meter.
And (3) testing the water resistance: uniformly coating the water-based ink on a BOPP film by using a 10-micron wire rod, then putting the BOPP film into a 55-DEG C oven to dry ink marks of the water-based ink to obtain a water-based ink scratch sample, and storing the scratch sample in the 40-DEG C oven for subsequent testing. And soaking half of the scraped water-based ink in water for 24h, taking out, naturally drying at room temperature, and finally observing and comparing the change degree of the soaked part and the non-soaked part and the dyeing condition of water, thereby judging whether the water resistance of the water-based ink is good or bad. According to the result rating, the water resistance can be divided into six different grades of 0-5, and the grades of 0-5 sequentially indicate that the water resistance is gradually reduced.
And (3) testing adhesion fastness: uniformly coating the water-based ink on a BOPP film by using a 10-micron wire rod, then putting the BOPP film into a 55-DEG C oven to dry ink marks of the water-based ink to obtain a water-based ink scratch sample, and storing the scratch sample in the 40-DEG C oven for subsequent testing. And marking a scratch sample on the ink film, peeling off the ink film by using a transparent adhesive tape, judging the adhesive force grade of the ink film according to the damage degree, and classifying into a grade of 0-5 according to the damage degree, wherein the grade of 0-5 shows that the adhesive force is gradually deteriorated.
Solid content test: weighing 1.5g of acrylate modified waterborne polyurethane binder sample, placing the sample in a weighed vessel, volatilizing a part of solvent at room temperature, then placing the sample in a 105 ℃ constant temperature drying oven to be heated for 2h, taking out the sample to be weighed on an analysis electronic balance, then placing the sample in the 105 ℃ constant temperature drying oven to be heated, taking out the sample at an interval of 25min and weighing again,repeating for several times until the mass difference is within 0.01g after two times of continuous weighing, and calculating the solid content according to the following formula: w ═ m2-m0/m1-m0) X is 100%; wherein W represents solid content/%; m is0Represents the mass of the vessel/g; m is1Is the total mass/g of the sample and the vessel before drying; m is2Is the total mass/g of the dried sample and vessel.
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Hiding power (g/m)2) | 12.6 | 12.3 | 12.8 | 12.1 | 9.3 | 10.2 |
| Whiteness (%) | 95.77 | 95.52 | 95.86 | 95.31 | 90.15 | 92.87 |
| Gloss (%) | 63.2 | 62.8 | 63.6 | 62.5 | 40.2 | 45.8 |
| Solid content | 40.32 | 39.83 | 40.63 | 39.50 | - | - |
| Water resistance | Level 1 | Level 1 | Level 1 | Level 1 | - | - |
| Fastness to adhesion | Level 0 | Level 0 | Level 0 | Level 0 | - | - |
From the above test results, it can be obtained that the inks prepared in examples 1 to 4 are superior in hiding power, whiteness and gloss to those of comparative example 1 and comparative example 2. The covering power, whiteness and glossiness of the ink prepared in the examples 1 to 4 are superior to those of the ink prepared in the comparative example 1 because the nano titanium dioxide pigment is easy to agglomerate in an aqueous medium, the nano titanium dioxide pigment is subjected to surface modification treatment in the example of the invention, and sodium silicate and aluminum sulfate are used as precursors to be hydrolyzed to generate Si (OH)4And Al (OH)3And a silicon-aluminum film layer is deposited and coated on the surface of the titanium dioxide, and the silicon-aluminum film layer has good wettability, so that the wetting and dispersing performance of the nano titanium dioxide pigment in the water-based ink is improved, and further, the whiteness value, the covering power and the luminosity value of the ink are improved. The covering power, whiteness and glossiness of the ink prepared in the examples 1-4 are superior to those of the ink prepared in the comparative example 2 because the silicon-aluminum thin film layer is easy to fall off and separate from the surface of the nano titanium dioxide under the stirring action in the ink ingredient stirring process, so that the performance improvement effect of the silicon-aluminum thin film layer on the nano titanium dioxide is greatly reduced, the nano titanium dioxide is further pretreated in the embodiment of the invention, a poly dopamine layer is coated on the surface of the nano titanium dioxide through the auto-oxidation polymerization reaction of dopamine, then the silicon-aluminum thin film layer is deposited and combined on the poly dopamine layer, more hydroxyl groups are loaded on the poly dopamine layer, and the hydroxyl groups loaded on the poly dopamine layer and Si (OH) are utilized4And Al (OH)3The silicon-aluminum thin film layer is tightly combined on the surface of the nano titanium dioxide by the action of hydrogen bonds and the adhesion action of the polydopamine layer, so that the silicon-aluminum thin film layer is prevented from falling off from the surface of the nano titanium dioxide in the subsequent ink ingredient stirring and mixing process, and the wetting and dispersing performance of the silicon-aluminum thin film layer coated with the nano titanium dioxide in the water-based ink is maintained. In addition, the solid content of the ink prepared in the embodiments 1-4 is more than 39%, the water resistance reaches 1 level, the fastness reaches 0 level, and the ink meets the ink performance requirement index.
Claims (7)
1. The environment-friendly acrylate modified waterborne polyurethane printing ink is characterized by comprising the following components in parts by weight:
40-50 parts of acrylic ester modified waterborne polyurethane,
20-25 parts of modified nano titanium dioxide,
1-3 parts of a defoaming agent,
0.5 to 1 portion of dispersant
30-40 parts of water;
the preparation method of the acrylate modified waterborne polyurethane comprises the following steps:
1) mixing polyethylene glycol adipate, polyoxypropylene glycol and 1, 4-dihydroxy butane-2-sodium sulfonate, then carrying out vacuum dehydration, adding isophorone diisocyanate, hexamethylene diisocyanate and a stannous octoate catalyst, and carrying out heat preservation reaction in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 1;
2) adding a chain extender into the polyurethane prepolymer, and carrying out heat preservation reaction in a nitrogen protection atmosphere to obtain a polyurethane prepolymer 2;
3) adding an end-capping reagent and 2-hydroxyethyl acrylate into a polyurethane prepolymer containing a hydrophilic monomer, carrying out a heat preservation reaction in a nitrogen protection atmosphere, and then adding deionized water for emulsification to obtain a waterborne polyurethane emulsion with a main chain introduced with active double bonds;
4) adding methyl methacrylate and butyl acrylate into the waterborne polyurethane emulsion with the main chain introduced with the active double bond, uniformly stirring, then adding an initiator, and carrying out free radical polymerization reaction in a nitrogen protection atmosphere to obtain acrylic ester modified waterborne polyurethane;
the preparation method of the modified nano titanium dioxide comprises the following steps:
adding dopamine hydrochloride into deionized water, stirring and dissolving to obtain a dopamine solution, dropwise adding a Tirs-HCl buffer solution and a sodium hydroxide solution to adjust the pH value of the dopamine solution to 8-9, then adding nano titanium dioxide, stirring and reacting for 2-5h, filtering, washing and drying to obtain dopamine-coated nano titanium dioxide, adding the dopamine-coated nano titanium dioxide into a sodium hexametaphosphate solution, stirring and dispersing uniformly to obtain a suspension, adjusting the pH value of the system to 8.5-10, heating to 70-80 ℃, slowly dropwise adding a sodium silicate solution and an aluminum sulfate solution into the suspension, standing and aging for 15-20h, and sequentially filtering, separating, washing, drying and grinding to obtain the modified nano titanium dioxide.
2. The environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in claim 1, wherein the mass ratio of the nano titanium dioxide to the dopamine hydrochloride is 1: 2-3.
3. The environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in claim 1, wherein the temperature of the heat preservation reaction in the step 1) is 75-85 ℃ and the time of the heat preservation reaction is 2-4 h.
4. The environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in claim 1, wherein the temperature of the heat preservation reaction in the step 2) is 30-40 ℃ and the time of the heat preservation reaction is 0.5-2 h.
5. The environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in claim 1, wherein the temperature of the heat preservation reaction in the step 3) is 40-60 ℃ and the time of the heat preservation reaction is 0.5-2 h.
6. The environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in claim 1, wherein the temperature of the heat preservation reaction in the step 4) is 70-90 ℃ and the time of the free radical polymerization reaction is 2-4 h.
7. A method for preparing the environment-friendly acrylate modified waterborne polyurethane printing ink as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps: adding the acrylate modified waterborne polyurethane, the defoaming agent and the deionized water into a stirring kettle, stirring for 30-50min at the stirring speed of 400-800 r/min, then adding the modified nano titanium dioxide and the dispersing agent, and stirring for 20-30min at the stirring speed of 600-800 r/min.
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| CN113246626A (en) * | 2021-06-16 | 2021-08-13 | 上海景条印刷有限公司 | Gravure printing process for paper packaging box |
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