CN109266103B - Reversible temperature-change water-based ink and preparation method and application thereof - Google Patents
Reversible temperature-change water-based ink and preparation method and application thereof Download PDFInfo
- Publication number
- CN109266103B CN109266103B CN201811185230.4A CN201811185230A CN109266103B CN 109266103 B CN109266103 B CN 109266103B CN 201811185230 A CN201811185230 A CN 201811185230A CN 109266103 B CN109266103 B CN 109266103B
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- aqueous
- weight
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to the technical field of ink, and particularly relates to reversible temperature-change water-based ink as well as a preparation method and application thereof. The reversible temperature change water-based ink provided by the invention comprises the following components: 25-35 parts of water-based binder, 10-25 parts of nano vanadium dioxide, 5-15 parts of nontoxic alcohol cosolvent and 15-25 parts of water. The water-based ink disclosed by the invention utilizes water and a small amount of nontoxic alcohols as a solvent to replace an organic solvent, is pollution-free, safe, nuisanceless, lower in price, low in color-changing temperature, sensitive in thermal response and good in printability, and can be widely applied to nontoxic anti-counterfeiting packages of various commodities such as foods, medicines, daily chemicals, cigarette and wine bags, toys for children and the like.
Description
Technical Field
The invention belongs to the technical field of ink, and particularly relates to reversible temperature-change water-based ink as well as a preparation method and application thereof.
Background
The printed products gradually show new trends of quality, individuation and customization while meeting the popular demands, and green printing and digital printing are rapidly developed. With the rise of digital printing, the digital anti-counterfeiting technology is also developed dramatically. Advanced anti-counterfeiting technology plays a good standard role in the intense market competition environment of commodities, and among a plurality of anti-counterfeiting technologies, temperature-sensitive ink is an important technical branch, relates to a plurality of scientific and technical categories including optics, chemistry, materials science, nanotechnology, computer science, printing technology and the like, and is the most studied part in the anti-counterfeiting technical field at home and abroad at present.
There are many types of temperature-sensitive inks, and the color change is mainly determined by the temperature-sensitive pigment part used. The temperature-change pigments are divided into two categories, reversible and irreversible, thermodynamically classified. The irreversible temperature change pigment mainly comprises inorganic salts of second main group elements, methyl violet, phenol compounds and the like, has high color change temperature, contains heavy metals, does not meet the requirement of environmental protection, and can not be generally used in the field of printing and packaging of foods, medicines or daily consumer goods. The reversible temperature-change pigment is divided into three types, namely inorganic, organic and liquid crystal, wherein the cost of the liquid crystal pigment is too high when the liquid crystal pigment is used for printing and packaging; most of organic pigments contain aromatic rings, which are not good for human health; inorganic pigments are mainly composed of metals, metal halides, and polycrystalline oxides of metals, and are widely used because of their advantages such as low price, environmental friendliness, and adjustable discoloration temperature. With the continuous attention of governments and people to green and environmental protection and the trend development of green printing and digital printing, the development of the green and efficient reversible temperature-variable water-based ink with low color-variable critical temperature, good anti-counterfeiting and temperature-indicating effects and important significance is achieved.
Disclosure of Invention
Aiming at the problems, the invention provides the reversible temperature-variable water-based ink which is low in color-variable temperature, sensitive in thermal response, strong in weather resistance, good in printing performance, green and efficient, and the preparation method and the application thereof.
Specifically, the invention provides the following technical scheme:
a reversible temperature-change water-based ink comprises the following components: 25-35 parts of water-based binder, 10-25 parts of nano vanadium dioxide, 5-15 parts of nontoxic alcohol cosolvent and 15-25 parts of water.
Preferably, in the water-based ink, the water-based binder is 25 to 30 parts by weight, the nano vanadium dioxide is 15 to 20 parts by weight, the nontoxic alcohol cosolvent is 8 to 15 parts by weight, and the water is 15 to 20 parts by weight.
Preferably, in the aqueous ink, the aqueous vehicle is one or more selected from the group consisting of aqueous polyurethane, aqueous polyacrylate, and aqueous acrylic-modified polyurethane.
Preferably, in the aqueous ink, the non-toxic alcohol co-solvent is one or more selected from ethanol, isopropanol and butanol.
Preferably, the water-based ink further comprises 10-25 parts by weight of a filler, wherein the filler is selected from nano silica powder and/or titanium oxide powder.
Preferably, the aqueous ink further comprises a drier and an aqueous antioxidant, wherein the drier is 0.5-2 parts by weight, and the aqueous antioxidant is 1-3 parts by weight.
The preparation method of the water-based ink comprises the following steps:
(1) uniformly mixing an aqueous binder, nano vanadium dioxide, a nontoxic alcohol cosolvent and water with a filler, a drier and/or an aqueous antioxidant which are added according to needs to obtain a standby color paste;
(2) and (3) regulating the pH value of the standby color paste obtained in the step (1) to be 8-9.5 by using a pH regulator to obtain the thermochromic water-based ink.
Preferably, in the above preparation method, in step (1), the preparation method of nano vanadium dioxide includes the following steps:
adding vanadium pentoxide and oxalic acid dihydrate into water, heating and stirring to form an aqueous solution, performing hydrothermal reaction to generate a precipitate, separating the precipitate, washing, drying, and performing high-temperature annealing in an inert atmosphere to obtain the nano vanadium dioxide.
Preferably, in the preparation method, the feeding molar ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1: 1-3.
Preferably, in the preparation method, the hydrothermal reaction temperature is 180-250 ℃; the hydrothermal reaction time is 24-48 h.
Preferably, in the preparation method, the high-temperature annealing temperature is 800-.
Preferably, in the above preparation method, in the step (2), the PH adjuster is one or more selected from the group consisting of ethanolamine, ammonia water and triethylamine.
Preferably, the reversible temperature-change water-based ink is obtained by the above preparation method.
Preferably, the water-based ink is applied to the field of anti-counterfeiting technology.
The invention has the beneficial effects that:
the reversible temperature-change water-based ink disclosed by the invention utilizes water and nontoxic alcohols as solvents to replace organic solvents, is pollution-free, safe, pollution-free, lower in price, low in color-change temperature, sensitive in thermal response and good in printability, and can be widely applied to nontoxic anti-counterfeiting packages of various commodities such as foods, medicines, daily chemicals, cigarette and wine bags, toys for children and the like.
Drawings
FIG. 1 is a particle size distribution diagram of the aqueous ink prepared in example 1.
FIG. 2 is a viscosity measurement chart of aqueous inks prepared in examples and comparative examples, wherein the symbols are as follows: 1-the aqueous ink prepared in example 1, 2-the aqueous ink prepared in example 2, 3-the aqueous ink prepared in example 3, 4-the aqueous ink prepared in example 4, 5-the aqueous ink prepared in example 5.
FIG. 3 is a graph of the color change temperature and the color reversion time of aqueous inks prepared in examples and comparative examples, as indicated in the following notation: 1-the aqueous ink prepared in example 1, 2-the aqueous ink prepared in example 2, 3-the aqueous ink prepared in example 3, 4-the aqueous ink prepared in example 4, 5-the aqueous ink prepared in example 5, 6-the aqueous ink prepared in comparative example 1, 7-the aqueous ink prepared in comparative example 2.
Detailed Description
With the continuous attention of governments and people to green and environmental protection and the trend development of green printing and digital printing, the development of the green and efficient reversible temperature-variable water-based ink with low color-variable critical temperature, good anti-counterfeiting and temperature-indicating effects and important significance is achieved. In view of the above, the present invention provides a reversible temperature-sensitive aqueous ink, which comprises the following components: 25-35 parts of water-based binder, 10-25 parts of nano vanadium dioxide, 5-15 parts of nontoxic alcohol cosolvent and 15-25 parts of water.
In a preferred embodiment of the present invention, the reversible temperature-sensitive aqueous ink comprises the following components: 25-35 parts of water-based binder, 10-25 parts of nano vanadium dioxide, 5-15 parts of nontoxic alcohol cosolvent, 15-25 parts of water, 10-25 parts of filler, 0.5-2 parts of drier and 1-3 parts of water-based antioxidant.
The water-based binder is one or more than two of water-based polyurethane, water-based polyacrylate and water-based acrylic acid modified polyurethane, the filler is selected from nano silicon dioxide powder and/or titanium oxide powder, and the non-toxic alcohol cosolvent is one or more than two of ethanol, isopropanol and butanol.
The invention also provides a preparation method of the reversible temperature-change water-based ink, which comprises the following specific steps in a preferred embodiment:
(1) uniformly mixing an aqueous binder, nano vanadium dioxide, a nontoxic alcohol cosolvent and water with a filler, a drier and/or an aqueous antioxidant which are added according to needs to obtain a standby color paste;
(2) and (3) regulating the pH value of the standby color paste obtained in the step (1) to be 8-9.5 by using a pH regulator to obtain the thermochromic water-based ink. Wherein the pH regulator is selected from one or more than two of ethanolamine, ammonia water and triethylamine.
In a preferred embodiment of the invention, the nano vanadium dioxide is prepared by the following steps:
adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1: 1-3, heating and stirring to form an aqueous solution, carrying out 180-DEG C hydrothermal reaction at 250 ℃ for 24-48h, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 800-DEG C and 850 ℃ under argon for 2-4h to obtain the nano vanadium dioxide.
The nano vanadium dioxide synthesized by the hydrothermal method is blue black, has uniform particle size distribution, has the phase change critical temperature of 68.8 ℃, is very close to the temperature of the daily environment, has fixed color change temperature limit, narrow interval and large color difference, and is sensitive to thermal stimulation response.
The invention also provides application of the reversible temperature-change water-based ink in the technical field of anti-counterfeiting.
In a preferred embodiment of the present invention, the reversible temperature-change water-based ink is prepared by the following steps:
step 1: synthesis of aqueous polyurethane dispersion: placing polyol with the molecular weight of 1000-2000 at the temperature of 100-120 ℃ for drying for 1-2 hours, then mixing and stirring the dried polyol and isophorone diisocyanate at the temperature of 80-100 ℃ for reaction for 2-3 hours, then adding a catalyst for accelerating the reaction for 0.5-1 hour, reducing the temperature of the system to 60-70 ℃, adding a chain extender for chain extension reaction for 15-30 minutes, heating to the initial reaction temperature, continuing the reaction for 2-3 hours, cooling to 40-50 ℃, adding 1, 4-butanediol and acetone to adjust the viscosity of the system to 10-16 mPa.s, continuously stirring for reaction for 1-2 hours to obtain an aqueous polyurethane prepolymer, cooling the temperature of the system to room temperature, adding deionized water and a certain amount of triethylamine, adjusting the pH value to 8.0-9.0, aging for 12-18 hours at the room temperature, removing unreacted organic solvent by rotary evaporation to obtain an aqueous polyurethane dispersion as a target ink binder, the number average molecular weight of the waterborne polyurethane of the invention is in the range of 2000-3000.
Step 2: preparing main pigment nano vanadium dioxide powder: adding vanadium pentoxide and oxalic acid dihydrate into deionized water, heating and stirring to uniformly mix the vanadium pentoxide and the oxalic acid dihydrate, placing the mixed solution into a hydrothermal reaction kettle, keeping the solution at a high temperature for a period of time to allow the mixture to fully react, taking out the mixture after the reaction is finished, naturally cooling the mixture to room temperature, separating out a precipitate, washing the precipitate with distilled water and ethanol, drying the precipitate to obtain nano vanadium dioxide powder, and annealing the nano vanadium dioxide powder at a high temperature under an inert atmosphere to obtain the target ink main pigment.
And step 3: according to the mass fraction, stirring and dispersing 25-35 parts of the binder obtained in the step 1, 10-25 parts of the main pigment obtained in the step 2, 10-25 parts of the filler, 5-15 parts of the alcohol auxiliary agent, 15-25 parts of water, 0.5-2 parts of the drier and 1-3 parts of the antioxidant by using a high-speed dispersing agent, grinding into a standby color paste, adjusting the pH value to 8-9.5, storing in a shady, cool and dark place, and directly using or using after diluting according to actual requirements.
More preferably, the polyol in step 1 is one or more of polyether polyol or polyester polyol.
More preferably, the catalyst used in the step 1 is an environment-friendly organic bismuth catalyst DY-20.
More preferably, the chain extender used in step 1 is dimethylolpropionic acid.
More preferably, the feeding molar ratio of the vanadium pentoxide to the oxalic acid dihydrate in the step 2 is 1: 1-3.
More preferably, the hydrothermal reaction temperature in the step 2 is 180-250 ℃, and the reaction time is 24-48 hours.
More preferably, the high-temperature annealing temperature in the step 2 is 800-850 ℃, the annealing time is 2-4 hours, and the inert protective atmosphere is argon.
More preferably, the alcohol auxiliary agent in step 3 is one or more of ethanol, isopropanol and butanol, and plays multiple roles of a defoaming agent, a resin diluent and a preservative.
More preferably, the filler in step 3 is one of nano silica powder or titanium oxide powder.
More preferably, the antioxidant in step 3 is an aqueous antioxidant.
More preferably, the pH stabilizer in step 3 is one of ethanolamine, ammonia water or triethylamine.
The reversible temperature change water-based ink of the present invention, its preparation method and application are further described by the following specific examples.
In the following examples, information on each reagent and apparatus used is shown in tables 1 and 2.
TABLE 1 information Table of reagents used in examples
Table 2 table of device information used in the examples
Example one
1. Preparing a waterborne polyurethane binder: vacuum drying polypropylene glycol with molecular weight of 2000 for 1.5h at 110 ℃, mixing and stirring the polypropylene glycol and isophorone diisocyanate for reaction for 1.5h at 90 ℃, then adding an environment-friendly organic bismuth catalyst DY-20 to continuously accelerate the reaction for 1h, then reducing the temperature of the system to 60 ℃, adding a chain extender dimethylolpropionic acid to perform chain extension reaction for 20min, heating to the initial reaction temperature of 90 ℃, continuing to react for 2h, then cooling to 50 ℃, adding 1, 4-butanediol and acetone to adjust the viscosity of the system to 13mPa.s, continuously stirring and reacting for 1h to obtain an aqueous polyurethane prepolymer, cooling the temperature of the system to room temperature, adding deionized water and a certain amount of ethanolamine, adjusting the pH value to be between 8.5, aging for 12 h at the room temperature, and performing rotary evaporation to remove unreacted organic solvent to obtain the aqueous polyurethane binder (the number average molecular weight of 3000).
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:2, heating and stirring to form a water solution, carrying out hydrothermal reaction at 200 ℃ for 30h, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 800 ℃ under argon for 4h to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: uniformly mixing 30 parts by weight of waterborne polyurethane binder, 15 parts by weight of nano vanadium dioxide, 10 parts by weight of non-toxic alcohol cosolvent and 20 parts by weight of water to obtain 30g of standby color paste, and adjusting the pH of the standby color paste to 8.5 by using triethylamine to obtain the thermochromic water-based ink.
FIG. 1 is a distribution diagram showing the particle size distribution of the water-based ink prepared in this example, and it can be seen that the particle size distribution of the water-based ink is mainly around 90nm, and the dispersion is uniform and stable.
Example two
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:1, heating and stirring to form a water solution, carrying out hydrothermal reaction at 180 ℃ for 48 hours, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 800 ℃ for 2 hours under argon to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: uniformly mixing 25 parts by weight of waterborne polyurethane binder, 25 parts by weight of nano vanadium dioxide, 5 parts by weight of non-toxic alcohol cosolvent, 25 parts by weight of water, 25 parts by weight of nano silicon dioxide powder, 0.5 part by weight of drier and 3 parts by weight of antioxidant to obtain 30g of standby color paste, and adjusting the pH of the standby color paste to 8 by ethanolamine to obtain the thermochromic waterborne ink.
EXAMPLE III
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:3, heating and stirring to form a water solution, carrying out hydrothermal reaction at 250 ℃ for 24 hours, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 850 ℃ under argon for 4 hours to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: uniformly mixing 35 parts by weight of waterborne polyurethane binder, 10 parts by weight of nano vanadium dioxide, 15 parts by weight of non-toxic alcohol cosolvent, 15 parts by weight of water, 10 parts by weight of titanium oxide powder, 2 parts by weight of drier and 1 part by weight of antioxidant to obtain 30g of standby color paste, and adjusting the pH of the standby color paste to 9.5 by ammonia water to obtain the thermochromic waterborne ink.
Example four
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:2, heating and stirring to form an aqueous solution, carrying out hydrothermal reaction at 220 ℃ for 35 hours, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 820 ℃ under argon for 3 hours to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: uniformly mixing 25 parts by weight of waterborne polyurethane binder, 20 parts by weight of nano vanadium dioxide, 8 parts by weight of non-toxic alcohol cosolvent, 20 parts by weight of water, 15 parts by weight of nano silicon dioxide powder, 1 part by weight of drier and 2 parts by weight of antioxidant to obtain 30g of standby color paste, and adjusting the pH of the standby color paste to 8.5 by triethylamine to obtain the thermochromic water-based ink.
EXAMPLE five
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:2, heating and stirring to form a water solution, carrying out hydrothermal reaction at 200 ℃ for 40h, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 810 ℃ for 3h under argon to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: according to the weight portion, 30 portions of waterborne polyurethane binder, 15 portions of nano vanadium dioxide, 15 portions of nontoxic alcohol cosolvent, 15 portions of water, 20 portions of titanium oxide powder, 1.5 portions of drier and 1.5 portions of antioxidant are uniformly mixed to obtain 30g of standby color paste, and the PH value of the standby color paste is adjusted to be 9 by ethanolamine to obtain the thermochromic waterborne ink.
Comparative example 1
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:2, heating and stirring to form an aqueous solution, carrying out hydrothermal reaction at 220 ℃ for 35 hours, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 820 ℃ under argon for 3 hours to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: uniformly mixing 60 parts by weight of waterborne polyurethane binder, 20 parts by weight of nano vanadium dioxide, 8 parts by weight of non-toxic alcohol cosolvent, 20 parts by weight of water, 15 parts by weight of nano silicon dioxide powder, 1 part by weight of drier and 2 parts by weight of antioxidant to obtain 30g of standby color paste, and adjusting the pH of the standby color paste to 8.5 by triethylamine to obtain the thermochromic water-based ink.
Comparative example No. two
1. Preparing a waterborne polyurethane binder: same as step 1 of example one.
2. Preparing nano vanadium dioxide: adding vanadium pentoxide and oxalic acid dihydrate into water according to the feeding molar ratio of 1:2, heating and stirring to form a water solution, carrying out hydrothermal reaction at 200 ℃ for 40h, cooling to room temperature, separating out a precipitate, washing with distilled water and ethanol, drying, and annealing at 810 ℃ for 3h under argon to obtain the nano vanadium dioxide.
3. Preparing reversible temperature change water-based ink: according to the weight portion, 30 portions of waterborne polyurethane binder, 15 portions of nano vanadium dioxide, 100 portions of nontoxic alcohol cosolvent, 200 portions of water, 20 portions of titanium oxide powder, 1.5 portions of drier and 1.5 portions of antioxidant are uniformly mixed to obtain 30g of standby color paste, and the PH value of the standby color paste is adjusted to be 9 by ethanolamine to obtain the thermochromic waterborne ink.
Comparison of effects
1. Viscosity detection
The viscosity of the water-based inks prepared in examples 1 to 5 was measured by a laser viscometer, and the results are shown in FIG. 2, which shows that the water-based inks prepared in the examples of the present invention had a viscosity of 350 to 500 mPaS and good printability.
2. Measurement of discoloration temperature and Return time
The aqueous inks prepared in examples 1 to 5 and comparative examples 1 to 2 were measured for discoloration temperature and reversion time using the following methods, and the results are shown in FIG. 3.
And (3) measuring the color change temperature: an ink sample of 2mg was taken, and placed in a capillary tube with one end closed, and the other end sealed with vaseline. The capillary tube was fixed to the thermometer with a rubber band, with the sample as close as possible to the mercury end. Put into a 150mL beaker containing 100mL of water and slowly heat the beaker. When the temperature rose, the discoloration was observed, the ink changed from dark blue to light brown, and the time taken for the color change was the discoloration time.
And (3) measuring the color reversion time: and taking the discolored capillary out of the hot water, and observing the time for changing the color of the sample to the original color along with the temperature reduction by naked eyes at room temperature.
As can be seen from FIG. 3, the color change temperature of the water-based ink prepared in each example of the invention is about 45-55 ℃, and the color reversion time is about 5-25 min, which shows that the water-based ink of the invention has low color change temperature and sensitive thermal response, and simultaneously, the color change temperature and the color reversion time are superior to those of the water-based ink of the comparative example.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (13)
1. The reversible temperature-change water-based ink is characterized by comprising the following components: 25-35 parts of water-based binder, 10-25 parts of nano vanadium dioxide, 5-15 parts of non-toxic alcohol cosolvent and 15-25 parts of water, wherein the non-toxic alcohol cosolvent is selected from one or more of ethanol, isopropanol and butanol;
the preparation method of the nano vanadium dioxide comprises the following steps:
adding vanadium pentoxide and oxalic acid dihydrate into water, heating and stirring to form an aqueous solution, performing hydrothermal reaction to generate a precipitate, separating the precipitate, washing, drying, and performing high-temperature annealing in an inert atmosphere to obtain nano vanadium dioxide;
wherein the feeding molar ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1: 1-3;
wherein the hydrothermal reaction temperature is 180-250 ℃; the hydrothermal reaction time is 24-48 h;
wherein the high-temperature annealing temperature is 800-850 ℃, and the annealing time is 2-4 h.
2. The aqueous ink of claim 1, wherein the aqueous binder is 25-30 parts by weight, the nano vanadium dioxide is 15-20 parts by weight, the non-toxic alcohol co-solvent is 8-15 parts by weight, and the water is 15-20 parts by weight.
3. The aqueous ink according to claim 1 or 2, wherein the aqueous vehicle is one or more selected from the group consisting of aqueous polyurethane, aqueous polyacrylate, and aqueous acrylic-modified polyurethane.
4. The water-based ink according to claim 1 or 2, further comprising 10 to 25 parts by weight of a filler selected from nano silica powder and/or titanium oxide powder.
5. The water-based ink according to claim 3, further comprising 10 to 25 parts by weight of a filler selected from nano silica powder and/or titanium oxide powder.
6. The aqueous ink according to claim 1 or 2, further comprising 0.5 to 2 parts by weight of a drier and 1 to 3 parts by weight of an aqueous antioxidant.
7. The aqueous ink according to claim 3, further comprising 0.5 to 2 parts by weight of a drier and 1 to 3 parts by weight of an aqueous antioxidant.
8. The aqueous ink according to claim 4, further comprising 0.5 to 2 parts by weight of a drier and 1 to 3 parts by weight of an aqueous antioxidant.
9. The aqueous ink according to claim 5, further comprising 0.5 to 2 parts by weight of a drier and 1 to 3 parts by weight of an aqueous antioxidant.
10. A method for preparing an aqueous ink according to any one of claims 1 to 9, comprising the steps of:
(1) uniformly mixing an aqueous binder, nano vanadium dioxide, a nontoxic alcohol cosolvent and water with a filler, a drier and/or an aqueous antioxidant which are added according to needs to obtain a standby color paste;
(2) adjusting the pH value of the standby color paste obtained in the step (1) to 8-9.5 by using a pH regulator to obtain thermochromic water-based ink;
in the step (1), the preparation method of the nano vanadium dioxide comprises the following steps:
adding vanadium pentoxide and oxalic acid dihydrate into water, heating and stirring to form an aqueous solution, performing hydrothermal reaction to generate a precipitate, separating the precipitate, washing, drying, and performing high-temperature annealing in an inert atmosphere to obtain nano vanadium dioxide;
wherein the feeding molar ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1: 1-3;
wherein the hydrothermal reaction temperature is 180-250 ℃; the hydrothermal reaction time is 24-48 h;
wherein the high-temperature annealing temperature is 800-850 ℃, and the annealing time is 2-4 h.
11. The method according to claim 10, wherein in the step (2), the pH adjusting agent is one or more selected from the group consisting of ethanolamine, aqueous ammonia and triethylamine.
12. The reversible temperature-change water-based ink obtained by the preparation method of claim 10 or 11.
13. Use of the reversible temperature-sensitive aqueous ink according to any one of claims 1 to 9 or 12 in the field of anti-counterfeiting technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811185230.4A CN109266103B (en) | 2018-10-11 | 2018-10-11 | Reversible temperature-change water-based ink and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811185230.4A CN109266103B (en) | 2018-10-11 | 2018-10-11 | Reversible temperature-change water-based ink and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109266103A CN109266103A (en) | 2019-01-25 |
| CN109266103B true CN109266103B (en) | 2021-08-20 |
Family
ID=65195865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811185230.4A Active CN109266103B (en) | 2018-10-11 | 2018-10-11 | Reversible temperature-change water-based ink and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109266103B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122071A (en) * | 2020-01-15 | 2021-07-16 | 丽水兴昌新材料科技股份有限公司 | Color-changing ink formula |
| CN111647313A (en) * | 2020-06-19 | 2020-09-11 | 深圳九星印刷包装集团有限公司 | Anti-counterfeiting color-changing ink |
| CN116925589A (en) * | 2023-06-06 | 2023-10-24 | 湖州乐通新材料科技有限公司 | Preparation method of thermochromic ink |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN106809877A (en) * | 2017-03-20 | 2017-06-09 | 武汉理工大学 | A kind of preparation method of D phase hypovanadic oxides |
| CN107189550A (en) * | 2017-06-22 | 2017-09-22 | 中国人民解放军国防科学技术大学 | Inkjet printing vanadium dioxide water-based ink and its preparation method and application |
| CN108424684A (en) * | 2018-04-23 | 2018-08-21 | 中国人民解放军国防科技大学 | Thermochromic emissivity-variable printing ink and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464354B (en) * | 2010-11-05 | 2015-01-21 | 中国科学院上海硅酸盐研究所 | Rutile-phase vanadium dioxide composition, coating containing same and performance of rutile-phase vanadium dioxide composition |
| CN105001863B (en) * | 2015-07-01 | 2017-06-06 | 哈尔滨工业大学 | It is a kind of to synthesize the monocline VO with low transformation temperature2Method |
-
2018
- 2018-10-11 CN CN201811185230.4A patent/CN109266103B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120615A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
| CN106809877A (en) * | 2017-03-20 | 2017-06-09 | 武汉理工大学 | A kind of preparation method of D phase hypovanadic oxides |
| CN107189550A (en) * | 2017-06-22 | 2017-09-22 | 中国人民解放军国防科学技术大学 | Inkjet printing vanadium dioxide water-based ink and its preparation method and application |
| CN108424684A (en) * | 2018-04-23 | 2018-08-21 | 中国人民解放军国防科技大学 | Thermochromic emissivity-variable printing ink and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109266103A (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109266103B (en) | Reversible temperature-change water-based ink and preparation method and application thereof | |
| CA2471529C (en) | Colorant compounds | |
| JP2007528929A (en) | Reversible pressure sensitive color change system | |
| CN107216718B (en) | Preparation method of temperature-controlled color-changing ink | |
| EP2890640A1 (en) | Blue inorganic colourants/pigments and process for preparation thereof | |
| CN105623239B (en) | A kind of photochromic composition and its application | |
| CN113897095A (en) | Thermochromic ink and preparation method thereof | |
| CN111410531B (en) | Up-conversion luminescence reversible regulation material based on photochromic effect and preparation method thereof | |
| ES2632624T3 (en) | Aqueous polyurethane coating compositions | |
| US5376349A (en) | Method of producing tantalum (V) nitride | |
| CN108048072B (en) | A kind of gallate ability of reverse photochromism material and preparation method thereof | |
| CN107187153A (en) | PP synthetic papers and its special-purpose ink that a kind of open air is used | |
| JP2007154048A (en) | Screen ink and formed article | |
| CN107699227B (en) | Niobate reversible photochromic material and preparation method thereof | |
| JPS63308087A (en) | Temperature-dependent photochromic composition | |
| CN113462233A (en) | Water-based reversible thermochromic ink and preparation method thereof | |
| JP3291684B2 (en) | Thermal history display ink composition and package having display by the composition | |
| CN109627945A (en) | A kind of temperature sensing color changing varnish and preparation method thereof | |
| US5032452A (en) | Identification of absorbent material with a thermostable colorant and process | |
| George et al. | Synthesis and characterization of environmentally benign nontoxic pigments: RE2Mo2O9 (RE= La or Pr) | |
| CN114316940A (en) | Hydrophilic bionic thermochromic system | |
| CN110684371B (en) | Cr-doped Bi24Al2O39Metal oxide mixed phase red inorganic pigment and preparation method thereof | |
| CN112500779A (en) | Antibacterial antioxidant aluminum foil protective agent and preparation method thereof | |
| CN113214704A (en) | Weather-resistant ink, manufacturing method and testing method thereof | |
| CN108219590A (en) | A kind of environmental-friendly microcapsule type anti-forgery ink and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210730 Address after: 225600 No. 1, Weixing Road, Gaoyou City, Yangzhou City, Jiangsu Province Applicant after: Jiangsu Satellite New Material Co.,Ltd. Address before: 225600 No. 1, Weixing Road, Gaoyou City, Yangzhou City, Jiangsu Province Applicant before: YANGZHOU XIANGHUA NEW MATERIAL TECHNOLOGY Co.,Ltd. Applicant before: XI'AN University OF TECHNOLOGY |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |