CN109266103A - Reversible temperature becomes water-based ink and its preparation method and application - Google Patents
Reversible temperature becomes water-based ink and its preparation method and application Download PDFInfo
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- CN109266103A CN109266103A CN201811185230.4A CN201811185230A CN109266103A CN 109266103 A CN109266103 A CN 109266103A CN 201811185230 A CN201811185230 A CN 201811185230A CN 109266103 A CN109266103 A CN 109266103A
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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
- C09D11/50—Sympathetic, colour changing or similar inks
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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
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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
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention belongs to technical field of ink, and in particular to a kind of Reversible temperature becomes water-based ink and its preparation method and application.Reversible temperature provided by the invention becomes water-based ink, including following components: waterborne binder 25-35 parts by weight, nano vanadium dioxide 10-25 parts by weight, nontoxic co-solvent 5-15 parts by weight and water 15-25 parts by weight.Water-based ink of the invention replaces organic solvent using water and a small amount of nontoxic alcohols as solvent, it is pollution-free, safety nuisance free and price is lower, discoloring temperature is low, thermal response is sensitive, printability is good, can be widely used for the nontoxic anti-counterfeit package of the extensive stocks such as food, drug, chemical product, tobacco and wine packet and toy for children.
Description
Technical field
The invention belongs to technical field of ink, and in particular to a kind of Reversible temperature becomes water-based ink and its preparation method and application.
Background technique
Product is printed while meeting popular demand, is gradually showed quality, personalization, customizing is newly become
Gesture, green printing, digital printing are developed rapidly.With the rise of digital printing, digital anti-counterfeiting technology also obtains prominent fly suddenly
Into development.Advanced anti-counterfeiting technology plays good standardization role in fierce market competition environment to commodity, and many
In anti-counterfeiting technology, temperature sensitive ink is a critically important technology branch, be related to include optics, chemistry, materialogy, nanotechnology,
Many scientific and technical classes such as computer science, printing technology, are the parts of domestic and international field of anti-counterfeit technology most study at present.
There are many kinds of temperature sensitive inks, and discolouration depends primarily on its warm variable pigments part used.From thermodynamically dividing, temperature becomes
Pigment is roughly divided into two kinds, Reversible temperature variable pigments, can not inversion variable pigments.Can not inversion variable pigments mainly by the second major element
Inorganic salts and the composition such as crystal violet, oxybenzene compound, discoloring temperature is high, contains heavy metal, does not meet environmental requirement, generally not
The printing packaging field of food, drug or common consumer product can be used as.Reversible temperature variable pigments be divided into it is inorganic, organic, three kinds of liquid crystal,
Wherein liquid crystal type pigment on printing packaging cost it is too high；Organic pigment then contains aromatic ring mostly, is harmful to human health；
Inorganic pigment is mainly made of the polycrystalline oxide of metal, metal halide, metal, because its valence is low, environmentally friendly, discoloring temperature
Many advantages, such as adjustable and be widely used.With government and people to green, environmental protection give more sustained attention and green printing, number
The trending development of word printing, it is low to develop a kind of discoloration critical-temperature, anti-fake, temperature indicating effect is good, the Reversible temperature change of green high-efficient
Water-based ink is of great significance.
Summary of the invention
In view of the above-mentioned problems, that the present invention provides a kind of discoloring temperatures is low, thermal response is sensitive, weatherability is strong, printing is good
Become water-based ink and its preparation method and application with the Reversible temperature of green high-efficient.
Specifically, the present invention provides the following technical scheme that
A kind of Reversible temperature change water-based ink, including following components: waterborne binder 25-35 parts by weight, nano vanadium dioxide
10-25 parts by weight, nontoxic co-solvent 5-15 parts by weight and water 15-25 parts by weight.
Preferably, in above-mentioned water-based ink, the waterborne binder is 25-30 parts by weight, the nano vanadium dioxide
For 15-20 parts by weight, the nontoxic co-solvent is 8-15 parts by weight and the water is 15-20 parts by weight.
Preferably, in above-mentioned water-based ink, the waterborne binder be selected from aqueous polyurethane, water polyacrylic acid and
One or more of aqueous acrylic modified polyurethane.
Preferably, in above-mentioned water-based ink, the nontoxic co-solvent in ethyl alcohol, isopropanol and butanol one
Kind is two or more.
It preferably, further include filler 10-25 parts by weight in above-mentioned water-based ink, the filler is selected from nanometer titanium dioxide
Silicon powder and/or titanium oxide powder.
It preferably, further include drier and aqueous antioxidant in above-mentioned water-based ink, the drier is 0.5-2
Parts by weight, the aqueous antioxidant are 1-3 parts by weight.
The preparation method of above-mentioned water-based ink, includes the following steps:
(1) by waterborne binder, nano vanadium dioxide, nontoxic co-solvent, water and filler to be added on demand, urge it is dry
Agent and/or aqueous antioxidant are uniformly mixed, and obtain standby color paste；
(2) PH of the standby color paste obtained by PH regulator regulating step (1) is 8~9.5, and it is aqueous to obtain thermochromism
Ink.
Preferably, in above-mentioned preparation method, in step (1), the preparation method of the nano vanadium dioxide includes following
Step:
Vanadic anhydride and oxalic acid dihydrate are added to the water, aqueous solution is formed by heating stirring, it is anti-by hydro-thermal
Should after generate precipitating, precipitation and separation washs, dry, obtains nano vanadium dioxide after high annealing under inert atmosphere.
Preferably, in above-mentioned preparation method, the molar ratio of the vanadic anhydride and oxalic acid dihydrate is 1:1
~3.
Preferably, in above-mentioned preparation method, the hydrothermal temperature is 180-250 DEG C；The hydro-thermal reaction time is 24-
48h。
Preferably, in above-mentioned preparation method, the high temperature anneal temperature is 800-850 DEG C, annealing time 2-4h.
Preferably, in above-mentioned preparation method, in step (2), the PH regulator is selected from ethanol amine, ammonium hydroxide and triethylamine
One or more of.
Preferably, the Reversible temperature that above-mentioned preparation method obtains becomes water-based ink.
Preferably, application of the above-mentioned water-based ink in field of anti-counterfeit technology.
The invention has the benefit that
Reversible temperature of the invention becomes water-based ink and replaces organic solvent using water and nontoxic alcohols as solvent, pollution-free,
Safety nuisance free and price is lower, discoloring temperature is low, and thermal response is sensitive, and printability is good, can be widely used for food, drug, daily use chemicals
The nontoxic anti-counterfeit package of the extensive stocks such as product, tobacco and wine packet and toy for children.
Detailed description of the invention
Fig. 1 is the grain size distribution of water-based ink prepared by embodiment 1.
Fig. 2 is the viscosity measurements figure of the water-based ink of embodiment and comparative example preparation, and mark and be described as follows in figure: 1- is implemented
The water-based ink of water-based ink, the preparation of 3- embodiment 3 prepared by the water-based ink of the preparation of example 1,2- embodiment 2, the system of 4- embodiment 4
The water-based ink of standby water-based ink, the preparation of 5- embodiment 5.
Fig. 3 is the discoloring temperature and color reversion time diagram of the water-based ink of embodiment and comparative example preparation, description of symbols in figure
It is as follows: the water-based ink of water-based ink, the preparation of 3- embodiment 3 prepared by the water-based ink of the preparation of 1- embodiment 1,2- embodiment 2,
The water-based ink of water-based ink, the preparation of 6- comparative example 1 prepared by the water-based ink of the preparation of 4- embodiment 4,5- embodiment 5,7- pairs
Water-based ink prepared by ratio 2.
Specific embodiment
With government and people to green, environmental protection give more sustained attention and the trending of green printing, digital printing develops,
It is low to develop a kind of discoloration critical-temperature, anti-fake, temperature indicating effect is good, the Reversible temperature of green high-efficient becomes water-based ink, has important meaning
Justice.In consideration of it, the present invention provides a kind of Reversible temperatures to become water-based ink comprising following components: waterborne binder 25-35 weight
Part, nano vanadium dioxide 10-25 parts by weight, nontoxic co-solvent 5-15 parts by weight and water 15-25 parts by weight.
In the preferred embodiment of the present invention, it includes following components that the Reversible temperature, which becomes water-based ink: aqueous company
Splicing 25-35 parts by weight, nano vanadium dioxide 10-25 parts by weight, nontoxic co-solvent 5-15 parts by weight, water 15-25 weight
Part, filler 10-25 parts by weight, drier 0.5-2 parts by weight, aqueous antioxidant 1-3 parts by weight.
Wherein, the waterborne binder is selected from aqueous polyurethane, water polyacrylic acid and aqueous acrylic modified poly-
One or more of urethane, the filler are selected from nano silica powder and/or titanium oxide powder, the non-toxic alcohol
Class cosolvent is selected from one or more of ethyl alcohol, isopropanol and butanol.
The present invention also provides the preparation methods that a kind of above-mentioned Reversible temperature becomes water-based ink, in a kind of preferred embodiment
In, the specific steps are as follows:
(1) by waterborne binder, nano vanadium dioxide, nontoxic co-solvent, water and filler to be added on demand, urge it is dry
Agent and/or aqueous antioxidant are uniformly mixed, and obtain standby color paste；
(2) PH of the standby color paste obtained by PH regulator regulating step (1) is 8~9.5, and it is aqueous to obtain thermochromism
Ink.Wherein, the PH regulator is selected from one or more of ethanol amine, ammonium hydroxide and triethylamine.
In the preferred embodiment of the present invention, the nano vanadium dioxide is prepared by following step:
Vanadic anhydride and oxalic acid dihydrate are added to the water with the molar ratio of 1:1~3, pass through heating stirring shape
It at aqueous solution, is cooled to room temperature after 180-250 DEG C of hydro-thermal reaction 24-48h, precipitating is then demultiplex out, with distilled water and second
Alcohol washing, it is dry, nano vanadium dioxide is obtained after 800-850 DEG C of annealing 2-4h under argon gas.
The nano vanadium dioxide of above-mentioned hydro-thermal method synthesis is in black-and-blue through the invention, and particle diameter distribution is uniform, and phase transformation is critical
Temperature is 68.8 DEG C, and very close with surroundings temperature, discoloring temperature boundary is fixed, section is narrow, color difference is big, is rung to thermostimulation
Answer sensitivity.
The present invention also provides above-mentioned Reversible temperatures to become application of the water-based ink in field of anti-counterfeit technology.
In the preferred embodiment of the present invention, the Reversible temperature becomes water-based ink and is prepared by following step:
Step 1: the polyalcohol of molecular weight 1000~2000 synthesis of aqueous polyurethane dispersion: being placed in 100~120 DEG C
At a temperature of dry 1~2 hour, then dry polyalcohol and isoflurane chalcone diisocyanate are mixed anti-at 80~100 DEG C
It answers 2~3 hours, is then added after catalyst accelerates reaction 0.5~1 hour and system temperature is reduced to 60~70 DEG C, be added and expand
Chain agent carries out chain extending reaction 15~30 minutes, is warming up to initial reaction temperature, is cooled to 40~50 after the reaction was continued 2~3 hours
DEG C, 1,4-butanediol is added and acetone regulation system viscosity is 10~16mPa.s and obtains water after being persistently stirred to react 1-2 hours
Property base polyurethane prepolymer for use as, system temperature is down to room temperature, deionized water and a certain amount of triethylamine is added, adjust pH value 8.0~
Between 9.0, aging 12~18 hours, rotary evaporation remove unreacted organic solvent at room temperature, obtain aqueous polyurethane dispersion
For body as target ink binder, aqueous polyurethane range of number-average molecular weight of the invention is 2000-3000.
Step 2: the preparation of body pigment nano vanadium dioxide powder: by vanadic anhydride and oxalic acid dihydrate addition go from
In sub- water, it is uniformly mixed the two by heating stirring, then mixed solution is placed in hydrothermal reaction kettle, protected at high temperature
A period of time is held, allows mixture sufficiently to react, takes out after the reaction was completed, cooled to room temperature isolates sediment, then again
It is washed with distilled water and ethyl alcohol, is finally dried to obtain nano vanadium dioxide powder, the nano vanadium dioxide powder that will be obtained
High annealing under an inert atmosphere obtains target ink body pigment.
Step 3: pressing mass fraction, by 25~35 parts of step 1 gained binder, 10~25 parts of step 2 gained body pigment, fill out
Expect that 10~25 parts, 5~15 parts of alcohol analog assistant, 15~25 parts of water, 0.5~2 part of drier, 1~3 part of antioxidant pass through high speed
Dispersing agent is dispersed with stirring, and is ground into standby color paste, is adjusted between pH to 8~9.5, is set the cool place place of being protected from light and is saved, according to being actually subjected to
Asking can be used directly or use after diluting.
It is furthermore preferred that polyalcohol described in step 1 is one of polyether polyol or polyester polyol or a variety of mixtures.
It is furthermore preferred that used catalyst is environment-friendly type organic bismuth catalyst DY-20 in step 1.
It is furthermore preferred that chain extender used is dihydromethyl propionic acid in step 1.
It is furthermore preferred that vanadic anhydride described in step 2 and the molar ratio of oxalic acid dihydrate are 1:1~3.
It is furthermore preferred that hydrothermal temperature is 180~250 DEG C in step 2, the reaction time is 24~48 hours.
It is furthermore preferred that step 2 high temperature annealing temperature is 800~850 DEG C, annealing time is 2~4 hours, inertia protection
Atmosphere is argon gas.
It is furthermore preferred that alcohol analog assistant is the one or more of ethyl alcohol, isopropanol, butanol in step 3, defoaming agent, tree are played
The multiple action of rouge diluent, preservative.
It is furthermore preferred that filler is one kind of nano silica powder or titanium oxide powder in step 3.
It is furthermore preferred that antioxidant selects aqueous antioxidant in step 3.
It is furthermore preferred that pH stabilizer is one kind of ethanol amine, ammonium hydroxide or triethylamine in step 3.
Further illustrate that Reversible temperature of the invention becomes water-based ink and its preparation method and application below by specific embodiment.
In the following embodiments, the information of each reagent used and equipment is as shown in Table 1 and Table 2.
Agents useful for same information table in 1 embodiment of table
Device therefor information table in 2 embodiment of table
Embodiment one
1. the preparation of aqueous polyurethane binder: by molecular weight be 2000 polypropylene glycol under the conditions of 110 DEG C vacuum do
Dry 1.5h reacts 1.5h in 90 DEG C of mixings with isoflurane chalcone diisocyanate, and environment-friendly type organic bismuth catalyst is then added
DY-20 continues to accelerate that system temperature is reduced to 60 DEG C after reaction 1h, and chain extender dihydromethyl propionic acid is added and carries out chain extending reaction
20min is warming up to 90 DEG C of initial reaction temperature, and 50 DEG C are cooled to after the reaction was continued 2h, and 1,4-butanediol is added and acetone is adjusted
System viscosity is 13mPa.s and obtains Waterborne Polyurethane Prepolymer after being persistently stirred to react 1h, and system temperature is down to room temperature, is added
Enter deionized water and a certain amount of ethanol amine, adjust pH value between 8.5, at room temperature aging 12 hours, rotary evaporation removes not anti-
The organic solvent answered obtains aqueous polyurethane binder (number-average molecular weight 3000).
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:2 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 200 DEG C of hydro-thermal reaction 30h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 800 DEG C of annealing 4h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 30 parts by weight of aqueous polyurethane binder, nanometer two
15 parts by weight of vanadium oxide, 10 parts by weight of nontoxic co-solvent are uniformly mixed with 20 parts by weight of water, obtain standby color paste 30g, are led to
Crossing triethylamine and adjusting the PH of standby color paste is 8.5, obtains thermochromism water-based ink.
Fig. 1 is the grain size distribution of water-based ink manufactured in the present embodiment, and as seen from the figure, the partial size of water-based ink mainly divides
Cloth is dispersed evenly and stably in 90nm or so.
Embodiment two
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:1 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 180 DEG C of hydro-thermal reaction 48h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 800 DEG C of annealing 2h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 25 parts by weight of aqueous polyurethane binder, nanometer two
25 parts by weight of vanadium oxide, 5 parts by weight of nontoxic co-solvent, 25 parts by weight of water, 25 parts by weight of nano silica powder, urge it is dry
0.5 parts by weight of agent and 3 parts by weight of antioxidant are uniformly mixed, and obtain standby color paste 30g, adjust standby color paste by ethanol amine
PH is 8, obtains thermochromism water-based ink.
Embodiment three
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:3 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after for 24 hours by 250 DEG C of hydro-thermal reactions, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 850 DEG C of annealing 4h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 35 parts by weight of aqueous polyurethane binder, nanometer two
10 parts by weight of vanadium oxide, 15 parts by weight of nontoxic co-solvent, 15 parts by weight of water, 10 parts by weight of titanium oxide powder, 2 weight of drier
It measures part and 1 parts by weight of antioxidant is uniformly mixed, obtain standby color paste 30g, be 9.5 by the PH that ammonium hydroxide adjusts standby color paste,
Obtain thermochromism water-based ink.
Example IV
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:2 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 220 DEG C of hydro-thermal reaction 35h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 820 DEG C of annealing 3h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 25 parts by weight of aqueous polyurethane binder, nanometer two
20 parts by weight of vanadium oxide, 8 parts by weight of nontoxic co-solvent, 20 parts by weight of water, 15 parts by weight of nano silica powder, urge it is dry
1 parts by weight of agent and 2 parts by weight of antioxidant are uniformly mixed, and obtain standby color paste 30g, and the PH of standby color paste is adjusted by triethylamine
It is 8.5, obtains thermochromism water-based ink.
Embodiment five
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:2 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 200 DEG C of hydro-thermal reaction 40h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 810 DEG C of annealing 3h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 30 parts by weight of aqueous polyurethane binder, nanometer two
15 parts by weight of vanadium oxide, 15 parts by weight of nontoxic co-solvent, 15 parts by weight of water, 20 parts by weight of titanium oxide powder, drier 1.5
Parts by weight and 1.5 parts by weight of antioxidant are uniformly mixed, and obtain standby color paste 30g, and the PH of standby color paste is adjusted by ethanol amine
It is 9, obtains thermochromism water-based ink.
Comparative example one
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:2 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 220 DEG C of hydro-thermal reaction 35h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 820 DEG C of annealing 3h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 60 parts by weight of aqueous polyurethane binder, nanometer two
20 parts by weight of vanadium oxide, 8 parts by weight of nontoxic co-solvent, 20 parts by weight of water, 15 parts by weight of nano silica powder, urge it is dry
1 parts by weight of agent and 2 parts by weight of antioxidant are uniformly mixed, and obtain standby color paste 30g, and the PH of standby color paste is adjusted by triethylamine
It is 8.5, obtains thermochromism water-based ink.
Comparative example two
1. the preparation of aqueous polyurethane binder: identical as the step 1 of embodiment one.
2. the preparation of nano vanadium dioxide: with molar ratio being that 1:2 is added by vanadic anhydride and oxalic acid dihydrate
In water, aqueous solution is formed by heating stirring, is cooled to room temperature after 200 DEG C of hydro-thermal reaction 40h, precipitating is then demultiplex out,
It is dry with distilled water and ethanol washing, under argon gas after 810 DEG C of annealing 3h, obtain nano vanadium dioxide.
3. the preparation of Reversible temperature change water-based ink: by weight by 30 parts by weight of aqueous polyurethane binder, nanometer two
15 parts by weight of vanadium oxide, 100 parts by weight of nontoxic co-solvent, 200 parts by weight of water, 20 parts by weight of titanium oxide powder, drier
1.5 parts by weight and 1.5 parts by weight of antioxidant are uniformly mixed, and obtain standby color paste 30g, adjust standby color paste by ethanol amine
PH is 9, obtains thermochromism water-based ink.
Contrast on effect
1. viscosity measurements
Using laser viscosity apparatus detection embodiment 1-5 preparation water-based ink viscosity, testing result as shown in Fig. 2, by
For figure it is found that the viscosity of water-based ink of various embodiments of the present invention preparation is 350~500mPaS, printing is good.
2. discoloring temperature and the measurement of color reversion time
When measuring the discoloring temperature and color reversion of the water-based ink of embodiment 1-5 and comparative example 1-2 preparation using following methods
Between, as a result as shown in Figure 3.
Discoloring temperature measurement: ink sample 2mg is taken, is fitted into capillary closed at one end, the other end is shut with vaseline.
Capillary is fixed to above thermometer with rubber band, sample is as close as possible to mercury one end.It is put into the 150mL equipped with 100mL water
Beaker in, be slowly heated beaker.When temperature is raised, metachromatism is observed, ink becomes light brown from navy blue, and color becomes
Changing the time used is Coloring Time.
The measurement of color reversion time: the capillary after discoloration is taken out from hot water, and room temperature naked-eye observation reduces sample with temperature
Color change to original color time.
From the figure 3, it may be seen that the water-based ink discoloring temperature of various embodiments of the present invention preparation is about 45~55 DEG C, the color reversion time is about
For 5~25min, showing that water-based ink discoloring temperature of the invention is low, thermal response is sensitive, meanwhile, discoloring temperature and color reversion time
The better than water-based ink of comparative example.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (14)
1. a kind of Reversible temperature becomes water-based ink, which is characterized in that including following components: waterborne binder 25-35 parts by weight, nanometer
Vanadium dioxide 10-25 parts by weight, nontoxic co-solvent 5-15 parts by weight and water 15-25 parts by weight.
2. water-based ink according to claim 1, wherein the waterborne binder is 25-30 parts by weight, the nanometer two
Vanadium oxide is 15-20 parts by weight, and the nontoxic co-solvent is 8-15 parts by weight and the water is 15-20 parts by weight.
3. water-based ink according to claim 1 or 2, wherein the waterborne binder is selected from aqueous polyurethane, aqueous poly-
One or more of acrylate and aqueous acrylic modified polyurethane.
4. water-based ink according to claim 1-3, wherein the nontoxic co-solvent is selected from ethyl alcohol, different
One or more of propyl alcohol and butanol.
5. water-based ink according to claim 1-4, wherein further include filler 10-25 parts by weight, the filler
Selected from nano silica powder and/or titanium oxide powder.
6. water-based ink according to claim 1-5, wherein further include drier and aqueous antioxidant, institute
Stating drier is 0.5-2 parts by weight, and the aqueous antioxidant is 1-3 parts by weight.
7. the preparation method of water-based ink described in claim 1-6, which is characterized in that include the following steps:
(1) by waterborne binder, nano vanadium dioxide, nontoxic co-solvent, water and on-demand filler to be added, drier
And/or aqueous antioxidant is uniformly mixed, and obtains standby color paste；
(2) PH of the standby color paste obtained by PH regulator regulating step (1) is 8~9.5, obtains the aqueous oil of thermochromism
Ink.
8. preparation method according to claim 7, wherein in step (1), the preparation method packet of the nano vanadium dioxide
Include following step:
Vanadic anhydride and oxalic acid dihydrate are added to the water, aqueous solution is formed by heating stirring, after hydro-thermal reaction
Precipitating is generated, precipitation and separation washs, and it is dry, nano vanadium dioxide is obtained after high annealing under inert atmosphere.
9. preparation method according to claim 8, wherein the vanadic anhydride and oxalic acid dihydrate feed intake mole
Than for 1:1~3.
10. preparation method according to claim 9, wherein the hydrothermal temperature is 180-250 DEG C；Hydro-thermal reaction
Time is 24-48h.
11. preparation method according to claim 9 or 10, wherein the high temperature anneal temperature is 800-850 DEG C, annealing
Time is 2-4h.
12. according to the described in any item preparation methods of claim 7-11, wherein in step (2), the PH regulator is selected from second
One or more of hydramine, ammonium hydroxide and triethylamine.
13. the Reversible temperature that the described in any item preparation methods of claim 7-12 obtain becomes water-based ink.
14. Reversible temperature described in any one of claim 1-6 or claim 13 becomes water-based ink in field of anti-counterfeit technology
Using.
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| 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 |
| CN114023486A (en) * | 2021-10-20 | 2022-02-08 | 西安理工大学 | Environment-friendly micro-nano composite waterborne conductive silver paste and preparation method thereof |
| 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 |
| CN114023486B (en) * | 2021-10-20 | 2024-05-24 | 西安理工大学 | Environment-friendly micro-nano composite water-based conductive silver paste and preparation method thereof |
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