CN109395676A - Cobalt ammonium salt low-temp reversible temperature becomes microscapsule powder and water-based ink and preparation method and application - Google Patents
Cobalt ammonium salt low-temp reversible temperature becomes microscapsule powder and water-based ink and preparation method and application Download PDFInfo
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- CN109395676A CN109395676A CN201811185416.XA CN201811185416A CN109395676A CN 109395676 A CN109395676 A CN 109395676A CN 201811185416 A CN201811185416 A CN 201811185416A CN 109395676 A CN109395676 A CN 109395676A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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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
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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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- 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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Abstract
Become microscapsule powder the present invention relates to Reversible temperature and cobalt ammonium salt low-temp reversible temperature becomes the preparation method and application of water-based ink and they.The Reversible temperature becomes camouflage paint and carrier of the microscapsule powder containing cobalt chloride hexahydrate and hexa；The ink is prepared by the raw material containing microscapsule powder, emulsifier, filler, resin binder, diluent resin, drier and defoaming agent.The preparation method of ink of the present invention includes that cobalt chloride hexahydrate and hexa are mixed after camouflage paint, filler and solvent is added and emulsifier is made Reversible temperature and becomes microscapsule powder, filler, resin binder and diluent resin, drier and defoaming agent is then added, ink is made.Temperature induced color changing microcapsules are made in temperature induced color changing pigment by the present invention, have not only been enhanced environmental suitability but also have been improved the compatibility of temperature induced color changing pigment and other materials, have shortened color-recovering time；Safe green environmental protection, good film-forming property.Improve viscosity, rate of drying and the printing quality of water-based ink.
Description
Technical field
The invention belongs to technology of fine chemicals, and in particular to the preparation of cobalt ammonium salt low-temp reversible temperature change water-based ink
Method.
Background technique
Temperature induced color changing ink is also known as temperature sensitive ink, ink for temperature indication, can rapidly change color with the variation of environment temperature,
Make by colouring substance have dynamic change color effect, quality-monitoring, it is anti-fake, in terms of have the work that can not be substituted
With.Temperature induced color changing ink is widely applied in function packaging field, and Related product is also seen everywhere in life, temperature indicating water
Cup, temperature induced color changing paper and various cigarette packets, cigarette-brand etc..The performance requirement of temperature sensitive ink is mainly reflected in following five aspects: right
Thermostimulation response is sensitive, and discoloring temperature boundary is fixed, section is narrow, color difference is big, and discoloring temperature is suitable, good weatherability, and printability is good.
First three items performance characteristics depend primarily on temperature and become material, i.e. camouflage paint.Afterwards two then depend on ink in filler, binder
And the dispersion of the compositions such as other auxiliary agents.Traditional alternating temperature ink is since its discoloring temperature is all relatively high, so that it was applied
Range critical constraints.In addition, adding government and various circles of society as printing packaging industry gradually moves towards functionalization, intelligence
Environmental protection, ecology are given more sustained attention, we also will constantly explore new process, develop novel environment-friendly functionality printing packaging material
Material.
From thermodynamically dividing, camouflage paint is roughly divided into two kinds, and Reversible temperature becomes material and can not inversion change material.Reversible temperature
Become material be divided into it is organic and inorganic, three kinds of liquid crystal, wherein liquid crystal type material is the heated diffraction and reflection for changing spatial arrangement to light
Polarization impacts, to play color changeable effect, technology, human cost are high, should not use in printing packaging field.And organic change
Color material contains aromatic ring mostly, very unfavorable to human health.Inorganic off-color material mainly includes the iodide of Ag, Hg, Co, network
It closes object or double salt and cobalt salt, nickel salt and methenamine is formed by compound etc..Since its price is low, environmentally friendly, discoloring temperature
Many advantages, such as adjustable and be widely used.Wherein cobalt amine salt is that a kind of low-temp reversible using crystallization water gain and loss Discoloration mechanism shows
Adiabator has very strong water solubility, and dissolves in common organic solvent.
Summary of the invention
However, inorganic off-color material cobalt amine salt has a significant drawback in the prior art, it is exactly and modulation ink process
In the high molecular materials such as the dispersion used and auxiliary agent compatibility it is poor.Therefore, by Reversible Thermochromic Materials at
Membrane substance is coated, and nanoscale core-shell microcapsule is made.It on the one hand, can be to avoid organic solvent, highly acid or impurity
It is irreversibly changed caused by pollution, enhances its environmental suitability；On the other hand it can improve thermochromic material and other materials
Compatibility expands its application field.
This project proposes to coat it using film forming matter using cobalt amine salt as reversible temperature induced color changing pigment, is made
The reversible temperature indicating microscapsule powder of nanoscale core-shell structure.Then relatively green, environmental protection dispersion system is selected to modulate oil
Ink develops a series of reversible temperature sensitive inks of Environment-friendlylow-temperature low-temperature suitable for food, drug, cigarette packet etc..Relative to traditional ink,
The dispersion of water-based ink replaces organic solvent using water and a small amount of nontoxic alcohols, esters as solvent, pollution-free, safety
Nuisanceless and price is lower.It is expected that the system it is safe and reliable it is non-harmful simultaneously, and can have certain mechanical strength, film forming
Good, in conjunction with other auxiliary agents, viscosity, rate of drying and the printing quality of ink can accomplish controllable.
Technical problem to be solved by the invention is to provide cobalt ammonium salt low-temp reversible temperature become water-based ink preparation method, with
Make prepared water-based ink that there is good mobility, printability and quick-drying, it is pollution-free and cheap, it is broadly applicable
In the print field of the packaging materials such as food, drug, cosmetics, cigarette packet.
Specifically, in order to solve the above technical problems, The present invention provides following technical solutions:
A kind of Reversible temperature becomes microscapsule powder, which is characterized in that it contains cobalt chloride hexahydrate and hexa
Camouflage paint and carrier.
Preferably, wherein the carrier is 8-25%, preferably 12-18% relative to the mass ratio of camouflage paint.
For preferably, for the microscapsule powder, wherein the carrier is selected from hydroxypropyl cellulose, methylol
One or more of cellulose, methylcellulose, ethyl cellulose, polyethylene substance；It is preferred that the carrier is ethyl cellulose
With the mixture of polyethylene, the mass ratio of more preferable ethyl cellulose and polyethylene is 1-1.2:1.
For preferably, for the microscapsule powder, wherein the quality of cobalt chloride hexahydrate and hexa
Ratio is 0.5-2:1, preferably 1:1.
The present invention also provides a kind of cobalt ammonium salt Reversible temperatures to become water-based ink, becomes containing the described in any item Reversible temperatures in front
Microscapsule powder, emulsifier, filler, resin binder, diluent resin, drier and defoaming agent.
For preferably, for the ink, by containing Reversible temperature described in front one become microscapsule powder,
Emulsifier, filler, resin binder, diluent resin, drier and defoaming agent raw material be prepared.
For preferably, for the ink, which is obtained by the preparation method containing following step:
Step 1, the preparation of camouflage paint:
Cobalt chloride hexahydrate and hexa are mixed, water is then added and forms paste, freeze-day with constant temperature is carried out and obtains
Camouflage paint；
Step 2, the Reversible temperature becomes the synthesis of microscapsule powder any one of before:
After carrier and solvent are mixed, it is condensed back, it is straight for stirring at low speed for 300-400r/min with mixing speed
It is all dissolved to carrier；The camouflage paint aqueous solution dissolved in step 1 is added and emulsifier is stirred speed as 700-
The high-speed stirred of 800r/min forms stable oil-water type emulsified particle；Then cooling stirring is carried out, product is removed into solvent, into
Reversible temperature, which is obtained, after row is dry becomes microscapsule powder；Wherein, the drying is preferably dried in vacuo；
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become microscapsule powder to mix with filler, and is added resin binder and tree
Ink is made after rouge diluent and drier and defoaming agent.
For preferably, for the preparation method of the cobalt ammonium salt irreversible temperature water-based ink, which is characterized in that the oil
Ink is obtained by the preparation method containing following step:
Step 1, the preparation of camouflage paint:
Cobalt chloride hexahydrate, hexa mixing are weighed, water is then added and stirs into paste, carries out freeze-day with constant temperature and obtains
To camouflage paint；
Step 2, Reversible temperature becomes the synthesis of microscapsule powder:
After carrier and solvent are mixed, it is condensed back, it is straight for stirring at low speed for 300-400r/min with mixing speed
It is all dissolved to carrier；The camouflage paint aqueous solution dissolved in step 1 is added and emulsifier is stirred speed as 700-
The high-speed stirred of 800r/min forms stable oil-water type emulsified particle；Then cooling stirring is carried out, product is removed into solvent, into
Reversible temperature, which is obtained, after row is dry becomes microscapsule powder；Wherein, the drying is preferably dried in vacuo；
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become microscapsule powder to mix with filler, and is added resin binder and tree
Ink is made after rouge diluent and drier and defoaming agent.
For preferably, for the preparation method, wherein cobalt chloride hexahydrate and hexa in step 1
Mass ratio be 0.5-2:1, the matter of the mixture and water of cobalt chloride hexahydrate and hexa in further preferred step 1
Amount is than being 1:1-1.2.
For preferably, for the preparation method, wherein freeze-day with constant temperature condition is 35-40 DEG C in step 1, preferably
Freeze-day with constant temperature 3-5h.
For preferably, become the preparation method of water-based ink for the cobalt ammonium salt Reversible temperature, which is characterized in that step
In 2, the carrier in hydroxypropyl cellulose, hydroxymethyl cellulose, methylcellulose, ethyl cellulose, polyethylene one
Kind or more substance；It is preferred that the carrier is the mixture of ethyl cellulose and polyethylene, more preferable ethyl cellulose and polyethylene
Mass ratio be 1-1.2:1；Wherein, the solvent mixed with the carrier is preferably selected from hexamethylene or tetrahydrofuran, molten
Agent dosage is preferably 35-40mL.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is that emulsifier described in step 2 is sorbitan fatty ester, is preferably selected from Span80；The more preferable emulsification
Agent is 0.3-0.8%, preferably 0.3-0.6% relative to the mass ratio of the camouflage paint aqueous solution.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is that rate of temperature fall is 5-10 DEG C of h-1 in step 2；Vacuum drying temperature is 25-40 DEG C in further preferred step 2；Into
The preferred vacuum drying time of one step is 100-120h.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is that filler described in step 3 is 1:1-3 relative to the mass ratio of the microscapsule powder., preferably 1:1-1:1.5；More
Preferred filler is one kind of 10-30nm talcum powder or aluminum oxide.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is, resin binder described in step 3 is water-base resin binder, selected from waterborne polyurethane resin, acrylic resin,
One of polyvinyl alcohol and epoxy resin are a variety of.
For preferably, become the preparation method of water-based ink for mentioned-above cobalt ammonium salt Reversible temperature, which is characterized in that
In step 3, the aqueous polyurethane is 1:2-5 relative to the mass ratio of the microscapsule powder；The diluent resin phase
Mass ratio for the microscapsule powder is 1:2-6.
For preferably, become the preparation method of water-based ink for mentioned-above cobalt ammonium salt Reversible temperature, which is characterized in that
In step 3, the resin binder is the aqueous polyurethane that molecular weight is 2000-3000, and diluent resin is acetone, diformazan
One of benzene, cyclohexanone, ethyl acetate, toluene, ethers or alcohols material；Wherein the alcohols material is selected from ethyl alcohol, positive third
Alcohol, isopropanol, n-butanol, one kind of isobutanol or combinations thereof, are more preferably selected from ethyl alcohol or normal propyl alcohol.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is that drier is 1:30-40 relative to the mass ratio of microscapsule powder in step 3；Drier is preferably cobalt iso-octoate
With the mixture of manganese iso-octoate, the more preferably mass ratio of the two is 1:0.1-10.
For preferably, cobalt ammonium salt Reversible temperatures described in any item for front become the preparation method of water-based ink, special
Sign is that the defoaming agent is 1:30-40 relative to the mass ratio of the microscapsule powder；It is preferred that the defoaming agent is selected from second
The mono- n-pentyl ether of glycol, the mono- n-hexyl ether of ethylene glycol and propylene glycol list n-butyl ether or silicone substance or water-white non-hydrogenated petroleum
Resin is more preferably selected from water-white hydrogenated petroleum resin P-140.
For preferably, the described in any item cobalt ammonium salts of microscapsule powders described in any item for front or front can
Inversion becomes application of the water-based ink in food, drug, cigarette packaging material.
The beneficial effects of the present invention are:
(1) using to thermostimulation response is sensitive, discoloring temperature boundary is fixed, section is narrow, color difference is big, cheap and nontoxic
The cobalt amine salt of environmental protection deploys the reversible temperature induced color changing water-based ink of Environment-friendlylow-temperature low-temperature as pigment.
(2) pigment is wrapped up using microcapsules technology, it on the one hand can be dirty to avoid organic solvent, highly acid or impurity
It is irreversibly changed caused by dye, enhances its environmental suitability；On the other hand it can improve the phase of temperature induced color changing pigment with other materials
Capacitive, and color-recovering time can be shortened, its application field of further expansion.
(3) use the aqueous polyurethane of uniform good dispersion, particle, high solid low viscosity and good fluidity as dispersing agent and company
Splicing substitutes traditional organic solvent, safe green environmental protection, good film-forming property.In conjunction with other auxiliary agents such as drier, defoaming agent
Deng viscosity, rate of drying and the printing quality of improvement temperature induced color changing water-based ink, so that discoloration water-based ink prepared by the present invention
Viscosity be in 20-40 pool range, just dry speed is that just dry speed is 10-15mm (30s)-1。
Detailed description of the invention
Fig. 1 is the FT-IR figure for the reversible temperature sensitive ink that the present invention is prepared；
Fig. 2 is the discoloring temperature of camouflage paint different quality ratio and color reversion time in reversible temperature sensitive ink prepared by the present invention
Figure；
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
For the present inventor in order to develop exploitation low temperature temperature sensitive ink, camouflage paint chooses nontoxic, pollution-free and low temperature
The ep-type material of discoloration, the dispersion system that dispersion selects environment relatively friendly.
In order to improve low temperature temperature sensitive ink, cobalt ammonium salt low-temp reversible temperature of the invention becomes the preparation method of water-based ink, packet
Include following steps: step 1, the preparation of camouflage paint；Step 2, Reversible temperature becomes the synthesis of microscapsule powder；Step 3, environment-friendly type temperature
The preparation of sensitive ink.The preparation method is using to thermostimulation response is sensitive, discoloring temperature section is narrow, color difference is big and asepsis environment-protecting
Cobalt amine salt as pigment, deploy the reversible temperature induced color changing water-based ink of Environment-friendlylow-temperature low-temperature.Using microencapsulation technology to pigment into
Row package, is made temperature induced color changing microcapsules for temperature induced color changing pigment, can not only enhance its environmental suitability but also can improve temperature induced color changing
The compatibility of pigment and other materials, and color-recovering time can be shortened.Using environment-friendly water-based polyurethane as dispersing agent and
Binder substitutes traditional organic solvent, safe green environmental protection, good film-forming property.In conjunction with other auxiliary agents, further improve aqueous oil
Viscosity, rate of drying and the printing quality of ink.
Specifically, the present invention provides a kind of Reversible temperature change microscapsule powder, which is characterized in that it contains six chloride hydrates
The camouflage paint and carrier of cobalt and hexa.
The present invention also provides a kind of cobalt ammonium salt Reversible temperatures to become water-based ink, becomes microcapsule powder containing Reversible temperature of the invention
End, emulsifier, filler, resin binder, diluent resin, drier and defoaming agent.
Wherein, any commercially available defoaming agent that defoaming agent can be conventional using this field, such as can be mono- just using ethylene glycol
Amyl ether, the mono- n-hexyl ether of ethylene glycol and propylene glycol list n-butyl ether or silicone defoaming agent or for example commercially available water-white hydrogenation
Petropols P-140.
Cobalt ammonium salt Reversible temperature of the invention becomes water-based ink and is obtained by the preparation method containing following step:
Step 1, the preparation of camouflage paint:
Cobalt chloride hexahydrate and hexa are mixed, water is then added and forms paste, freeze-day with constant temperature is carried out and obtains
Camouflage paint；
Step 2, Reversible temperature becomes the synthesis of microscapsule powder:
After carrier and solvent are mixed, it is condensed back, it is straight for stirring at low speed for 300-400r/min with mixing speed
It is all dissolved to carrier；The camouflage paint aqueous solution dissolved in step 1 is added and emulsifier is stirred speed as 700-
The high-speed stirred of 800r/min forms stable oil-water type emulsified particle；Then cooling stirring is carried out, product is removed into solvent, into
Reversible temperature, which is obtained, after row is dry becomes microscapsule powder；Wherein, the drying is preferably dried in vacuo；
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become microscapsule powder to mix with filler, and is added resin binder and tree
Ink is made after rouge diluent and drier and defoaming agent.
Specifically, the factors such as the viscosity of the formation of microcapsules drop and starting liq, the speed of stirring and temperature are to micro-
The size of capsule has an impact.The hydrophilic protection of stabilizer function is played used in method in step 2 of the invention in water
Property colloid includes surfactant and polyethylene etc..If not using protective colloid, the yield of microcapsules sharply declines.And
And when protective colloid dosage deficiency, it can also occur inversely to convert, come out Release of core material, be formed and only have polymer composition
Bead.Fine droplet forming step decides the size and distribution of microcapsules.Mixing speed is that dispersion is controlled in continuous phase
The major parameter of phase drop size, the average-size of microcapsule granule can be reduced by being gradually increased mixture mixing speed.This hair
Bright stirred at low speed by control makes prepared capsule size less than 10 microns with the speed of high-speed stirred link.
In a kind of specific embodiment of the invention, the present invention provides the system that cobalt ammonium salt low-temp reversible temperature becomes water-based ink
Preparation Method, which comprises the following steps:
Step 1, the preparation of camouflage paint:
Weigh cobalt chloride hexahydrate, hexa is added in beaker after mixing, grind and mix under normal temperature and pressure
It closes uniformly, 10g water uniform stirring is then added into paste, be placed in thermostatic drying chamber after drying and sealed up for safekeeping with bag；Wherein six water
The mass ratio for closing cobalt chloride and hexa is 0.5-2:1, the mixture of cobalt chloride hexahydrate and hexa with
The mass ratio of water is 1:1-1.2, and freeze-day with constant temperature condition is 35-40 DEG C of freeze-day with constant temperature 3-5h.
Step 2, Reversible temperature becomes the synthesis of microscapsule powder:
Ethyl cellulose, polyethylene and solvent hexamethylene are mixed and are placed in three-necked flask, is condensed back at 85-90 DEG C
Stream stirs at low speed (mixing speed 300-400r/min) until ethyl cellulose and polyethylene all dissolve.It is added in step 1
The camouflage paint aqueous solution dissolved and suitable emulsifier carry out high-speed stirred (mixing speed 700-800r/min) and are formed
Stable oil-water type emulsified particle.Stop stirring under certain rate of temperature fall, separatory funnel will be poured into after product stratification
In, it collects lower layer's product and is placed in a beaker, hexamethylene is added and is sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum
Drying box, be transferred to after 25 DEG C of vacuum drying 100-120h it is finely ground in agate mortar, can be obtained Reversible temperature become microcapsule powder
End；Wherein ethyl cellulose, polyethylene mass ratio are 1-1.2:1, and emulsifier Span80, rate of temperature fall is 5-10 DEG C of h-1。
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become into microscapsule powder and filler is thoroughly mixed uniformly, by binder and tree
Rouge diluent is sufficiently mixed, and is sanded after drier, defoaming agent is added, ink is finally made after filtering；Wherein fill out
Material is one kind of 10-30nm talcum powder or aluminum oxide, and binder is the aqueous polyurethane that molecular weight is 2000-3000, tree
Rouge diluent is ethyl alcohol, and drier is the mixture of cobalt iso-octoate and manganese iso-octoate, and defoaming agent is water-white hydrogenated petroleum resin P-
140。
In the present invention, used aqueous polyurethane is the conventional commercially available or homemade any aqueous poly- ammonia in this field
Ester.Preferably use number-average molecular weight for the aqueous polyurethane of 2000-3000 in the present invention.
To sum up, the present invention can prepare a kind of reversible temperature induced color changing water-based ink of Environment-friendlylow-temperature low-temperature, and discoloring temperature is suitable, resistance to
Time property is good, cheap, environmentally protective.
Below by specific embodiment, present invention be described in more detail.
In the present invention all embodiment 1-7 disclosed below, aqueous poly- ammonia that used number-average molecular weight is 3000
The specific preparation process of ester binder is as follows:
The preparation of aqueous polyurethane binder: the polypropylene glycol for being 2000 by molecular weight is (chemical purchased from Shanghai Chinese medicines group
Reagent) under the conditions of 110 DEG C it is dried in vacuo 1.5h, 1.5h is reacted in 90 DEG C of mixings with isoflurane chalcone diisocyanate, so
Environment-friendly type organic bismuth catalyst DY-20 (industrial goods are purchased from 100,000 chemical industry of Shandong) is added afterwards to continue after accelerating reaction 1h, by system
Temperature is reduced to 60 DEG C, and chain extender dihydromethyl propionic acid is added and carries out chain extending reaction 20min, is warming up to initial reaction temperature 90
DEG C, it is cooled to 50 DEG C after the reaction was continued 2h, 1,4-butanediol and acetone regulation system viscosity is added to 13mPas, and persistently stir
Waterborne Polyurethane Prepolymer is obtained after mixing reaction 1h, system temperature is down to room temperature, deionized water and ethanol amine is added, adjusts pH
Value cures 12 hours at room temperature between 8.5, and rotary evaporation removes unreacted organic solvent, obtains aqueous polyurethane connection
Expect (number-average molecular weight 3000).
Wherein, instrument model when measuring infrared spectrum are as follows: fourier transform infrared spectroscopy instrument, SHIMADIU FTIR-
8400S (CE), measuring method is as follows:
(1) potassium bromide is placed into 4h in 80 DEG C of baking ovens in advance, carried out except water process, be then rolled into it is powdered,
It reuses tablet press machine and carries out tabletting, the kbr tablet pressed is sealed in tableting processes, prevents the potassium bromide moisture absorption；
(2) waterborne polyurethane film about 0.2g is weighed to be dissolved in 5mL acetone；
(3) dissolved aqueous polyurethane/acetone liquid drop is placed in 40 DEG C of baking ovens on kbr tablet, makes acetone
Volatilization；
(4) computer and instrument are opened；
(5) experiment software is opened, relevant information and sample parameters are filled in, the potassium bromide that any sample is not added dropwise for measurement is thin
Piece is set as background；
(6) measurement is numbered in the potassium bromide thin slice that aqueous polyurethane is added dropwise.
Discoloring temperature measuring method is as follows in the following examples of the present invention: ink sample 2mg is packed into closed at one end
In capillary, 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 beaker of the 150mL equipped with 100mL water, is slowly heated beaker.When temperature is raised, notice that observation discoloration is existing
As becoming the light blue time used from lightpink is Coloring Time.The measurement of color reversion time: it is taken out from hot water after discoloration, room
Warm naked-eye observation reduces color sample variation with temperature and restores from light blue to the time of original lightpink.
In the present invention, the color refers to the color being observed visually, light pink as the common sense of those skilled in the art
Color wavelength is in 620-760nm, and light blue wavelength is in 440~475nm.
Viscosity measurement is as follows: ink generally in 90 degrees Celsius of lower 30s can surface drying, this namely embodiment of the present invention
The rate of drying of middle ink refers to just dry speed, and the environmental condition of detection is: ambient humidity: (20 ± 1) DEG C, relative humidity:
(65 ± 5) %.Specific continuous mode is to take a certain amount of tested black sample, is dripped at 100 μm of fineness scraper plate instrument, rapid with scraper plate
It scrapes and opens simultaneously manual time-keeping.Drawdown sheet edge is aligned at scraper plate zero graduation line when 30s, and smooth on groove,
Once with palm ram compression, paper is opened, measurement is not smeared with the length of ink marks, unit mm.
Embodiment 1
Step 1: weighing 3g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 10g water uniform stirring is then added into paste, is placed in 35 DEG C of freeze-day with constant temperature dry 5h, and use bag
It seals up for safekeeping.
Step 2: 1g ethyl cellulose, 1g polyethylene and 40mL hexamethylene being mixed and are placed in three-necked flask, at 85 DEG C
It is condensed back, with mixing speed stirring at low speed until ethyl cellulose and polyethylene all dissolve for 300r/min.Step is added
The camouflage paint aqueous solution and 0.1g emulsifier Span80 (sale of Wenzhou District of Zhejiang Province Clear and Bright chemical plant) dissolved in rapid 1 is stirred
Speed is that the high-speed stirred of 700r/min forms stable oil-water type emulsified particle.In 10 DEG C of h-1Rate of temperature fall under stop stirring
It mixes, will be poured into separatory funnel after product stratification, collect lower layer's product and be placed in a beaker, 100mL hexamethylene is added and carries out
Sufficiently washing.Using vacuum filtration, filter cake is placed in vacuum oven, is transferred to agate mortar after 25 DEG C of vacuum drying 100h
It is interior finely ground, Reversible temperature can be obtained and become microscapsule powder.
Step 3: pressing mass fraction, weigh 30 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 20 parts of talcum
Powder (partial size 10nm), which is thoroughly mixed, uniformly (obtains total 8g mixture), is 3000 by 10 mass fraction average molecular weights
Aqueous polyurethane and 10 mass parts ethyl alcohol are sufficiently mixed, and the mixture that 1 mass parts cobalt iso-octoate and manganese iso-octoate is added is (different
Cobalt octoate and manganese iso-octoate mass ratio are laggard for 1:1), the water-white hydrogenated petroleum resin P-140 of 1 mass parts (sale of Jitian's chemical industry)
Row is sanded, and ink is finally made after filtering.
Embodiment 2
Step 1: weighing 6g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 14g water uniform stirring is then added into paste, is placed in 38 DEG C of freeze-day with constant temperature dry 4h, and use bag
It seals up for safekeeping.
Step 2: 1.1g ethyl cellulose, 1g polyethylene and 40mL hexamethylene being mixed and are placed in three-necked flask, 88
It DEG C is condensed back, with mixing speed stirring at low speed until ethyl cellulose and polyethylene all dissolve for 350r/min.It is added
The camouflage paint aqueous solution and 0.15g emulsifier Span80 (sale of Wenzhou District of Zhejiang Province Clear and Bright chemical plant) dissolved in step 1 carries out
Mixing speed is that the high-speed stirred of 750r/min forms stable oil-water type emulsified particle.In 8 DEG C of h-1Rate of temperature fall under stop
It only stirs, will be poured into separatory funnel after product stratification, collect lower layer's product and be placed in a beaker, 100mL hexamethylene is added
Sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum oven, is transferred to agate after 25 DEG C of vacuum drying 110h
It is finely ground in mortar, Reversible temperature can be obtained and become microscapsule powder.
Step 3: pressing mass fraction, weigh 33 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 22 parts of three oxygen
Change two aluminium (partial size 15nm) and is thoroughly mixed uniform (obtaining total 8g mixture), the water for being 3000 by 10 number average molecular weights
Property polyurethane and 12 parts of ethyl alcohol be sufficiently mixed, the mass ratio that 1 part of cobalt iso-octoate and manganese iso-octoate is added is the mixing of 1:5
It is sanded after object, 1 part of water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry), ink is finally made after filtering.
Embodiment 3
Step 1: weighing 12g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 18g water uniform stirring is then added into paste, is placed in 40 DEG C of freeze-day with constant temperature dry 3h, and use bag
It seals up for safekeeping.
Step 2: 1.2g ethyl cellulose, 1g polyethylene and 40mL hexamethylene being mixed and are placed in three-necked flask, 90
It DEG C is condensed back, mixing speed is that 400r/min is stirred at low speed until ethyl cellulose and polyethylene all dissolve.Step is added
The camouflage paint aqueous solution and 0.2g emulsifier Span80 (sale of Wenzhou District of Zhejiang Province Clear and Bright chemical plant) dissolved in rapid 1 is stirred
Speed is that the high-speed stirred of 800r/min forms stable oil-water type emulsified particle.In 5 DEG C of h-1Rate of temperature fall under stop stirring
It mixes, will be poured into separatory funnel after product stratification, collect lower layer's product and be placed in a beaker, 100mL hexamethylene is added and carries out
Sufficiently washing.Using vacuum filtration, filter cake is placed in vacuum oven, is transferred to agate mortar after 40 DEG C of vacuum drying 120h
It is interior finely ground, Reversible temperature can be obtained and become microscapsule powder.
Step 3: pressing mass fraction, weigh 30 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 20 parts of three oxygen
Change two aluminium (partial size 30nm) and is thoroughly mixed uniform (obtaining total 8g mixture), the water for being 3000 by 15 number average molecular weights
Property polyurethane and 15 parts of ethyl alcohol be sufficiently mixed, the mass ratio that 1 part of cobalt iso-octoate and manganese iso-octoate is added is the mixing of 5:1
It is sanded after object, 1 part of water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry), ink is finally made after filtering.
Embodiment 4
Step 1: weighing 6g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 12g water uniform stirring is then added into paste, is placed in 35 DEG C of freeze-day with constant temperature dry 6h, and use bag
It seals up for safekeeping.
Step 2: 1g ethyl cellulose, 1g polyethylene and 60mL tetrahydrofuran being mixed and are placed in three-necked flask, 65
It DEG C is condensed back, with mixing speed stirring at low speed until ethyl cellulose and polyethylene all dissolve for 400r/min.It is added
The camouflage paint aqueous solution and 0.192g emulsifier Span80 (sale of Wenzhou District of Zhejiang Province Clear and Bright chemical plant) dissolved in step 1 carries out
High-speed stirred with mixing speed for 700r/min forms stable oil-water type emulsified particle.In 7 DEG C of h-1Rate of temperature fall under
Stop stirring, will be poured into separatory funnel after product stratification, collects lower layer's product and be placed in a beaker, 60mL tetrahydro furan is added
It mutters and is sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum oven, is transferred to Ma after 30 DEG C of vacuum drying 120h
It is finely ground in Nao mortar, Reversible temperature can be obtained and become microscapsule powder.
Step 3: pressing mass fraction, weigh 30 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 30 parts of talcum
Powder (partial size 25nm) be thoroughly mixed uniformly (obtains total 8g mixture), by 7.5 number average molecular weights be 3000 it is aqueous
Polyurethane and 7.5 parts of normal propyl alcohols are sufficiently mixed, and the mass ratio that 0.86 part of cobalt iso-octoate and manganese iso-octoate is added is 1:0.1
Mixture, be sanded after 0.86 part of water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry), be finally made after filtering
Ink.
Embodiment 5
Step 1: weighing 6g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 12g water uniform stirring is then added into paste, is placed in 35 DEG C of freeze-day with constant temperature dry 6h, and use bag
It seals up for safekeeping.
Step 2: 1g ethyl cellulose, 1g polyethylene and 35mL tetrahydrofuran being mixed and are placed in three-necked flask, 65
It DEG C is condensed back, with mixing speed stirring at low speed until ethyl cellulose and polyethylene all dissolve for 400r/min.It is added
The camouflage paint aqueous solution and 0.072g emulsifier Span80 (sale of Wenzhou District of Zhejiang Province Clear and Bright chemical plant) dissolved in step 1 carries out
High-speed stirred with mixing speed for 750r/min forms stable oil-water type emulsified particle.In 7 DEG C of h-1Rate of temperature fall under
Stop stirring, will be poured into separatory funnel after product stratification, collects lower layer's product and be placed in a beaker, 100mL tetrahydro is added
Furans is sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum oven, is transferred to after 35 DEG C of vacuum drying 105h
It is finely ground in agate mortar, Reversible temperature can be obtained and become microscapsule powder.
Step 3: pressing mass fraction, weigh 30 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 10 parts of talcum
Powder (partial size 25nm) be thoroughly mixed uniformly (obtains total 8g mixture), by 6 number average molecular weights be 3000 it is aqueous poly-
Urethane and 5 parts of normal propyl alcohols are sufficiently mixed, and 0.75 part of cobalt iso-octoate and manganese iso-octoate mass ratio is added as the mixing of 1:10
It is sanded after object, 0.75 part of water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry), ink is finally made after filtering.
After also having carried out many experiments using embodiment 1-5 similar operating procedure, obtained ink is carried out red
The measurement of outer spectrogram and and discoloration test, result is as depicted in figs. 1 and 2 after test.
Wherein Fig. 1 is the infrared spectrum of the sample of the ink of embodiment 2, and as seen from Figure 1, spectral line is in 3578-3340cm-1
There is apparent N-H stretching vibration characteristic absorption peak in place, occurs the characteristic absorption of ester group (C=O) at 1660-1645cm-1
, there is the stretching vibration peak of C-O-C at 1133-1095cm-1 in peak, is all typical aqueous polyurethane absorption peak, illustrates this
Compound ink material contains aqueous polyurethane, for the water-based ink of aqueous polyurethane dispersion.
The experimental result picture of the preparation gained ink such as embodiment 1-5 being prepared Fig. 2 shows the present invention, which is to become
The graph of relation of color pigment cobalt chloride hexahydrate and hexa mass ratio and discoloring temperature and color reversion time, by scheming
2 as can be seen that the discoloring temperature of ink prepared by the present invention is in 40 DEG C of -58 DEG C of ranges, when cobalt chloride hexahydrate and six methylenes
When the mass ratio of urotropine is 1:1, the color reversion time most short needs 1 hour, cobalt chloride hexahydrate and hexa matter
Ratio is measured within the scope of 0.5-2:1, the mass ratio is changing colour further away from 1:1 on curve, closer to numberical range described in mass ratio
2 endpoints, then the color reversion time is longer, and longest is also only 1.5 hours；In addition, working as cobalt chloride hexahydrate and hexa
Mass ratio when being within the scope of 0.5-2:1, with quality shared by the bigger i.e. cobalt chloride hexahydrate of the two weight ratio more it is big then
Discoloring temperature is lower, and minimum 40 DEG C of discoloring temperature, the mass ratio shared by cobalt chloride hexahydrate the low, and discoloring temperature is up to
To about 58 DEG C.
Viscosity is in 20-40 pool range prepared ink after measured in 1-5 of the embodiment of the present invention, and just dry speed is
10-15mm(30s)-1。
Embodiment 6
Step 1: weighing 6g cobalt chloride hexahydrate, 20g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 30.42g water uniform stirring is then added into paste, is placed in 38 DEG C of freeze-day with constant temperature dry 4h, is used in combination
Bag is sealed up for safekeeping.
Step 2: 2.275g ethyl cellulose, 2.275g polyethylene and 40mL hexamethylene being mixed and are placed on three-necked flask
In, it is condensed back at 88 DEG C, with mixing speed stirring at low speed until ethyl cellulose and polyethylene are all molten for 350r/min
Solution.(Wenzhou District of Zhejiang Province Clear and Bright chemical plant goes out the camouflage paint aqueous solution and 0.305g emulsifier Span80 dissolved in addition step 1
Sell) it carries out high-speed stirred with mixing speed for 750r/min and forms stable oil-water type emulsified particle.In 8 DEG C of h-1Cooling
Stop stirring under rate, will be poured into separatory funnel after product stratification, collects lower layer's product and be placed in a beaker, be added
100mL hexamethylene is sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum oven, in 25 DEG C of vacuum drying 110h
After be transferred to it is finely ground in agate mortar, can be obtained Reversible temperature become microscapsule powder.
Step 3: pressing mass fraction, weigh 33 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 22 parts of three oxygen
Change two aluminium (partial size 15nm) be thoroughly mixed uniformly (obtain total 8g mixture), by 10 parts of molecular weight be 2000 it is aqueous poly-
Urethane and 12 parts of ethyl alcohol are sufficiently mixed, and the mass ratio that 1 part of cobalt iso-octoate and manganese iso-octoate is added is the mixture of 1:5,1
It is sanded after the water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry) of part, ink is finally made after filtering.
Obtained ink finds that discoloring temperature is 25 DEG C, low after being tested according to method identical with embodiment 1-5
In 30 DEG C, however its color reversion time is up to 115min.
Embodiment 7
Step 1: weighing 15g cobalt chloride hexahydrate, 6g hexa is added in beaker after mixing, normal temperature and pressure
Lower grinding is simultaneously uniformly mixed, and 21g water uniform stirring is then added into paste, is placed in 35 DEG C of freeze-day with constant temperature dry 6h, and use bag
It seals up for safekeeping.
Step 2: 0.872g ethyl cellulose, 0.872g polyethylene and 60mL tetrahydrofuran being mixed and are placed on three-necked flask
In, it is condensed back at 65 DEG C, with mixing speed stirring at low speed until ethyl cellulose and polyethylene are all molten for 350r/min
Solution.(Wenzhou District of Zhejiang Province Clear and Bright chemical plant goes out the camouflage paint aqueous solution and 0.336g emulsifier Span80 dissolved in addition step 1
Sell) it carries out high-speed stirred with mixing speed for 750r/min and forms stable oil-water type emulsified particle.In 7 DEG C of h-1Cooling
Stop stirring under rate, will be poured into separatory funnel after product stratification, collects lower layer's product and be placed in a beaker, be added
100mL tetrahydrofuran is sufficiently washed.Using vacuum filtration, filter cake is placed in vacuum oven, is dried in vacuo at 30 DEG C
Be transferred to after 120h it is finely ground in agate mortar, can be obtained Reversible temperature become microscapsule powder.
Step 3: pressing mass fraction, weigh 30 parts of Reversible temperatures obtained in step 2 and become microscapsule powder and 30 parts of talcum
Powder (partial size 25nm), which is thoroughly mixed, uniformly (obtains total 8g mixture), the aqueous poly- ammonia for being 3000 by 7.5 parts of molecular weight
Ester and 7.5 parts of normal propyl alcohols are sufficiently mixed, and the mass ratio that 0.86 part of cobalt iso-octoate and manganese iso-octoate is added is the mixed of 1:0.1
It is sanded after closing object, 0.86 part of water-white hydrogenated petroleum resin P-140 (sale of Jitian's chemical industry), oil is finally made after filtering
Ink.
Obtained ink finds that discoloring temperature is up to 70 DEG C after being tested according to method identical with embodiment 1-5,
Higher than 60 DEG C, however its color reversion time is up to 110min.
Claims (20)
1. a kind of Reversible temperature becomes microscapsule powder, which is characterized in that its change for containing cobalt chloride hexahydrate and hexa
Color pigment and carrier.
2. microscapsule powder according to claim 1, wherein the carrier is 8- relative to the mass ratio of camouflage paint
25%, preferably 12-18%.
3. microscapsule powder according to claim 1 or 2, wherein it is fine that the carrier is selected from hydroxypropyl cellulose, methylol
Tie up one or more of element, methylcellulose, ethyl cellulose, polyethylene substance；It is preferred that the carrier be ethyl cellulose and
The mass ratio of the mixture of polyethylene, more preferable ethyl cellulose and polyethylene is 1-1.2:1.
4. microscapsule powder according to claim 1-3, wherein cobalt chloride hexahydrate and hexa
Mass ratio is 0.5-2:1, preferably 1:1.
5. a kind of cobalt ammonium salt Reversible temperature becomes water-based ink, become microcapsules containing the described in any item Reversible temperatures of claim 1-4
Powder, emulsifier, filler, resin binder, diluent resin, drier and defoaming agent.
6. ink according to claim 5, by becoming microcapsules containing the described in any item Reversible temperatures of claim 1-4
Powder, emulsifier, filler, resin binder, diluent resin, drier and defoaming agent raw material be prepared.
7. ink described in claim 5 or 6, which is obtained by the preparation method containing following step:
Step 1, the preparation of camouflage paint:
Cobalt chloride hexahydrate and hexa are mixed, water is then added and forms paste, freeze-day with constant temperature is carried out and is changed colour
Pigment；
Step 2, any one of claim 1-4 Reversible temperature becomes the synthesis of microscapsule powder:
It after carrier and solvent are mixed, is condensed back, with mixing speed stirring at low speed until carrying for 300-400r/min
Body all dissolves；The camouflage paint aqueous solution dissolved in step 1 is added and emulsifier is stirred speed as 700-800r/
The high-speed stirred of min forms stable oil-water type emulsified particle；Then cooling stirring is carried out, product is removed into solvent, is done
Reversible temperature is obtained after dry becomes microscapsule powder；Wherein, the drying is preferably dried in vacuo；
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become microscapsule powder to mix with filler, and is added resin binder and resin is dilute
Ink is made after releasing agent and drier and defoaming agent.
8. the preparation method of cobalt ammonium salt irreversible temperature water-based ink described in claim 5 or 6, which is characterized in that the ink is logical
The preparation method containing following step is crossed to obtain:
Step 1, the preparation of camouflage paint:
Cobalt chloride hexahydrate, hexa mixing are weighed, water is then added and stirs into paste, carries out freeze-day with constant temperature and is become
Color pigment；
Step 2, Reversible temperature becomes the synthesis of microscapsule powder:
It after carrier and solvent are mixed, is condensed back, with mixing speed stirring at low speed until carrying for 300-400r/min
Body all dissolves；The camouflage paint aqueous solution dissolved in step 1 is added and emulsifier is stirred speed as 700-800r/
The high-speed stirred of min forms stable oil-water type emulsified particle；Then cooling stirring is carried out, product is removed into solvent, is done
Reversible temperature is obtained after dry becomes microscapsule powder；Wherein, the drying is preferably dried in vacuo；
Step 3, the preparation of environment-friendly type temperature sensitive ink:
Reversible temperature obtained in step 2 is become microscapsule powder to mix with filler, and is added resin binder and resin is dilute
Ink is made after releasing agent and drier and defoaming agent.
9. preparation method according to claim 8, wherein the matter of cobalt chloride hexahydrate and hexa in step 1
Amount is than being 0.5-2:1, the mass ratio of the mixture and water of cobalt chloride hexahydrate and hexa in further preferred step 1
For 1:1-1.2.
10. preparation method according to claim 8 or claim 9, wherein freeze-day with constant temperature condition is 35-40 DEG C in step 1, preferably
Freeze-day with constant temperature 3-5h.
11. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-10, feature exists
In in step 2, the carrier is selected from hydroxypropyl cellulose, hydroxymethyl cellulose, methylcellulose, ethyl cellulose, polyethylene
One or more of substance；It is preferred that the carrier be ethyl cellulose and polyethylene mixture, more preferable ethyl cellulose and
The mass ratio of polyethylene is 1-1.2:1.
12. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-11, feature exists
In emulsifier described in step 2 is sorbitan fatty ester, is preferably selected from Span80；The more preferable emulsifier phase
Mass ratio for the camouflage paint aqueous solution is 0.3-0.8%, preferably 0.3-0.6%.
13. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-12, feature exists
In rate of temperature fall is 5-10 DEG C of h in step 2-1；Vacuum drying temperature is 25-40 DEG C in further preferred step 2；Further
It is preferred that vacuum drying time is 100-120h.
14. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-13, feature exists
In filler described in step 3 is 1:1-3, preferably 1:1-1:1.5 relative to the mass ratio of the microscapsule powder；More preferably
Filler is one kind of 10-30nm talcum powder or aluminum oxide.
15. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-14, feature exists
In resin binder described in step 3 is water-base resin binder, is selected from waterborne polyurethane resin, acrylic resin, poly- second
One of enol and epoxy resin are a variety of.
16. the preparation method that cobalt ammonium salt Reversible temperature according to claim 15 becomes water-based ink, which is characterized in that step 3
In, the aqueous polyurethane is 1:2-5 relative to the mass ratio of the microscapsule powder；The diluent resin is relative to institute
The mass ratio for stating microscapsule powder is 1:2-6.
17. the preparation method that cobalt ammonium salt Reversible temperature according to claim 16 becomes water-based ink, which is characterized in that step 3
In, the resin binder is the aqueous polyurethane that molecular weight is 2000-3000, and diluent resin is acetone, dimethylbenzene, hexamethylene
One of ketone, ethyl acetate, toluene, ethers or alcohols material；Wherein the alcohols material is selected from ethyl alcohol, normal propyl alcohol, isopropyl
Alcohol, n-butanol, one kind of isobutanol or combinations thereof, are more preferably selected from ethyl alcohol or normal propyl alcohol.
18. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-17, feature exists
In drier is 1:30-40 relative to the mass ratio of microscapsule powder in step 3；Drier is preferably cobalt iso-octoate and different
The mixture of manganese octoate, the more preferably mass ratio of the two are 1:0.1-10.
19. becoming the preparation method of water-based ink according to the described in any item cobalt ammonium salt Reversible temperatures of claim 8-18, feature exists
In the defoaming agent is 1:30-40 relative to the mass ratio of the microscapsule powder；It is preferred that the defoaming agent is selected from ethylene glycol
Mono- n-pentyl ether, the mono- n-hexyl ether of ethylene glycol and propylene glycol list n-butyl ether or silicone substance or water-white non-hydrogenated petroleum tree
Rouge is more preferably selected from water-white hydrogenated petroleum resin P-140.
20. the described in any item microscapsule powders of claim 1-4 or the described in any item cobalt ammonium salts of claim 5-7 are reversible
Temperature becomes application of the water-based ink in food, drug, cigarette packaging material.
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| CN114196261A (en) * | 2021-12-23 | 2022-03-18 | 江苏集萃智能液晶科技有限公司 | Reversible constant-temperature color-changing ink and temperature indicator |
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