CN107629548A - A kind of antibacterial aqueous ink containing compound cellulose aeroge and preparation method thereof - Google Patents
A kind of antibacterial aqueous ink containing compound cellulose aeroge and preparation method thereof Download PDFInfo
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- CN107629548A CN107629548A CN201610567986.XA CN201610567986A CN107629548A CN 107629548 A CN107629548 A CN 107629548A CN 201610567986 A CN201610567986 A CN 201610567986A CN 107629548 A CN107629548 A CN 107629548A
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Abstract
The present invention relates to ink area, discloses a kind of antibacterial aqueous ink containing compound cellulose aeroge, includes the component of following parts by weight：30 40 parts of water-based acrylic resin liquid；8 12 parts of bletilla striata colloids；8 12 parts carry silver-colored compound cellulose aerogel particle；0.5 1.5 parts of Tea Saponins；10 20 parts of water；5 15 parts of ethanol；10 20 parts of organic pigments；0.5 1.5 parts of defoamers；12 parts of levelling agents；12 parts of buffers.The invention also discloses the preparation method of above-mentioned antibacterial aqueous ink.The antibacterial aqueous ink of the present invention is green, has outstanding antibacterial effect, and dispersiveness, suitable printing, good film-forming property, while have good wearability, pull resistance and light fastness aging after the solidification of ink film forming.
Description
Technical field
The present invention relates to ink area, more particularly to a kind of antibacterial aqueous ink containing compound cellulose aeroge and its
Preparation method.
Background technology
In recent years, water-based ink does not contain substantial amounts of organic volatile solvent due to its environmental protection characteristic, gradual in some fields
It instead of organic solvent ink.Particularly in packaging for foodstuff print field, because hygienic requirements is very high, it is impossible to germy to deposit
, therefore ink nonhazardous itself, environmental protection are not required nothing more than, and need ink that also there is certain antibiotic property.
Wang Can is just waited《Packaging Engineering》A kind of antibacterial water is disclosed in " the Tipping Paper Antibacterial Water-based Ink research " delivered
Property ink, its formula are：Benzidine yellow 5%, titanium dioxide 25%, water-based acrylic resin liquid 45%, ethanol 15% and water 10%.
The water-based ink has good printability on cork paper, and has good antibacterial effect.But weak point is two
Titanium oxide and other compositions are only physical mixed, although serving antibacterial action, dispersiveness is general.
Chinese invention patent CN 102952431A disclose a kind of cigarette cork paper water-based ink and preparation method thereof, bag
Include aqueous emulsifying resinon 50-60 parts+iron oxide pigment 10-20 parts+water 10-20 parts+defoamer, sagging inhibitor, levelling agent, profit
One or more kinds of 0.5-1 parts in humectant, antiseptic, wetting dispersing agent, surface tension agent aid.The cigarette water of the invention
Loose paper water-based ink has fineness small, and rate of drying is fast, and denseness is high, and viscosity is low, and dispersion stabilization is good, no scleroma property precipitation, nothing
Cohesion, the advantages that noresidue peculiar smell, bactericide is directly incorporated in water-based ink by the invention, although the bactericide can rise
To bactericidal action, but the broad-spectrum of single bactericide is small, and bactericidal effect is limited, can also may additionally have to human body
Evil, causes side effect.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of antibacterial aqueous oil containing compound cellulose aeroge
Ink and preparation method thereof.The antibacterial aqueous ink of the present invention is green, has outstanding antibacterial effect, and dispersiveness, printability
Brush, good film-forming property, while there is good wearability, pull resistance and light fastness aging after the solidification of ink film forming.
The present invention concrete technical scheme be：A kind of antibacterial aqueous ink containing compound cellulose aeroge, including with
The component of lower parts by weight：
30-40 part water-based acrylic resin liquid；
8-12 part bletilla striata colloids；
8-12 parts carry silver-colored compound cellulose aerogel particle；
0.5-1.5 part Tea Saponins；
10-20 part water；
5-15 part ethanol；
10-20 part organic pigments；
0.5-1.5 part defoamers；
1-2 part levelling agents；
1-2 part buffers.
Preferably, the preparation method of the silver-colored compound cellulose aerogel particle of load is as follows：
（1）Carry the preparation of the chitin modified brucite fiber of silver：
Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution
Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge
3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5
Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation
Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Silver-colored chitosan will be carried and be configured to the load silver chitosan that concentration is 2-4wt%
Solution, take 10 parts of brucite fibers to be added to 60-80 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wavelength-division
Dissipate, after standing 4-6h, be centrifuged, take obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified shepardite of silver it is fine
Dimension.
The present invention first makes chitosan be complexed silver particles, is in elemental silver in reduction, makes elemental silver load and chitosan
On, it then will carry silver-colored chitosan and brucite fiber be modified, obtain carrying the chitin modified brucite fiber of silver.Wherein silver is single
Matter, chitosan, brucite fiber itself are respectively provided with certain antibiotic property, and in the case where together coordinating, antibacterial spectrum is higher, antibacterial effect
Fruit is more preferable.
（2）Carry the preparation of silver-colored compound cellulose aerogel particle：
By cellulose dissolution in cellulose solvent, the cellulose solution that concentration is 6-10wt% is made, takes 1-3 parts to carry silver-colored shell and gathers
The modified brucite fiber of sugar is added in 100 parts of cellulose solutions, and ultrasonic wave is carried out after stirring and is disperseed, then by solution
Freezed 2-4 days in -4 DEG C to -8 DEG C of environment；Then frozen material is obtained cellulose aquagel, uses ethanol in thaw at RT
Solvent displacement is carried out to cellulose aquagel, obtains cellulose alcogel；Supercritical carbon dioxide is carried out to cellulose alcogel
After fluid drying and crushing, it is made and carries silver-colored compound cellulose aerogel particle.
Above-mentioned number is parts by weight.
To carry the chitin modified brucite fiber of silver and cellulose it is compound after be prepared into aeroge, aeroge has superelevation
Surface area and light, makes an addition in water-based ink, acts not only as antiseptic, and can be used as simultaneously water-based in right amount
The binder of ink uses, it is possible to increase wearability, toughness and tensile strength after ink film forming.In addition, ink was printing
Cheng Zhong, when ink rigid connection is contacted on printable fabric surface, a tunic is formed, specific surface area becomes big suddenly, compound due to carrying silver
Cellulose aerogels particle possesses the specific surface area of super large, and large quantity of moisture is fled from, and water-based ink rate of drying is very fast, when being dried to
When to a certain degree, due to the osmotic pressure of water-based ink binder inside and outside, rate of drying gradually slows down so that water-based ink has foot
The enough time is penetrated into printable fabric, enhancing and the adhesive force of printable fabric, and now the content of moisture is less, will not lead
Cause attribute ink to adhere on dancing roll, printed matter is tarnished, therefore the suitable printing of water-based ink is good.
Wherein, in silver-colored compound cellulose aerogel particle is carried, the side of effect one of the chitin modified brucite fiber of silver is carried
Face is to provide antibacterial functions, on the other hand, after brucite fiber and other celluloses are compound, can strengthen and carry silver-colored compound cellulose
The degree of cross linking of aeroge itself, so as to lift toughness and pull resistance.
Preferably, the preparation method of the cellulose is as follows：100 parts of bamboo silks are added to 300-500 parts 10wt% hydrogen
In potassium oxide solution, decompression boiling is then carried out, temperature is 190-210 DEG C, time 4-6h；Bamboo silk is taken out after boiling, is cleaned
Bamboo silk is added in 1000-1400 parts 50wt% ethanol water afterwards, and is heated to 90-100 DEG C, be incubated 1-2h；Then cross
Leaching solid；After solid is cleaned, it is beaten successively, is cleaned, is dried to obtain cellulose.
Two cellulose of the above method, reactivity is high, particularly suitable for preparing the load silver compound cellulose gas of the present invention
Gel particle.
Preferably, the cellulose solvent is made up of following components：Sodium hydroxide 8-12wt%, thiocarbamide 4-8wt%, more than water
Amount.
Preferably, the particle diameter for carrying silver-colored compound cellulose aerogel particle is 1-3 microns.
Preferably, the water-based acrylic resin liquid is titania modified water-based acrylic resin liquid.
Preferably, the preparation method of the titania modified water-based acrylic resin liquid is as follows：
A, by nano titanium oxide, ethanol, water and silane coupler it is well mixed after in 60 DEG C of water-bath back flow reaction 8-16h, so
After be down to room temperature, product obtains silane coupler modified inorganic nano-particle, the nano-silica by centrifuging and washing
The weight consumption ratio for changing titanium, ethanol, water and silane coupler is 1:30-50:5-15:1-3.
B, 30-60 parts water and 1-3 part emulsifying agents are put into reactor and are heated to 80 DEG C, then by 10-20 part alkyl propylene
Acid ester monomer, 10-20 part hydroxyalkyl acrylates monomer, the silane coupler modified inorganic nano-particle obtained by 15-25 part steps a
Son, 3-5 parts polyethylene glycol and 0.25-0.5 part water soluble starters stir after being put into reactor, after being incubated 0.5-1 hours,
0.25-0.5 part water soluble starters were at the uniform velocity added in 2 hours, are then incubated 4-8 hours again, are stirred afterwards while adding
Enter ammoniacal liquor to be neutralized, make between pH value of solution maintains 7.5-8.5, then vacuumize and remove free ammoniacal liquor, be finally filtrated to get
Titania modified water-based acrylic resin liquid, above material number is parts by weight.
Nano titanium oxide is modified using silane coupler, can be copolymerized with acrylate monomer, by nanometer
Titanium dioxide and hydroxyalkyl are incorporated on water-based acrylic resin, and the nano titanium oxide after modification directly participates in polymerizeing,
Being evenly distributed in resin, to the modified effect of water-based acrylic resin more preferably.Nano titanium oxide has remarkably fast light old
Change performance and antibacterial and mouldproof performance.
Preferably, described alkyl acrylate monomer is methyl methacrylate, EMA or third
Olefin(e) acid butyl ester；The hydroxyalkyl acrylates monomer is hydroxyethyl methacrylate or hydroxy propyl methacrylate.
Preferably, the preparation method of the bletilla striata colloid is as follows：By the bletilla striata powder of 100-200 mesh sieves and water excessively by weight
Compare 2-3:1 mixing, is heated to boiling water, is then ground to jelly, is crushed again after drying, crosses 300-500 mesh sieves.
Bletilla striata powder is heated in boiling water, ground, and discharges colloid substance, is had good film forming, is suitable as water-based
The binder of ink, green, nonhazardous；It can also be embedded simultaneously to carrying silver-colored compound cellulose aerogel particle.Lifting
The stability of water-based ink.
A kind of preparation method of the above-mentioned antibacterial aqueous ink containing compound cellulose aeroge, comprises the following steps：
The water of bletilla striata colloid, water-based acrylic resin liquid, half amount is mixed and stirred for uniformly by proportioning；Then it is multiple to carry silver for addition
Condensating fiber element aerogel particle simultaneously stirs, and then proceedes to add the water of surplus, ethanol, organic pigment, Tea Saponin, defoaming
Agent, levelling agent and buffer, the antibacterial aqueous ink containing compound cellulose aeroge is finally obtained after grinding distribution.
Tea Saponin is with the addition of in the formula of water-based ink, Tea Saponin possesses outstanding emulsification, wetting, dispersive property,
Dispersant can be played a part of in water-based ink, moreover, Tea Saponin also has certain sterilizing function, to golden yellow Portugal
Grape coccus, Escherichia coli etc. have good rejection ability, and Tea Saponin dissolubility in alcohol solution is good, as water-based ink
Dispersant and antiseptic have bright prospects, although Tea Saponin has the problem of being bubbled under oscillatory condition, pass through defoaming
Agent can solve.
It is compared with the prior art, the beneficial effects of the invention are as follows：The antibacterial aqueous ink of the present invention is green, has
The antibacterial effect of color, and dispersiveness, suitable printing, good film-forming property, while there is good wearability after the solidification of ink film forming, resist
Drawing property and light fastness aging.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of antibacterial aqueous ink containing compound cellulose aeroge, include the component of following parts by weight：
35 parts of titania modified water-based acrylic resin liquid；
10 parts of bletilla striata colloids；
10 parts carry silver-colored compound cellulose aerogel particle；
1 part of Tea Saponin；
15 parts of water；
10 parts of ethanol；
15 parts of organic pigments；
1 part of defoamer；
1.5 parts of levelling agents；
1.5 parts of buffers.
The preparation method of the above-mentioned antibacterial aqueous ink containing compound cellulose aeroge, comprises the following steps：
The preparation of titania modified water-based acrylic resin liquid：
A, by nano titanium oxide, ethanol, water and silane coupler it is well mixed after in 60 DEG C of water-bath back flow reaction 12h, then
Room temperature is down to, product obtains silane coupler modified inorganic nano-particle, the nanometer titanium dioxide by centrifuging and washing
Titanium, ethanol, the weight consumption ratio of water and silane coupler are 1:40:10:2.
B, 45 parts of water and 2 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 15 parts of methyl methacrylates, 15 parts
Silane coupler modified inorganic nano-particle obtained by hydroxyethyl methacrylate, 20 parts of step a, 4 parts of polyethylene glycol and 0.4 part
Water soluble starter is stirred after being put into reactor, and after being incubated 0.75 hour, 0.4 part of water solubility was at the uniform velocity added in 2 hours
Initiator, is then incubated 6 hours again, stirs neutralized while adding ammoniacal liquor afterwards, pH value of solution is maintained 7.5-8.5
Between, then vacuumize and remove free ammoniacal liquor, finally it is filtrated to get titania modified water-based acrylic resin liquid.
The preparation of bletilla striata colloid：The bletilla striata powder and water by weight 2.5 of 100 mesh sieves will be crossed:1 mixing, is heated to boiling water,
Then it is ground to jelly, is crushed again after drying, crosses 400 mesh sieves.
Carry the preparation of silver-colored compound cellulose aerogel particle：
Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution
Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge
3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5
Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation
Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Will carry silver-colored chitosan be configured to concentration be 3wt% load silver chitosan it is molten
Liquid, take 10 parts of brucite fibers to be added to 70 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wave and disperse, it is quiet
After putting 5h, it is centrifuged, takes and obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified brucite fiber of silver.
100 parts of bamboo silks are added in 400 parts of 10wt% potassium hydroxide solution, then carry out decompression boiling, temperature is
200 DEG C, time 5h；Bamboo silk is taken out after boiling, is added to bamboo silk in 1200 parts of 50wt% ethanol water after cleaning, and
95 DEG C are heated to, is incubated 1.5h；Then solid is filtered to take；After solid is cleaned, it is beaten, is cleaned successively, be dry
To cellulose.
By cellulose dissolution in cellulose solvent（Sodium hydroxide 10wt%, thiocarbamide 6wt%, water surplus）In, obtained concentration is
8wt% cellulose solution, take 2 parts to carry the chitin modified brucite fiber of silver and be added in 100 parts of cellulose solutions, stirring is equal
Ultrasonic wave is carried out after even to disperse, and then freezes solution 3 days in -6 DEG C of environment；Then frozen material is obtained in thaw at RT
To cellulose aquagel, solvent displacement is carried out to cellulose aquagel with ethanol, obtains cellulose alcogel；Cellulose alcohol is coagulated
After glue carries out supercritical carbon dioxide fluid drying and crushed, the load silver compound cellulose airsetting that particle diameter is 1-3 microns is made
Glue particle.
The water of bletilla striata colloid, titania modified water-based acrylic resin liquid, half amount is mixed and stirred for by proportioning
It is even；Then addition carries silver-colored compound cellulose aerogel particle and stirred, and then proceedes to add the water of surplus, ethanol, has
Machine pigment, Tea Saponin, defoamer, levelling agent and buffer, finally obtained after grinding distribution containing compound cellulose airsetting
The antibacterial aqueous ink of glue.
Embodiment 2
A kind of antibacterial aqueous ink containing compound cellulose aeroge, include the component of following parts by weight：
30 parts of titania modified water-based acrylic resin liquid；
12 parts of bletilla striata colloids；
12 parts carry silver-colored compound cellulose aerogel particle；
1.5 parts of Tea Saponins；
10 parts of water；
15 parts of ethanol；
10 parts of organic pigments；
1.5 parts of defoamers；
2 parts of levelling agents；
2 parts of buffers.
A kind of preparation method of the above-mentioned antibacterial aqueous ink containing compound cellulose aeroge, comprises the following steps：
The preparation of titania modified water-based acrylic resin liquid：
A, in 60 DEG C of water-bath back flow reaction 8h after being well mixed nano titanium oxide, ethanol, water and silane coupler, then drop
To room temperature, product obtains silane coupler modified inorganic nano-particle, the nanometer titanium dioxide by centrifuging and washing
Titanium, ethanol, the weight consumption ratio of water and silane coupler are 1:30:5:1.
B, 30 parts of water and 1 part of emulsifying agent are put into reactor and are heated to 80 DEG C, then by 10 parts of EMAs, 10 parts
Silane coupler modified inorganic nano-particle obtained by hydroxy propyl methacrylate, 15 parts of step a, 3 parts of polyethylene glycol and 0.25
Part water soluble starter stirs after being put into reactor, after insulation 0.5 hour, at the uniform velocity added in 2 hours 0.25 part it is water-soluble
Property initiator, is then incubated 4 hours, stirs neutralized while adding ammoniacal liquor afterwards, pH value of solution is maintained 7.5- again
Between 8.5, then vacuumize and remove free ammoniacal liquor, be finally filtrated to get titania modified water-based acrylic resin liquid.
The preparation of bletilla striata colloid：The bletilla striata powder and water by weight 2 of 200 mesh sieves will be crossed:1 mixing, is heated to boiling water, so
After be ground to jelly, dry after crushed again, cross 300 mesh sieves.
Carry the preparation of silver-colored compound cellulose aerogel particle：
Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution
Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge
3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5
Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation
Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Will carry silver-colored chitosan be configured to concentration be 2wt% load silver chitosan it is molten
Liquid, take 10 parts of brucite fibers to be added to 60 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wave and disperse, it is quiet
After putting 4h, it is centrifuged, takes and obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified brucite fiber of silver.
100 parts of bamboo silks are added in 300 parts of 10wt% potassium hydroxide solution, then carry out decompression boiling, temperature is
190 DEG C, time 6h；Bamboo silk is taken out after boiling, is added to bamboo silk in 1000 parts of 50wt% ethanol water after cleaning, and
90 DEG C are heated to, is incubated 2h；Then solid is filtered to take；After solid is cleaned, it is beaten, is cleaned, is dried to obtain successively
Cellulose.
By cellulose dissolution in cellulose solvent（Sodium hydroxide 8wt%, thiocarbamide 4wt%, water surplus）In, obtained concentration is
6wt% cellulose solution, take 1-3 parts to carry the chitin modified brucite fiber of silver and be added in 100 parts of cellulose solutions, stir
Ultrasonic wave is carried out after uniformly to disperse, and then freezes solution 4 days in -4 DEG C of environment；Then by frozen material in thaw at RT,
Cellulose aquagel is obtained, solvent displacement is carried out to cellulose aquagel with ethanol, obtains cellulose alcogel；To cellulose alcohol
After gel carries out supercritical carbon dioxide fluid drying and crushed, the load silver compound cellulose gas that particle diameter is 1-3 microns is made
Gel particle.
The water of bletilla striata colloid, titania modified water-based acrylic resin liquid, half amount is mixed and stirred for by proportioning
It is even；Then addition carries silver-colored compound cellulose aerogel particle and stirred, and then proceedes to add the water of surplus, ethanol, has
Machine pigment, Tea Saponin, defoamer, levelling agent and buffer, finally obtained after grinding distribution containing compound cellulose airsetting
The antibacterial aqueous ink of glue.
Embodiment 3
A kind of antibacterial aqueous ink containing compound cellulose aeroge, include the component of following parts by weight：
40 parts of titania modified water-based acrylic resin liquid；
8 parts of bletilla striata colloids；
8 parts carry silver-colored compound cellulose aerogel particle；
0.5 part of Tea Saponin；
20 parts of water；
5 parts of ethanol；
20 parts of organic pigments；
0.5 part of defoamer；
1 part of levelling agent；
1 part of buffer.
A kind of preparation method of the above-mentioned antibacterial aqueous ink containing compound cellulose aeroge, comprises the following steps：
The preparation of titania modified water-based acrylic resin liquid：
A, by nano titanium oxide, ethanol, water and silane coupler it is well mixed after in 60 DEG C of water-bath back flow reaction 16h, then
Room temperature is down to, product obtains silane coupler modified inorganic nano-particle, the nanometer titanium dioxide by centrifuging and washing
Titanium, ethanol, the weight consumption ratio of water and silane coupler are 1: 50:15:3.
B, 60 parts of water and 3 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 20 parts of butyl acrylates, 10-20 parts
Silane coupler modified inorganic nano-particle obtained by hydroxyethyl methacrylate, 25 parts of step a, 5 parts of polyethylene glycol and 0.5 part
Water soluble starter is stirred after being put into reactor, and after being incubated 1 hour, 0.5 part of water-soluble initiation was at the uniform velocity added in 2 hours
Agent, is then incubated 8 hours again, stirs neutralized while adding ammoniacal liquor afterwards, make pH value of solution maintain 7.5-8.5 it
Between, then vacuumize and remove free ammoniacal liquor, finally it is filtrated to get titania modified water-based acrylic resin liquid.
The preparation of bletilla striata colloid：The bletilla striata powder and water by weight 3 of 200 mesh sieves will be crossed:1 mixing, is heated to boiling water, so
After be ground to jelly, dry after crushed again, cross 500 mesh sieves.
Carry the preparation of silver-colored compound cellulose aerogel particle：
Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution
Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge
3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5
Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation
Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Will carry silver-colored chitosan be configured to concentration be 4wt% load silver chitosan it is molten
Liquid, take 10 parts of brucite fibers to be added to 80 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wave and disperse, it is quiet
After putting 6h, it is centrifuged, takes and obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified brucite fiber of silver.
100 parts of bamboo silks are added in 500 parts of 10wt% potassium hydroxide solution, then carry out decompression boiling, temperature is
210 DEG C, time 4h；Bamboo silk is taken out after boiling, is added to bamboo silk in 1400 parts of 50wt% ethanol water after cleaning, and
100 DEG C are heated to, is incubated 1h；Then solid is filtered to take；After solid is cleaned, it is beaten, is cleaned, is dried to obtain successively
Cellulose.
By cellulose dissolution in cellulose solvent（Sodium hydroxide 12wt%, thiocarbamide 8wt%, water surplus）In, obtained concentration is
10wt% cellulose solution, take 3 parts to carry the chitin modified brucite fiber of silver and be added in 100 parts of cellulose solutions, stirring is equal
Ultrasonic wave is carried out after even to disperse, and then freezes solution 2 days in -8 DEG C of environment；Then frozen material is obtained in thaw at RT
To cellulose aquagel, solvent displacement is carried out to cellulose aquagel with ethanol, obtains cellulose alcogel；Cellulose alcohol is coagulated
After glue carries out supercritical carbon dioxide fluid drying and crushed, the load silver compound cellulose airsetting that particle diameter is 1-3 microns is made
Glue particle.
The water of bletilla striata colloid, titania modified water-based acrylic resin liquid, half amount is mixed and stirred for by proportioning
It is even；Then addition carries silver-colored compound cellulose aerogel particle and stirred, and then proceedes to add the water of surplus, ethanol, has
Machine pigment, Tea Saponin, defoamer, levelling agent and buffer, finally obtained after grinding distribution containing compound cellulose airsetting
The antibacterial aqueous ink of glue.
Embodiment 4
A kind of antibacterial aqueous ink containing compound cellulose aeroge, include the component of following parts by weight：
35 parts of titania modified water-based acrylic resin liquid；
10 parts of bletilla striata colloids；
10 parts carry silver-colored compound cellulose aerogel particle；
1 part of Tea Saponin；
15 parts of water；
10 parts of ethanol；
15 parts of organic pigments；
1 part of defoamer；
1.5 parts of levelling agents；
1.5 parts of buffers.
The preparation method of the above-mentioned antibacterial aqueous ink containing compound cellulose aeroge, comprises the following steps：
The preparation of titania modified water-based acrylic resin liquid：
A, by nano titanium oxide, ethanol, water and silane coupler it is well mixed after in 60 DEG C of water-bath back flow reaction 12h, then
Room temperature is down to, product obtains silane coupler modified inorganic nano-particle, the nanometer titanium dioxide by centrifuging and washing
Titanium, ethanol, the weight consumption ratio of water and silane coupler are 1:40:10:2.
B, 45 parts of water and 2 parts of emulsifying agents are put into reactor and are heated to 80 DEG C, then by 15 parts of methyl methacrylates, 15 parts
Silane coupler modified inorganic nano-particle obtained by hydroxyethyl methacrylate, 20 parts of step a, 4 parts of polyethylene glycol and 0.4 part
Water soluble starter is stirred after being put into reactor, and after being incubated 0.75 hour, 0.4 part of water solubility was at the uniform velocity added in 2 hours
Initiator, is then incubated 6 hours again, stirs neutralized while adding ammoniacal liquor afterwards, pH value of solution is maintained 7.5-8.5
Between, then vacuumize and remove free ammoniacal liquor, finally it is filtrated to get titania modified water-based acrylic resin liquid.
The preparation of bletilla striata colloid：The bletilla striata powder and water by weight 2.5 of 100 mesh sieves will be crossed:1 mixing, is heated to boiling water,
Then it is ground to jelly, is crushed again after drying, crosses 400 mesh sieves.
Carry the preparation of silver-colored compound cellulose aerogel particle：
Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution
Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge
3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5
Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation
Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Will carry silver-colored chitosan be configured to concentration be 3wt% load silver chitosan it is molten
Liquid, take 10 parts of brucite fibers to be added to 70 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wave and disperse, it is quiet
After putting 5h, it is centrifuged, takes and obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified brucite fiber of silver.
By cellulose dissolution in cellulose solvent（Sodium hydroxide 10wt%, thiocarbamide 6wt%, water surplus）In, obtained concentration is
8wt% cellulose solution, take 2 parts to carry the chitin modified brucite fiber of silver and be added in 100 parts of cellulose solutions, stirring is equal
Ultrasonic wave is carried out after even to disperse, and then freezes solution 3 days in -6 DEG C of environment；Then frozen material is obtained in thaw at RT
To cellulose aquagel, solvent displacement is carried out to cellulose aquagel with ethanol, obtains cellulose alcogel；Cellulose alcohol is coagulated
After glue carries out supercritical carbon dioxide fluid drying and crushed, the load silver compound cellulose airsetting that particle diameter is 1-3 microns is made
Glue particle.
The water of bletilla striata colloid, titania modified water-based acrylic resin liquid, half amount is mixed and stirred for by proportioning
It is even；Then addition carries silver-colored compound cellulose aerogel particle and stirred, and then proceedes to add the water of surplus, ethanol, has
Machine pigment, Tea Saponin, defoamer, levelling agent and buffer, finally obtained after grinding distribution containing compound cellulose airsetting
The antibacterial aqueous ink of glue.
Raw materials used in the present invention, equipment, it is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, it is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and the equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (10)
- A kind of 1. antibacterial aqueous ink containing compound cellulose aeroge, it is characterised in that：Include the component of following parts by weight：30-40 part water-based acrylic resin liquid；8-12 part bletilla striata colloids；8-12 parts carry silver-colored compound cellulose aerogel particle；0.5-1.5 part Tea Saponins；10-20 part water；5-15 part ethanol；10-20 part organic pigments；0.5-1.5 part defoamers；1-2 part levelling agents；1-2 part buffers.
- 2. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 1, it is characterised in that described The preparation method for carrying silver-colored compound cellulose aerogel particle is as follows：（1）Carry the preparation of the chitin modified brucite fiber of silver：Take 10 parts of chitosans and made an addition to stirring in 100 parts of water and extremely dissolve, then 10 parts of nitric acid are added into chitosan solution Silver, diluted nitric acid aqueous solution is added dropwise after stirring until pH value of solution is 3-4, then 60 DEG C of agitating and heatings of water-bath under the conditions of lucifuge 3h, then by suspension successively be centrifuged, take solid matter washing, vacuum drying after, take 10 parts of above-mentioned solid matters and 0.5 Part sodium borohydride is added in 0.01mol/L sodium hydrate aqueous solution, adds water to adjust pH to 7.5-8, last agitated, centrifugation Separation takes solid, washs, is dried to obtain the silver-colored chitosan of load；Silver-colored chitosan will be carried and be configured to the load silver chitosan that concentration is 2-4wt% Solution, take 10 parts of brucite fibers to be added to 60-80 parts and carry in silver-colored chitosan solution and stir, then carry out ultrasonic wavelength-division Dissipate, after standing 4-6h, be centrifuged, take obtain after washing of precipitate, vacuum drying, crushing carrying the chitin modified shepardite of silver it is fine Dimension；（2）Carry the preparation of silver-colored compound cellulose aerogel particle：By cellulose dissolution in cellulose solvent, the cellulose solution that concentration is 6-10wt% is made, takes 1-3 parts to carry silver-colored shell and gathers The modified brucite fiber of sugar is added in 100 parts of cellulose solutions, and ultrasonic wave is carried out after stirring and is disperseed, then by solution Freezed 2-4 days in -4 DEG C to -8 DEG C of environment；Then frozen material is obtained cellulose aquagel, uses ethanol in thaw at RT Solvent displacement is carried out to cellulose aquagel, obtains cellulose alcogel；Supercritical carbon dioxide is carried out to cellulose alcogel After fluid drying and crushing, it is made and carries silver-colored compound cellulose aerogel particle；Above-mentioned number is parts by weight.
- 3. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 2, it is characterised in that described The preparation method of cellulose is as follows：100 parts of bamboo silks are added in 300-500 parts 10wt% potassium hydroxide solution, then carried out Boiling is depressurized, temperature is 190-210 DEG C, time 4-6h；Bamboo silk is taken out after boiling, bamboo silk is added to 1000- after cleaning In 1400 parts of 50wt% ethanol water, and 90-100 DEG C is heated to, is incubated 1-2h；Then solid is filtered to take；By solid After cleaning, it is beaten successively, is cleaned, is dried to obtain cellulose；Above-mentioned number is parts by weight.
- 4. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 2, it is characterised in that described Cellulose solvent is made up of following components：Sodium hydroxide 8-12wt%, thiocarbamide 4-8wt%, water surplus.
- 5. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 1, it is characterised in that described The particle diameter for carrying silver-colored compound cellulose aerogel particle is 1-3 microns.
- 6. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 1, it is characterised in that described Water-based acrylic resin liquid is titania modified water-based acrylic resin liquid.
- 7. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 6, it is characterised in that described The preparation method of titania modified water-based acrylic resin liquid is as follows：A, by nano titanium oxide, ethanol, water and silane coupler it is well mixed after in 60 DEG C of water-bath back flow reaction 8-16h, so After be down to room temperature, product obtains silane coupler modified inorganic nano-particle, the nano-silica by centrifuging and washing The weight consumption ratio for changing titanium, ethanol, water and silane coupler is 1:30-50:5-15:1-3；B, 30-60 parts water and 1-3 part emulsifying agents are put into reactor and are heated to 80 DEG C, then by 10-20 part alkyl acrylate Monomer, 10-20 part hydroxyalkyl acrylates monomer, the silane coupler modified inorganic nano-particle obtained by 15-25 part steps a, 3-5 parts polyethylene glycol and 0.25-0.5 part water soluble starters stir after being put into reactor, after being incubated 0.5-1 hours, 2 0.25-0.5 part water soluble starters are at the uniform velocity added in hour, 4-8 hours is then incubated again, stirs afterwards while adding ammonia Water is neutralized, and is made between pH value of solution maintains 7.5-8.5, then is vacuumized and removed free ammoniacal liquor, is finally filtrated to get dioxy Change titanium modified aqueous acrylic acid resin liquid, above material number is parts by weight.
- 8. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 7, it is characterised in that described Alkyl acrylate monomer be methyl methacrylate, EMA or butyl acrylate；The hydroxyalkyl third Olefin(e) acid ester monomer is hydroxyethyl methacrylate or hydroxy propyl methacrylate.
- 9. a kind of antibacterial aqueous ink containing compound cellulose aeroge as claimed in claim 1, it is characterised in that described The preparation method of bletilla striata colloid is as follows：By the bletilla striata powder of 100-200 mesh sieves excessively with water by weight 2-3:1 mixing, is heated to water Boiling, then it is ground to jelly, is crushed again after drying, cross 300-500 mesh sieves.
- A kind of 10. preparation side of antibacterial aqueous ink containing compound cellulose aeroge as described in claim 1-9 is any Method, it is characterised in that comprise the following steps：The water of bletilla striata colloid, water-based acrylic resin liquid, half amount is mixed and stirred for uniformly by proportioning；Then it is multiple to carry silver for addition Condensating fiber element aerogel particle simultaneously stirs, and then proceedes to add the water of surplus, ethanol, organic pigment, Tea Saponin, defoaming Agent, levelling agent and buffer, the antibacterial aqueous ink containing compound cellulose aeroge is finally obtained after grinding distribution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
| CN111440516A (en) * | 2020-04-16 | 2020-07-24 | 江苏斯迪克新材料科技股份有限公司 | Protective film with antibacterial function |
| CN113235314A (en) * | 2021-05-21 | 2021-08-10 | 深圳市华创汇能技术有限公司 | High-temperature direct-injection dispersion water-based ink and preparation method thereof |
| CN113583183A (en) * | 2021-07-27 | 2021-11-02 | 西南科技大学 | Preparation and use methods of biomass settling agent for radioactive aerosol adsorption settling fixation |
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2016
- 2016-07-19 CN CN201610567986.XA patent/CN107629548A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
| CN110229384B (en) * | 2019-06-19 | 2021-07-23 | 安徽农业大学 | Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof |
| CN111440516A (en) * | 2020-04-16 | 2020-07-24 | 江苏斯迪克新材料科技股份有限公司 | Protective film with antibacterial function |
| CN113235314A (en) * | 2021-05-21 | 2021-08-10 | 深圳市华创汇能技术有限公司 | High-temperature direct-injection dispersion water-based ink and preparation method thereof |
| CN113583183A (en) * | 2021-07-27 | 2021-11-02 | 西南科技大学 | Preparation and use methods of biomass settling agent for radioactive aerosol adsorption settling fixation |
| CN113583183B (en) * | 2021-07-27 | 2023-09-01 | 西南科技大学 | Preparation and use methods of biomass sedimentation agent for radioactive aerosol adsorption sedimentation fixation |
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Application publication date: 20180126 |