CN102875822B - Preparation method of photochromic latex emulsion - Google Patents
Preparation method of photochromic latex emulsion Download PDFInfo
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Abstract
The invention discloses a preparation method of a photochromic latex emulsion, which comprises the following steps: preparing an organic solvent solution of spiropyrane and spiro(oxa)zine organic chromic compound and a colloidal solution of cellulose/hemicellulose or derivatives thereof; adding an optical bleaching agent or mixture of the optical bleaching agent and one or two of PVA (polyvinyl alcohol), PEG (polyethylene glycol) and starch into the colloidal solution; and by using the hydrophilic latex presheared by a dispersion machine as a carrier, dropwisely adding the chromic compound organic solvent solution and the colloidal solution of cellulose/hemicellulose or derivatives into the presheared hydrophilic latex under low rotation speed, thereby preparing the photochromic latex emulsion. The photochromic latex emulsion disclosed by the invention is used in optical decorating materials, daily necessities and anti-counterfeiting materials. The method obviously increases the chromic speed and discoloration speed of the spiropyrane and spiro(oxa)zine organic chromic compound, and the chromic and discoloration sensitivities under irradiation can be respectively enhanced by more than 1.5 times/13 times.
Description
Technical field
The present invention relates to a kind of preparation method of photochromic latex emulsion, the photochromic latex making can be applied in respectively light finishing material, on daily necessities and anti-fake material.
Background technology
In recent decades, photochromic compound is widely used in modern science and technology and daily product field, and its high using value receives the very big concern of chemist.At present, nearly twenties classes of photochromic compound, hundreds of kinds, wherein major part is organic compound, minority is crystal and uncolored type inorganic substance, the wherein spiro-pyrans in organic compound (Spiroan) and spiral shell (Evil) piperazine (Spiroxazina) photochromic compounds, it is a photochromic compounds quasi-representative, important, be research and application the earliest, one of photochromic compounds the most widely, and obtain paying attention to more and more widely of chemical researcher.Around spiro-pyrans (Spiroan) and spiral shell (Evil) research of the aspects such as preparation, modification and application of piperazine (Spiroxazina) photochromic compounds is also increasing, its preparation and method of modifying are particularly seen in patent documentation, wherein about preparing photochromic material, photochromic coating, the method of photochromic latex, is disclosed by following patent documentation:
1, Chinese invention patent specification sheets publication number CN101376755A(discloses day on March 4th, 2009) " photochromic coating " disclosed a kind of photochromic coating, the neccessary composition that contains conventional coating, the tinting material of coating consists of jointly mineral dye and organic dye, wherein the color of mineral dye is not subject to sun-exposed impact substantially, and organic dye is to be subject to the impact of irradiate light and the dyestuff of variable color, can be changed into the complementary color of mineral dye color.There is light color, when illumination weakens, recover again the characteristic of primary colors.
In this invention, not mentioned by make the dissolution system of spiro-pyrans, spiral shell (Evil) piperazine photochromic compound change using latex particle as carrier, and do not relate to control and the adjusting to allochroic paint variable color efficiency.
2, open day on February 19th, 2003 of Chinese invention patent specification sheets publication number CN1398268A() " method of preparing photochromic latex " and publication number CN1531556A(open day on September 22nd, 2004) " the method for preparing stable photochromic latex, the latex obtaining and the purposes in opticianry " a kind of preparation method of photochromic latex disclosed, the method mainly comprises two parts: (1) utilizes Micro Fluid device to process by alkyl methacrylate organic monomer, look rare or (Evil) piperazine class photochromic compounds, the mixture that tensio-active agent and stablizer etc. form, obtain pre-emulsion, (2) pre-emulsion is transferred in reactor, under nitrogen atmosphere, stirred degassedly, after degassed end, introduce polymerization primer and make pre-emulsion poly-by heating
Close and obtain variable color latex.Utilize the standby latex property of this legal system comparatively to stablize and can be applied to the use of the aspects such as opticianry lens.
Foregoing invention method photochromic compound used is selected from chromene and spiral shell piperazine equally, but its preparation method is mainly to utilize under the effect of polymerization primer, by letex polymerization, to prepare photochromic latex with the alkyl methacrylate of C=C base, still the not mentioned dissolution system that makes spiral shell (Evil) piperazine photochromic compound using latex particle as carrier occurs to change and the control to variable color latex variable color efficiency, does not also relate to and products thereof the application aspect false proof.
In prior art, around spiro-pyrans (Spiroan) and spiral shell (Evil) result of study of preparation, modification and the application of piperazine (Spiroxazina) photochromic compounds shows, spiro-pyrans, spiral shell (Evil) photochromic compounds such as piperazine is difficult to dissolve in a large number in water, and its hydrophobic nature also becomes a major reason that limits its widespread use in the middle of water-based system.Therefore, at present a kind of water-based system that can be dissolved in is urgently developed in photochromic compounds market, and has spiro-pyrans, the spiral shell (Evil of higher photosensitivity and photochemical stability) the photochromic water-based material of piperazine, to expand its Application Areas.
Summary of the invention
The object of the invention is for solving spiro-pyrans, spiral shell (Evil) piperazine photochromic compounds is difficult to be applied to the problem in water-based system, a kind of preparation method of photochromic latex emulsion is provided, the method is by the spiro-pyrans of preparation, spiral shell (Evil) organic solvent solution of the organic electrochromic compound of piperazine, the colloidal solution of Mierocrystalline cellulose/hemicellulose class material or derivatives thereof of preparation and optical whitening agent or optical whitening agent that in colloidal solution, selectivity is added and be rich in the mixture of the polymkeric substance of hydroxyl, or in colloidal solution, do not add optical whitening agent, adopt dispersion machine to shear in advance hydrophilic gel breast, compared with under the slow speed of revolution, the colloidal solution of the organic solvent solution of above-mentioned electrochromic compound and Mierocrystalline cellulose/hemicellulose class material or derivatives thereof dropwise joins in the hydrophilic carrier latex emulsion after pre-shearing, thereby make photochromic latex emulsion, and then solved spiro-pyrans, spiral shell (Evil) piperazine photochromic compounds is difficult to the problem of a large amount of dissolvings and stable for extended periods of time existence in water-based system, and can make it be applied to light finishing material, the field such as daily necessities and anti-fake material.
For realizing object of the present invention, the technical scheme adopting is:
A preparation method for photochromic latex emulsion, is characterized in that: preparation method comprises one) preparation photochromic compounds organic solvent solution; Two) colloidal solution of preparation Mierocrystalline cellulose/hemicellulose class material or derivatives thereof; Three) in colloidal solution, selectivity is added optical whitening agent or optical whitening agent and is rich in the mixture of the polymkeric substance of hydroxyl, or in colloidal solution, does not add optical whitening agent; Four) the pre-aqueous carrier latex emulsion that obtains modest viscosity of shearing; Five) preparation of photochromic latex emulsion;
Its preparation and preparation process are as follows:
One) organic solvent solution of preparation photochromic compounds
Get photochromic compounds and join in organic solvent, photochromic compounds is dissolved in solvent completely and prepares to obtain the organic solvent solution of photochromic compounds, the mass ratio of photochromic compounds and solvent is 1:30 ~ 60;
Two) colloidal solution of preparation Mierocrystalline cellulose/hemicellulose class material or derivatives thereof
Get 0.1g ~ 0.3g Mierocrystalline cellulose/hemicellulose class material or derivatives thereof, in wherein adding 1mL ~ 6mL distilled water, prepare to obtain the homogeneous colloidal solution of Mierocrystalline cellulose/hemicellulose class material or derivatives thereof;
Three) in colloidal solution, selectivity is added optical whitening agent or optical whitening agent and is rich in the mixture of the polymkeric substance of hydroxyl, or in colloidal solution, does not add optical whitening agent
Optionally by a kind of optical whitening agent, or optical whitening agent respectively with polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), starch one or both polymkeric substance that are rich in hydroxyl wherein add in colloidal solution together, or do not add optical whitening agent in colloidal solution;
Four) the pre-aqueous carrier latex emulsion that obtains modest viscosity of shearing
Utilize dispersion machine pre-latex that is used as photochromic compounds carrier of shearing under the rotating speed of 15000r/min ~ 22000r/min, obtaining viscosity is the aqueous carrier latex emulsion of 0.23 ~ 0.26 Pas;
Five) preparation of photochromic latex emulsion
At 5000r/min ~ 15000r/min compared with under the slow speed of revolution, in hydrotropisms's carrier latex emulsion, dropwise drip the organic solvent solution of photochromic compounds and the colloidal solution of Mierocrystalline cellulose/hemicellulose class material or derivatives thereof, after dropping finishes, improve rotating speed to 15000r/min ~ 22000r/min, the organic solvent solution of photochromic compounds, colloidal solution fully mixes with carrier latex, thereby makes the photochromic latex emulsion of water-based.
Described organic electrochromic compound, is spiro-pyrans, spiral shell (Evil) mixture of one or both electrochromic compounds of piperazine photochromic compounds, optionally wherein a kind of.
Described organic solvent, is methyl alcohol, ethanol, and the mixture of one or both solvents in acetone, optionally wherein a kind of.
The described latex using as carrier, is styrene-acrylic latex, styrene-butadiene latex, polyvinyl acetate (PVAC), the mixture of polyvinylidene dichloride (PVDC) one or both latex wherein.
The derivative of described Mierocrystalline cellulose/hemicellulose class material, is nanocrystal cellulose (NCC) carboxyl nanocrystal cellulose (CNCC), Microcrystalline Cellulose (MFC), optional wherein a kind of or the wherein mixture of two kinds of compositions.
Described optical whitening agent, is Stilbene-based 4,4 ,-diaminobenzil-2,2 ,-disulfonic acid (four
Sulfonic acid, six sulfonic acid) type optical whitening agent, coumarin type optical whitening agent, pyrazoline type optical whitening agent, phenylpropyl alcohol oxygen nitrogen type optical whitening agent, Phthalimide type optical whitening agent, optional wherein a kind of or wherein two kinds of mixtures that optical whitening agent forms.
Described making an addition to the polymkeric substance that is rich in hydroxyl in colloidal solution together with optical whitening agent, is polyvinyl alcohol, polyoxyethylene glycol, and starch one or both mixture wherein, optionally wherein a kind of; Described polyvinyl alcohol is that molecular weight is 10000 ~ 200000, degree of hydrolysis 30% ~ 98%, and preferably 80% ~ 98%, polyvinyl alcohol solution concentration is 0.1% ~ 20%, preferably 1% ~ 10%; Described molecular weight polyethylene glycol is 200 ~ 200000, preferably 2000 ~ 15000; Described starch is Sumstar 190, anionic starch, cationic starch, preferential oxidation starch.
Advantage and beneficial effect
Compared with prior art, the present invention has advantage and beneficial effect are as follows:
Advantage
Preparation technology is simple, easy to operate, is the scheme of favorable repeatability.
Beneficial effect
1, make organic electrochromic compound system transition of hydrophobic nature for hydrophilic system, and can steady in a long-termly exist.The transformation of dissolution system can achieve and the dissolving each other of multiple hydrophilic component, thereby makes the range of application of this electrochromic compound by original single hydrophobic nature field, expanded to the field of wetting ability and hydrophobic nature.
2, the color depth after variable color can make the variable color intensity of electrochromic compound improve adding of aqueous carrier latex, more than can reach the twice of former organic electrochromic compound.
Can also make the variable color efficiency of organic electrochromic compound and the efficiency of fading obviously improve the adding of latex of 3, using as carrier, wherein the initial needed time of variable color can shorten to 2s by original 5s, and remove the time of fading completely after light source, can foreshorten to 25s by original 6min.
4, Mierocrystalline cellulose/hemicellulose class material or derivatives thereof adds the change/fading time that can effectively control variable color latex.
5, by controlling ambient conditions, adding of Mierocrystalline cellulose/hemicellulose class material or derivatives thereof can also make variable color latex possess anti-counterfeiting characteristic.
6, the Application Areas of photochromic latex emulsion of the present invention is extensive, can be used for phototropic coating, making and the production of phototropic wallpaper, phototropic metope wax, phototropic hard floor paint, phototropic floor wax; Can add among the steeping fluid and coating fluid of finishing material wearing layer, ornament layer body paper; Can also be applied to the fields such as phototropic ink and anti-fake material in addition.
Embodiment
Below in conjunction with embodiment to the detailed description of the invention:
Embodiment 1
A preparation for photochromic latex emulsion, its preparation manipulation is as follows:
Preparation spiral shell (Evil) ethanolic soln of piperazine photochromic compounds
Get spiro-pyrans or spiral shell (Evil) mixture of one or both electrochromic compounds of piperazine photochromic compounds, a kind of commercially available spiral shell (Evil of the present embodiment design) piperazine photochromic compounds, join and contain methyl alcohol, ethanol, in the mixture of one or both organic solvents in acetone, the organic solvent of the present embodiment is designed to commercially available ethanol chemical reagent, mass ratio 1:30 ~ 60 of organic electrochromic compound and organic solvent, the present embodiment spiral shell (Evil) mass ratio of piperazine photochromic compound and alcohol solvent is 1:50, prepare to obtain spiral shell (Evil) ethanolic soln of piperazine photochromic compounds,
The colloidal solution of preparation of nano crystal fibre element (NCC) does not add optical whitening agent in colloidal solution
Take the nanocrystal cellulose (NCC) that 0.1g is selected from the derivative of Mierocrystalline cellulose/hemicellulose class material, carboxyl nanocrystal cellulose (CNCC) and Microcrystalline Cellulose (MFC) a kind of nanocrystal cellulose (NCC) powder wherein, it is joined in 2mL distilled water, obtain the colloidal solution of the nanocrystal cellulose (NCC) of 5% concentration;
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 10g solid content and be 50% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, the pre-aqueous carrier styrene-butadiene latex emulsion of shearing under the rotating speed of 5000r/min, pre-shear time 5min, obtaining viscosity is the aqueous carrier styrene-butadiene latex emulsion of 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 15000r/min by above-mentioned spiral shell (Evil) ethanolic soln of the organic electrochromic compound of piperazine and the colloidal solution of nanocrystal cellulose (NCC), dropwise join in aqueous carrier styrene-butadiene latex emulsion, after dropping finishes, adjust the rotating speed of dispersion machine to 22000r/min, shearing treatment 8min, above-mentioned emulsion is fully mixed, thereby it is high to be prepared into stability, can be dissolved in the organic photochromic latex emulsion in water-based system.
Embodiment 2
Preparation spiral shell (Evil) acetone soln of piperazine photochromic compounds
1:30, prepares to obtain spiral shell (Evil in mass ratio) acetone soln of piperazine photochromic compounds;
The colloidal solution of preparation of nano crystal fibre element (NCC) adds optical whitening agent in colloidal solution
Take 0.1g nanocrystal cellulose (NCC) powder, it is joined in 2mL distilled water, obtain the NCC colloidal solution of 5% concentration, by solid content, be 0.6% 4,4 ,-diaminobenzil-2,2,-disulfonic acid type optical whitening agent (OBA) adds evenly mixing in NCC colloidal solution to, glimmering to give product
Light security feature, the OBA concentration in NCC colloidal solution is 100ppm;
The pre-aqueous carrier styrene-acrylic latex emulsion that obtains modest viscosity of shearing
Take 12g solid content and be 50% aqueous carrier styrene-acrylic latex emulsion, adopt IKA T25 dispersion machine, the pre-aqueous carrier styrene-acrylic latex emulsion of shearing under the rotating speed of 8000r/min, pre-shear time 2min, obtaining viscosity is the aqueous carrier styrene-acrylic latex emulsion of 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 12000r/min by above-mentioned spiral shell (Evil) acetone soln of the organic electrochromic compound of piperazine and the NCC colloidal solution that contains optical whitening agent, dropwise join in styrene-acrylic latex emulsion, after dropping finishes, adjust rotating speed and process 5min to 18000r/min, mixed solution is mixed, then adjust dispersing speed to 22000r/min, shearing treatment 8 min, fully mix above-mentioned emulsion and make photochromic latex emulsion.
Embodiment 3
Preparation spiral shell (Evil) methanol solution of piperazine photochromic compounds
1:60 preparation spiral shell (Evil in mass ratio) methanol solution of the organic electrochromic compound of piperazine;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent
Get 0.2g carboxyl nanocrystal cellulose (CNCC) powder and join that in 2.5mL distilled water, to obtain concentration be 8% CNCC colloidal solution, in CNCC colloidal solution, to add 250mg polyoxyethylene glycol (PEG), solid content be 0.5% 4,4,-diaminobenzil-2,2,-tetrasulfonic acid type optical whitening agent (OBA) solution mixes, to give product fluorescence falsification preventing characteristic
,the concentration that makes OBA in CNCC colloidal solution is 100 ppm, and selected PEG molecular weight is 2000 ~ 15000;
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 9g solid content and be 50% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, under the speed of 8000r/min, the pre-aqueous carrier styrene-butadiene latex emulsion 2min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 12000r/min in wherein dropwise adding above-mentioned spiral shell (Evil) methanol solution of the organic electrochromic compound of piperazine, the colloidal solution of CNCC, dropping finishes rear adjustment rotating speed to 22000r/min, and shearing action 12 min fully mix it and make photochromic latex emulsion.
Embodiment 4
Preparation spiral shell (Evil) ethanolic soln of piperazine photochromic compounds
1:50 preparation spiral shell (Evil in mass ratio) ethanolic soln of piperazine photochromic compounds;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent
Get 0.1g carboxyl nanocrystal cellulose (CNCC) powder and join the CNCC colloidal solution that obtains 5% concentration in 2mL distilled water, in wherein to add 25 mg polyvinyl alcohol (PVA), solid content be 0.5% 4,4,-diaminobenzil-2,2,-six sulfonic acid type optical whitening agent (OBA) solution mix, to give product fluorescence falsification preventing characteristic, the concentration that makes OBA in CNCC colloidal solution is 120 ppm, selected PVA molecular weight is 10000 ~ 200000, degree of hydrolysis 80% ~ 98%, its strength of solution is 1% ~ 10%;
The pre-aqueous carrier styrene-acrylic latex emulsion that obtains modest viscosity of shearing
Take 10g solid content and be 50% aqueous carrier styrene-acrylic latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 6000r/min, the pre-3min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 13000r/min in wherein dropwise adding above-mentioned spiral shell (Evil) ethanolic soln of piperazine photochromic compounds and the colloidal solution of CNCC, dropping finishes rear adjustment rotating speed to 19000r/min effect 20 min, makes it fully be mixed to get photochromic latex emulsion.
Embodiment 5
Preparation spiral shell (Evil) acetone soln of piperazine photochromic compounds
1:30 preparation spiral shell (Evil in mass ratio) acetone soln of the organic electrochromic compound of piperazine;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent and Sumstar 190
Getting 0.3g carboxyl nanocrystal cellulose (CNCC) powder adds 6mL distilled water to obtain the CNCC colloidal solution of 5% concentration, the Sumstar 190 solution that to add 250mg polyoxyethylene glycol (PEG), 0.5 g concentration in CNCC colloidal solution be 5% mixes, and the molecular weight of selected PEG is 2000 ~ 15000;
The pre-aqueous carrier styrene-acrylic latex emulsion that obtains modest viscosity of shearing
Take 15g solid content and be 50% aqueous carrier styrene-acrylic latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 10000r/min, the pre-aqueous carrier styrene-acrylic latex emulsion 2min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 10000r/min, dropwise add above-mentioned spiral shell (Evil) acetone soln of the organic electrochromic compound of piperazine and the colloidal solution of CNCC, drip and finish rear adjustment rotating speed to 20000r/min effect 10 min, make it
Fully be mixed to get photochromic latex emulsion.
Embodiment 6
Preparation spiral shell (Evil) methanol solution of piperazine photochromic compounds
1:60 preparation spiral shell (Evil in mass ratio) methanol solution of the organic electrochromic compound of piperazine;
The colloidal solution of preparation of nano crystal fibre element (NCC), and in colloidal solution, add optical whitening agent
Getting 0.3g nanocrystal cellulose (NCC) powder adds 5mL distilled water to obtain the NCC colloidal solution of 6% concentration, and in NCC colloidal solution, add the pyrazoline type optical whitening agent (OBA) that 25 mg polyvinyl alcohol (PVA), 250mg polyoxyethylene glycol (PEG), solid content are 0.5% and mix, to give product fluorescence falsification preventing characteristic, the concentration that makes OBA in its colloidal solution is 200 ppm, selected PVA molecular weight is 10000 ~ 200000, degree of hydrolysis 80% ~ 98%, its strength of solution is that 1% ~ 10%, PEG molecular weight is 2000 ~ 15000;
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 12g solid content and be 50% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 12000r/min, the pre-aqueous carrier styrene-butadiene latex emulsion 2min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 15000r/min, dropwise add above-mentioned spiral shell (Evil) methanol solution of the organic electrochromic compound of piperazine and the colloidal solution of NCC, drip and finish rear adjustment rotating speed to 22000r/min effect 8 min, make it fully be mixed to get photochromic latex emulsion.
Embodiment 7
The methanol solution of preparation spiro-pyrans photochromic compounds
1:50 prepares the methanol solution of the organic electrochromic compound of spiro-pyrans in mass ratio;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent
Getting 0.2g carboxyl nanocrystal cellulose (CNCC) powder adds 4mL distilled water to obtain the CNCC colloidal solution of 5% concentration, in CNCC colloidal solution, add solid content and be 0.8% benzo oxygen nitrogen type optical whitening agent (OBA) solution and mix, to give product fluorescence falsification preventing characteristic
,the concentration that makes OBA in CNCC colloidal solution is 150 ppm;
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 10g solid content and be 50% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 10000r/min, the pre-aqueous carrier styrene-butadiene latex emulsion 2min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 12000r/min, dropwise add the methanol solution of the organic electrochromic compound of above-mentioned spiro-pyrans and the colloidal solution of CNCC, drip and finish rear adjustment rotating speed to 20000r/min effect 10 min, it is fully mixed, make photochromic latex emulsion.
Embodiment 8
The ethanolic soln of preparation spiro-pyrans photochromic compounds
1:40 prepares the ethanolic soln of the organic electrochromic compound of spiro-pyrans in mass ratio;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent
Getting 0.1g carboxyl nanocrystal cellulose (CNCC) powder adds 1.25mL distilled water to obtain the CNCC colloidal solution of 8% concentration, coumarin type optical whitening agent (OBA) solution that to add 200mg polyoxyethylene glycol (PEG), 30 mg polyvinyl alcohol (PVA), solid content in CNCC solution be 0.2% mixes, to give product fluorescence falsification preventing characteristic, making the OBA concentration in its colloidal solution is 200 ppm, selected PEG molecular weight is 2000 ~ 15000, PVA is molecular weight 10000 ~ 200000, degree of hydrolysis 80% ~ 98%, its strength of solution is 1% ~ 10%;
The pre-aqueous carrier styrene-acrylic latex emulsion that obtains modest viscosity of shearing
Take 10g solid content and be 50% aqueous carrier styrene-acrylic latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 8000r/min, the pre-aqueous carrier styrene-acrylic latex emulsion 3min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 15000r/min, dropwise add the ethanolic soln of the organic electrochromic compound of above-mentioned spiro-pyrans and the colloidal solution of CNCC, drip and finish rear adjustment rotating speed to 16000r/min effect 20 min, make it fully be mixed to get photochromic latex emulsion.
Embodiment 9
The acetone soln of preparation spiro-pyrans photochromic compounds
1:30 prepares the acetone soln of the organic electrochromic compound of spiro-pyrans in mass ratio;
The colloidal solution of preparation carboxyl nanocrystal cellulose (CNCC), and in colloidal solution, add optical whitening agent
Getting 0.3g carboxyl nanocrystal cellulose (CNCC) powder adds 5mL distilled water to obtain the CNCC colloidal solution of 6% concentration, Phthalimide type optical whitening agent (OBA) solution that to add 30 mg polyvinyl alcohol (PVA), solid content in CNCC colloidal solution be 0.5% mixes, to give product fluorescence falsification preventing characteristic, making the OBA concentration in its colloidal solution is 120 ppm, selected PVA molecular weight is 10000 ~ 200000, degree of hydrolysis 80% ~ 98%, its strength of solution is 1% ~ 10%;
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 12g solid content and be 55% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 10000r/min, the pre-aqueous carrier styrene-butadiene latex emulsion 2min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 10000r/min, dropwise add the acetone soln of the organic electrochromic compound of above-mentioned spiro-pyrans and the colloidal solution of CNCC, drip and finish rear adjustment rotating speed to 20000r/min effect 10 min, it is fully mixed, make photochromic latex emulsion.
Embodiment 10
The acetone soln of preparation spiro-pyrans photochromic compounds
The acetone soln of spiro-pyrans photochromic compounds is put in 1:50 preparation in mass ratio;
The colloidal solution of preparation of nano crystal fibre element (NCC), and in colloidal solution, add optical whitening agent
Getting 0.2g nanocrystal cellulose (NCC) powder adds 4mL distilled water to obtain the NCC colloidal solution of 5% concentration, in NCC colloidal solution, add 30 mg polyvinyl alcohol (PVA), 250mg polyoxyethylene glycol (PEG), solid content be 0.3% 4, 4,-diaminobenzil-2, 2,-disulfonic acid type optical whitening agent (OBA) solution mixes, to give product fluorescence falsification preventing characteristic, the concentration that makes OBA in its colloidal solution is 180 ppm, selected PVA molecular weight is 10000 ~ 200000, degree of hydrolysis 80% ~ 98%, its strength of solution is 1% ~ 10%, PEG molecular weight is 2000 ~ 15000,
The pre-aqueous carrier styrene-butadiene latex emulsion that obtains modest viscosity of shearing
Take 15g solid content and be 50% aqueous carrier styrene-butadiene latex emulsion, adopt IKA T25 dispersion machine, under the rotating speed of 12000r/min, the pre-aqueous carrier styrene-butadiene latex emulsion 3min that shears, makes its viscosity reach 0.23 ~ 0.26 Pas;
The preparation of photochromic latex emulsion
Under the rotating speed of 13000r/min, dropwise add the acetone soln of above-mentioned spiro-pyrans photochromic compounds and the colloidal solution of NCC, drip and finish rear adjustment rotating speed to 21000r/min effect 15 min, make it fully be mixed to get photochromic latex emulsion.
In the present invention, select spiro-pyrans or spiral shell (Evil) piperazine.Spiro-pyrans has good photochromic characteristic, and spiral shell (Evil) piperazine is the compound that a class that 20 century 70s grow up on spiro-pyrans basis has good photochromic properties, possessing the advantages such as anti-fatigue performance is high, light stability is good, is the photochromic material that is hopeful to enter Application Areas most.
The photochromic latex being made by aforesaid method, it is of many uses, it can be applied to the wearing layer of phototropic finishing material, coating fluid or the steeping fluid of ornament layer body paper, phototropic wallpaper, phototropic metope wax, phototropic hard floor paint, phototropic floor wax, and phototropic ink, the fields such as phototropic coating and anti-fake material.
Variable color speed and the fading rate of photochromic latex emulsion prepared by the inventive method obviously increase, the sensitivity that illumination becomes/fades can improve 1.5 times/more than 13 times.
The above is only the preferred embodiment of the present invention; it should be pointed out that the person skilled in the art for the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. a preparation method for photochromic latex emulsion, is characterized in that: its preparation methods steps comprises:
One) organic solvent solution of preparation photochromic compounds
Two) colloidal solution of the derivative of preparation Mierocrystalline cellulose/hemicellulose class material, the derivative of described Mierocrystalline cellulose/hemicellulose class material, is nanocrystal cellulose, carboxyl nanocrystal cellulose, Microcrystalline Cellulose, optional one or both mixture wherein
Three) in colloidal solution, selectivity is added optical whitening agent or optical whitening agent and is rich in the mixture of the polymkeric substance of hydroxyl, or in colloidal solution, does not add optical whitening agent
Four) the pre-aqueous carrier latex emulsion that obtains modest viscosity of shearing
Five) make organic photochromic latex emulsion;
Above steps operation is as follows:
One) organic solvent solution of preparation photochromic compounds
Get photochromic compounds and join in organic solvent, photochromic compounds is dissolved in solvent completely and prepares to obtain the organic solvent solution of organic electrochromic compound, the mass ratio of photochromic compounds and solvent is 1:30 ~ 60;
Two) colloidal solution of the derivative of preparation Mierocrystalline cellulose/hemicellulose class material
Get the derivative of 0.1g ~ 0.3g Mierocrystalline cellulose/hemicellulose class material, in wherein adding 1mL ~ 6mL distilled water, prepare to obtain the homogeneous colloidal solution of derivative of Mierocrystalline cellulose/hemicellulose class material;
Three) in colloidal solution, selectivity is added optical whitening agent or optical whitening agent and is rich in the mixture of the polymkeric substance of hydroxyl, or in colloidal solution, does not add optical whitening agent
By a kind of optical whitening agent, or optical whitening agent respectively with the polyvinyl alcohol that is rich in the polymkeric substance of hydroxyl, polyoxyethylene glycol, after being mixed together, add in colloidal solution starch one or both materials wherein, or in colloidal solution, do not add optical whitening agent, wherein polyvinyl alcohol is molecular weight 10000 ~ 200000, degree of hydrolysis 30% ~ 98%, polyvinyl alcohol solution concentration is 0.1% ~ 20%, described molecular weight polyethylene glycol is 200 ~ 200000, described starch is Sumstar 190, anionic starch, cationic starch;
Four) the pre-aqueous carrier latex emulsion that obtains modest viscosity of shearing
Utilize dispersion machine pre-latex emulsion that is used as photochromic compound carrier of shearing under the rotating speed of 15000r/min ~ 22000r/min, obtaining viscosity is the aqueous carrier latex emulsion of 0.23 ~ 0.26 Pas;
Five) make photochromic latex emulsion
At 5000r/min ~ 15000r/min compared with under the slow speed of revolution, in hydrotropisms's carrier latex emulsion, dropwise drip the colloidal solution of the organic solvent solution of photochromic compounds and the derivative of Mierocrystalline cellulose/hemicellulose class material, after dropping finishes, improve rotating speed to 15000r/min ~ 22000r/min, the organic solvent solution of photochromic compounds, colloidal solution fully mixes with aqueous carrier latex, thereby makes photochromic latex emulsion.
2. the preparation method of photochromic latex emulsion according to claim 1, is characterized in that: described photochromic compounds is spiro-pyrans, spiral shell (Evil) mixture of one or both electrochromic compounds of the organic electrochromic compound of piperazine.
3. the preparation method of photochromic latex emulsion according to claim 1, is characterized in that: described organic solvent is methyl alcohol, ethanol, the mixture of one or both solvents in acetone.
4. the preparation method of photochromic latex emulsion according to claim 1, is characterized in that: the latex using as carrier is styrene-acrylic latex, styrene-butadiene latex, polyvinyl acetate, polyvinylidene dichloride, the optional wherein a kind of or mixture of two kinds of latex wherein.
5. the preparation method of photochromic latex emulsion according to claim 1, it is characterized in that: described optical whitening agent is Stilbene-based 4,4,-diaminobenzil-2,2 ,-disulfonic acid type optical whitening agent, coumarin type optical whitening agent, pyrazoline type optical whitening agent, phenylpropyl alcohol oxygen nitrogen type optical whitening agent, Phthalimide type optical whitening agent, optional wherein a kind of or the wherein mixture of two kinds of optical whitening agents.
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