CN103254676A - Cadmium sulfide-containing two-wavelength light absorption aqueous anti-counterfeiting ink additive preparation process - Google Patents
Cadmium sulfide-containing two-wavelength light absorption aqueous anti-counterfeiting ink additive preparation process Download PDFInfo
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Abstract
The present invention provides a cadmium sulfide-containing two-wavelength light absorption aqueous anti-counterfeiting ink additive preparation process. The preparation process comprises: carrying out uniform ultrasonic dispersion on nanometer cadmium sulfide, deionized water and a surfactant to obtain a nanometer cadmium sulfide solution; mixing a polystyrene sulfonic acid doped polyethylenedioxythiophene solution with a solid content of 1.3-1.7% and deionized water, adding an anion surfactant, and carrying out uniform ultrasonic dispersion to obtain a solution A; mixing the nanometer cadmium sulfide solution and the solution A to obtain a mixing solution B; and heating the mixing solution B to a temperature of 40-70 DEG C, adding an alcohol solvent and powder with a particle size of 200-1000 nm to the mixing solution B under stirring, and carrying out a reaction for 40-60 min to obtain the cadmium sulfide-containing two-wavelength light absorption aqueous anti-counterfeiting ink additive, wherein the cadmium sulfide-containing two-wavelength light absorption aqueous anti-counterfeiting ink additive has absorption at an infrared wave band of 1000-1200 nm and an ultraviolet wave band of 280-330 nm, and can be adopted as an aqueous anti-counterfeiting ink additive.
Description
Technical field
The present invention relates to a kind of preparation technology of anti-forgery ink additive, be specifically related to a kind of preparation technology of dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium.
Background technology
Anti-forgery ink is used very wide in printing industry, and optical anti-counterfeiting printing ink is integral part very important in the anti-forgery ink.Optical anti-counterfeiting printing ink in the Valued Securities printing at present, it is false proof to be mainly ultraviolet ray, commonplace in the application in market, but the problem that exists is that its anti-counterfeit capability is on the low side, and be easy to imitated; In order to satisfy the false proof demand on the market, be badly in need of the anti-counterfeiting technology of development of new.
Summary of the invention
The present invention is directed to above deficiency, a kind of preparation technology of dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium is provided.
In order to achieve the above object, the technical solution used in the present invention may further comprise the steps:
1) Nano cadmium sulphide is placed deionized water, add tensio-active agent then, at room temperature utilize ultrasonic wave that the mixed system that obtains is uniformly dispersed, namely obtain Nano cadmium sulphide solution; Wherein, the mass ratio of Cadmium Sulfide, deionized water, tensio-active agent is (4-5): (100-200): (0.20-0.35), tensio-active agent is cats product and/or nonionogenic tenside;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with deionized water according to the mass ratio of 1:1 with solid content, add anion surfactant then, under 20-70 ℃, utilize ultrasonic dispersing even again, obtain solution A; Wherein, the poly-enedioxy thiophene solution of polystyrolsulfon acid doping and the mass ratio of anion surfactant are 10:0.02;
3) with Nano cadmium sulphide solution and solution A with 1:(1-1.5) mass ratio mix, obtain mixing solutions B; Then mixing solutions B is heated to 40-70 ℃, under agitation adds alcoholic solvent in the mixing solutions B again and particle diameter is the powder of 200-1000nm, reacted 40-60 minute, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the alcoholic solvent that adds accounts for the 25-40% of Nano cadmium sulphide solution quality in the step 3), and alcoholic solvent is ethylene glycol or glycerol; The powder that adds accounts for the 5-10% of Nano cadmium sulphide solution quality in the step 3), and powder is polynite or carboxymethyl starch.
The particle diameter of Nano cadmium sulphide is 80-200nm in the described step 1).
Cats product is that rope Luo Ming A, handkerchief Sa Ming A, oleoyl are for aminoethyl diethylamide, A Keweier A, polyethylene polyamines salt, imidazoline surfactant, high fatty amine salt, quaternary ammonium salt cationic surfactant, N in the described step 1)
αThe mixture of one or more arbitrary proportions in-coconut acyl arginine ethyl ester, pyridine salt type cats product, quinolinium type cats product, double quaternary ammonium salt type cats product, the sulfonium salt type cats product, phosphonium salt type cats product, Arsenic salt type cats product;
Nonionogenic tenside is the mixture of one or more arbitrary proportions in polyoxyethylene-type surfactant, polyoxyethylene polyoxypropylene block type polyethers, EPE polyol EPE, triethanolamine monostearate, phosphorous nonionogenic tenside, the amino acid derivative nonionogenic tenside.
Described polyethylene polyamines salt is quaternized poly 4 vinyl pyridine, poly-sulfuric acid trimethylammonium polyethylene ammonium or polyvinyl lactam hydrochloride;
Described imidazoline surfactant is 1-hydroxyethyl-2-alkyl-tetrahydroglyoxaline, and wherein, the carbonatoms of alkyl is 5-20 in 1-hydroxyethyl-2-alkyl-tetrahydroglyoxaline;
Described high fatty amine salt is to utilize in hydrochloric acid, formic acid or the acetic acid and product that senior primary amine, senior secondary amine or senior tertiary amine obtain;
Described quaternary ammonium salt cationic surfactant is that alkyl trimethyl quaternary ammonium salt, alkyl dimethyl benzyl quaternary ammonium salt, alkyl dimethyl ethoxyl quaternary ammonium salt, fatty acyl are for the mixture of one or more arbitrary proportions in amino tri alkyl quaternary ammonium salt, the imidazoline type quaternary ammonium salt;
Described polyoxyethylene-type surfactant is the mixture of one or more arbitrary proportions in fatty acyl alkanolamine, Viscotrol C ethylene oxide adduct, long-chain fat polyoxyethylenated alcohol, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, the fatty acyl alkanolamine Soxylat A 25-7;
Described polyoxyethylene polyoxypropylene block type polyethers is the mixture of one or more arbitrary proportions in polyoxyethylene polyoxypropylene block type polyethers, polyoxyethylene polyoxypropylene polyoxyethylene blocks type polyethers, the polyoxyethylene polyoxypropylene polyoxypropylene block type polyethers;
Described EPE polyol EPE is the mixture of one or more arbitrary proportions in glyceryl ester type tensio-active agent, polyglycerol fatty acid ester, pentaerythritol fatty ester, dehydration Xylitol fatty acid ester, Span, sorbitan fatty acid ester, tween, sucrose fatty ester, alkyl glycoside, the Polyglycerine poly monoricinolein;
The acid amides of the nonionogenic tenside that described amino acid derivative nonionogenic tenside is glutamic acid derivatives, the ester class of N-acylamino acid, N-acylamino acid, the mixture of one or more arbitrary proportions in the urea groups methylene oleylamide.
Anion surfactant in the described step 3) is sodium laurylsulfonate, benzene sulfonic acid sodium salt, sulfonated, alpha-sulfo monocarboxylic acid or Yi Jiebang A.
Preferably, described senior primary amine is ROCH
2NH
2, one or more arbitrary proportions in the coconut amine, tallow amine, rosin Amine D mixture; Wherein, ROCH
2NH
2In substituent R be that carbonatoms is the alkyl of 11-17; Senior secondary amine is R
2The mixture of one or more arbitrary proportions among the NH; Wherein, the substituent R in the senior secondary amine is that carbonatoms is the alkyl of 6-9; Senior tertiary amine is RN (CH
3)
2, fatty acyl is for the mixture of one or more arbitrary proportions in the aminoethyl diethylamide, fatty group tetrahydroglyoxaline, triethanolamine monostearate; Wherein, RN (CH
3)
2In substituent R be that carbonatoms is the alkyl of 10-16.
Preferably, described pyridine salt type cats product is
And
In substituent R be that carbonatoms is the alkyl of 12-18, X is Cl or Br.
Preferably, described quinolinium type cats product is
And
In substituent R be that carbonatoms is the alkyl of 12-18, X is Cl or Br.
Preferably, described sulfonium salt type cats product is dodecyl dimethyl methyl-sulfuric acid sulfonium.
Preferably, Suo Shu De phosphonium salt type cats product is dodecyl dimethyl phenyl phosphonium bromide, dodecyl three p-methylphenyl phosphonium bromides, tetrakis hydroxymethyl phosphonium chloride or tetradecyl tributyl phosphonium chloride.
Preferably, Suo Shu De Arsenic salt type cats product is octyl dimethyl benzyl Xiuization Arsenic.
Preferably, described phosphorous nonionogenic tenside is polyoxyethylene two (dodecyl) phosphoric acid ester or two polyoxy ethene list tridecyl phosphoric acid ester.
Preferably, described alkyl trimethyl quaternary ammonium salt is alkyl trimethyl ammonium chloride or alkyl trimethyl ammonium bromide, and the carbonatoms of the alkyl in alkyl trimethyl ammonium chloride and the alkyl trimethyl ammonium bromide is 5-18.
Preferably, described alkyl dimethyl benzyl quaternary ammonium salt is
And
In substituent R be that carbonatoms is the alkyl of 5-18.
Preferably, described alkyl dimethyl ethoxyl quaternary ammonium salt is
Or
And
With
In substituent R be that carbonatoms is the alkyl of 5-18.
Preferably, described fatty acyl is that stearoyl replaces aminoethyl diethyl benzyl ammonium chloride, stearoyl to replace the aminopropyl dimethyl benzyl ammonium chloride for aminoethyl trimethylammonium ammonium sulfate or mnyristoyl for amino tri alkyl quaternary ammonium salt.
Preferably, described imidazoline type ammonium salt is 1-hydroxyethyl-1 benzyl-2-alkyl imidazoline ammonium chloride; And the carbonatoms of the alkyl in 1-hydroxyethyl-1 benzyl-2-alkyl imidazoline ammonium chloride is 5-18.
Preferably, described fatty acyl alkanolamine is
Or
Wherein,
With
In substituent R be that carbonatoms is the alkyl of 5-20.
Preferably, to add up to be 40 to the oxyethane addition in the described Viscotrol C ethylene oxide adduct.
Preferably, the general formula of described long-chain fat polyoxyethylenated alcohol is:
And
Middle substituent R is that carbonatoms is the alkyl of 8-20.
Preferably, described alkylphenol polyoxyethylene is
And
In substituent R be that H or carbonatoms are the alkyl of 1-10.
Preferably, the general formula of described polyoxyethylene carboxylate is:
Wherein,
Middle substituent R is that carbonatoms is the alkyl of 8-20.
Preferably, described aliphatic amine polyoxyethylene ether is
Or
In the mixture of one or both arbitrary proportions, wherein,
With
In substituent R be that carbonatoms is the alkyl of 8-20.
Preferably, described fatty acyl alkanolamine Soxylat A 25-7 is:
Or
In the mixture of one or more arbitrary proportions, wherein,
With
In substituent R be that carbonatoms is the alkyl of 8-20.
Preferably, described glyceryl ester type tensio-active agent is Zerol, Stearic diglyceride, glyceryl monooleate, glycerol dioleate, the glycerine monopalmitate, dipalmitin, Tetradecanoic acid, monoester with 1,2,3-propanetriol, glycerine two myristinates, glyceryl monolaurate, Lauric acid, diester with glycerol, the acetic acid glycerol mono fatty acid ester, acetic acid dialycerides fat acid esters, the lactic acid glycerol mono fatty acid ester, lactic acid dialycerides fat acid esters, the polyoxyethylene glycerol mono fatty acid ester, the mixture of one or more arbitrary proportions in the polyoxyethylene dialycerides fat acid esters.
Preferably, the general formula of described polyglycerol fatty acid ester is:
And
Middle substituent R is that carbonatoms is the alkyl of 5-20, substituent R
1And R
2Be that H or carbonatoms are the alkyl of 5-20.
Preferably, the general formula of described pentaerythritol fatty ester is:
And
Middle substituent R is that carbonatoms is the alkyl of 5-20.
Preferably, the described dehydration Xylitol fatty acid ester mixture that is one or more arbitrary proportions in xylitan monostearate or the polyoxyethylene xylitan monostearate.
Preferably, the general formula of described Span is:
And
Middle substituent R is that carbonatoms is the alkyl of 5-20.
Preferably, described sorbitan fatty acid ester is the mixture of one or more arbitrary proportions in sorbitan mono-laurate, anhydrous sorbitol monopalmitate, sorbitan monooleate, sorbitan monostearate, Witconol AL 69-66 and the anhydrous sorbitol tristearate.
Preferably, described tween is polysorbas20, tween 4, polysorbate40, polysorbate60, tween 61, polysorbate65, tween 80, sorbimacrogol oleate100 or polysorbate85.
Preferably, the nonionogenic tenside of described glutamic acid derivatives be pyrrolidone carboxylic acid's glyceryl monooleate or
In the mixture of one or more arbitrary proportions, and
In substituent R be that carbonatoms is the alkyl of 5-20.
Preferably, the ester class of described N-acylamino acid is the mixture of one or both arbitrary proportions in N-alkyloyl glutamate or the N-lauroyl glutamate dibutyl acid amides.
The dual wavelength extinction aqueous anti-counterfeiting easer of the Containing Sulfur cadmium of method preparation of the present invention has absorption at the infrared band of 1000-1200nm and the ultraviolet band of 280-330nm; So the dual wavelength extinction aqueous anti-counterfeiting easer of the Containing Sulfur cadmium of the present invention's preparation is a kind of light absorbing material of dual wavelength; Simultaneously, this dual wavelength light absorbing material can strengthen the anti-counterfeit capability of anti-forgery ink as extinction aqueous anti-counterfeiting easer, can be used as a kind of high-end false proof means and uses, and makes anti-counterfeit capability more reliable.In addition, the tensio-active agent that the present invention adds not only can improve the security feature of printing ink, but also the printing ink after the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium of the present invention is added has good levelling property and good film forming properties.
Description of drawings
Fig. 1 is the illuminated diagram of the dual wavelength extinction aqueous anti-counterfeiting easer of the Containing Sulfur cadmium for preparing of the present invention, and wherein ordinate zou is absorbancy, and X-coordinate is wavelength, and unit is nm.
Embodiment
Below in conjunction with drawings and Examples the present invention is further elaborated.
Embodiment 1:
1) is the deionized water that the Cadmium Sulfide of 80-200nm places 100g with the 4g particle diameter, adds the polysorbate60 of 0.30g then, at room temperature utilize ultrasonic wave with the mixed system ultra-sonic dispersion 120min that obtains again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 80min again, obtain solution A;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1, obtain mixing solutions B; Then mixing solutions B is heated to 40 ℃, under high-speed stirring, adds ethylene glycol in the mixing solutions B again and particle diameter is the polynite of 200-1000nm, reacted 60 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the ethylene glycol that adds accounts for 40% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the polynite of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 5%.
Embodiment 2:
1) with the 4g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 100g, the polyoxyethylene xylitan monostearate and the glycerine monopalmitate that add 0.30g then, at room temperature utilize ultrasonic cleaner with the mixed system ultra-sonic dispersion 120min that obtains again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic echography dispersion 60min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1, obtain mixing solutions B; Then mixing solutions B is heated to 40 ℃, under high-speed stirring, adds ethylene glycol in the mixing solutions B again and particle diameter is the polynite of 200-1000nm, reacted 60 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the ethylene glycol that adds accounts for 40% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the polynite of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 5%.
Embodiment 3:
1) with the 4g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 100g, the lactic acid glycerol mono fatty acid ester and the lactic acid dialycerides fat acid esters that add 0.30g then, at room temperature utilize ultrasonic wave with the mixed system ultra-sonic dispersion 120min that obtains, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, the sodium laurylsulfonate of adding 0.02g utilizes ultrasonic dispersing 40min to obtain solution A again under 20 ℃;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1, obtain mixing solutions B; Then mixing solutions B is heated to 40 ℃, under high-speed stirring, adds ethylene glycol in the mixing solutions B again and particle diameter is the polynite of 200-1000nm, reacted 60 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the ethylene glycol that adds accounts for 40% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the polynite of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 5%.
Embodiment 4:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, the quaternized poly 4 vinyl pyridine and the polysorbas20 that add 0.20g then, at room temperature utilize ultrasonic wave that the mixed system that obtains is disperseed 120min again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the benzene sulfonic acid sodium salt of 0.02g then, under 70 ℃, utilize ultrasonic dispersing 80min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 5:
1) is the deionized water that the Cadmium Sulfide of 80-200nm places 200g with the 4.2g particle diameter, adds the coconut amine hydrochloride of 0.20g then, at room temperature utilize ultrasonic wave that the mixed system that obtains is disperseed 120min again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 35 ℃, utilize ultrasonic dispersing 60min to obtain solution A;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 6:
1) is the deionized water that the Cadmium Sulfide of 80-200nm places 200g with the 4.2g particle diameter, adds the high fatty amine salt of 0.20g then, at room temperature utilize ultrasonic wave that the mixed system that obtains is disperseed 120min again, namely obtain Nano cadmium sulphide solution; High fatty amine salt is by in the hydrochloric acid and the product that obtains of tallow amine and rosin Amine D;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 80min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
High fatty amine salt in embodiment 6 step 1) can also adopt in hydrochloric acid, formic acid or the acetic acid and high fatty amine is made, and acid and the high fatty amine specifically selected for use are as shown in table 1:
Table 1
Embodiment 13
1) is the deionized water that the Cadmium Sulfide of 80-200nm places 150g with the 5g particle diameter, adds the A Keweier A of 0.35g then, at room temperature utilize ultrasonic wave with the mixed system ultra-sonic dispersion 120min that obtains, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, the sulfonated that adds 0.02g then, under 42 ℃, utilize ultrasonic dispersing 40min to obtain solution A again, wherein, the general formula of described sulfonated is RCH=CHCH
2SO
3Na, and RCH=CHCH
2SO
3Substituent R among the Na is that carbonatoms is the alkyl of 5-20;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.2, obtain mixing solutions B; Then mixing solutions B is heated to 70 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 40 minutes, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 25% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 10%.
Embodiment 14:
1) with the 5g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 150g, the rope Luo Ming A and the octadecyl trimethyl ammonium chloride that add 0.35g then, at room temperature utilize ultrasonic cleaner that the mixed system ultra-sonic dispersion that obtains is even again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 40min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.2, obtain mixing solutions B; Then mixing solutions B is heated to 70 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 40 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 25% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 10%.
Embodiment 15:
1) with the 4.5g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 120g, the sucrose fatty ester and the stearyl dimethyl benzyl ammonium chloride that add 0.25g then, at room temperature utilize ultrasonic wave that the mixed system ultra-sonic dispersion that obtains is even again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 80min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 50 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 55 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 25% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 8%.
Sucrose fatty ester in embodiment 15 step 1) and stearyl dimethyl benzyl ammonium chloride can also adopt other cats product and/or nonionogenic tenside to replace, and cats product and/or the nonionogenic tenside specifically selected for use are as shown in table 2:
Table 2
Embodiment 26:
1) with the 4g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 100g, 1-hydroxyethyl-2-heptadecyl-the tetrahydroglyoxaline that adds 0.30g then, at room temperature utilize ultrasonic wave that the mixed system ultra-sonic dispersion that obtains is even again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the alpha-sulfo monocarboxylic acid of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 40min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1, obtain mixing solutions B; Then mixing solutions B is heated to 40 ℃, under high-speed stirring, adds ethylene glycol in the mixing solutions B again and particle diameter is the polynite of 200-1000nm, reacted 60 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the ethylene glycol that adds accounts for 40% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the polynite of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 5%.
Embodiment 27:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, add the stearoyl of 0.20g then for aminoethyl diethyl benzyl ammonium chloride and 1-hydroxyethyl-1-benzyl-2-tridecyl tetrahydroglyoxaline ammonium chloride, at room temperature utilize ultrasonic wave that the mixed system ultra-sonic dispersion that obtains is even again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, the sodium laurylsulfonate of adding 0.02g utilizes ultrasonic dispersing 60min to obtain solution A again under 20 ℃;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 28:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate that adds 0.20g then, at room temperature utilize ultrasonic wave that the mixed system ultra-sonic dispersion that obtains is even again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, at room temperature utilize ultrasonic dispersing 80min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 29:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, the N that adds 0.20g then, N-double hydroxyethyl laurylamide at room temperature utilizes ultrasonic wave that the mixed system ultra-sonic dispersion that obtains is even again, namely obtains Nano cadmium sulphide solution;
2) just the 10g solid content is that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g, adds the sodium laurylsulfonate of 0.02g then, at room temperature utilizes ultrasonic dispersing 50min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 30:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, polyoxyethylene two (dodecyl) phosphoric acid ester that adds 0.20g then, at room temperature utilize ultrasonic wave that the mixed system that obtains is uniformly dispersed again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the Yi Jiebang A of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 70min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Embodiment 31:
1) with the 4.2g particle diameter is the deionized water that the Cadmium Sulfide of 80-200nm places 200g, add the mnyristoyl of 0.20g then for the aminopropyl dimethyl benzyl ammonium chloride, at room temperature utilize ultrasonic wave that the mixed system that obtains is uniformly dispersed again, namely obtain Nano cadmium sulphide solution;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with the deionization water of 10g with the 10g solid content, add the sodium laurylsulfonate of 0.02g then, under 20 ℃, utilize ultrasonic dispersing 80min to obtain solution A again;
3) Nano cadmium sulphide solution is mixed with the mass ratio of solution A with 1:1.5, obtain mixing solutions B; Then mixing solutions B is heated to 65 ℃, under high-speed stirring, adds glycerol in the mixing solutions B again and particle diameter is the carboxymethyl starch of 200-1000nm, reacted 50 minutes, finally obtain the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium; Wherein, the glycerol that adds accounts for 30% of Nano cadmium sulphide solution quality in the step 3), the particle diameter that adds be the carboxymethyl starch of 200-1000nm account for Nano cadmium sulphide solution quality in the step 3) 7%.
Mnyristoyl in the step 1) can also be replaced in order to following cats product and/or nonionogenic tenside for the aminopropyl dimethyl benzyl ammonium chloride, and is specifically as shown in table 3:
Table 3
As seen from Figure 1, the absorbing wavelength of the dual wavelength extinction anti-forgery ink additive of the Containing Sulfur cadmium of the present invention's preparation is 1000-1200nm and 280-330nm, the absorbancy of 280-330nm part can be measured by the long ultraviolet spectrophotometer of all-wave, as seen, the dual wavelength extinction anti-forgery ink additive of Containing Sulfur cadmium all has absorption within ultraviolet, infrared band, show that it is a kind of dual wavelength extinction additive.
More than the poly-enedioxy thiophene solution that mixes of polystyrolsulfon acid among all embodiment namely poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (PEDOT/PSS), and the cats product of not listing one by one in above-described embodiment and/or nonionogenic tenside, all can replace cats product and/or the nonionogenic tenside specifically selected for use in above-described embodiment step 1), thereby make the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium.
Claims (5)
1. the preparation technology of the dual wavelength extinction aqueous anti-counterfeiting easer of a Containing Sulfur cadmium is characterized in that, may further comprise the steps:
1) Nano cadmium sulphide is placed deionized water, add tensio-active agent then, at room temperature utilize ultrasonic wave that the mixed system that obtains is uniformly dispersed, namely obtain Nano cadmium sulphide solution; Wherein, the mass ratio of Cadmium Sulfide, deionized water, tensio-active agent is (4-5): (100-200): (0.20-0.35), tensio-active agent is cats product and/or nonionogenic tenside;
2) be that the poly-enedioxy thiophene solution that the polystyrolsulfon acid of 1.3-1.7% mixes mixes with deionized water according to the mass ratio of 1:1 with solid content, add anion surfactant then, under 20-70 ℃, utilize ultrasonic dispersing even again, obtain solution A; Wherein, the poly-enedioxy thiophene solution of polystyrolsulfon acid doping and the mass ratio of anion surfactant are 10:0.02;
3) with Nano cadmium sulphide solution and solution A with 1:(1-1.5) mass ratio mix, obtain mixing solutions B; Then mixing solutions B is heated to 40-70 ℃, under agitation adds alcoholic solvent in the mixing solutions B again and particle diameter is the powder of 200-1000nm, reacted 40-60 minute, finally obtain the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium; Wherein, the alcoholic solvent that adds accounts in the step 3) 25-40% of Nano cadmium sulphide solution quality in the step 3), and alcoholic solvent is ethylene glycol or glycerol; The powder that adds accounts in the step 3) 5-10% of Nano cadmium sulphide solution quality in the step 3), and powder is polynite or carboxymethyl starch.
2. the preparation technology of the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium according to claim 1, it is characterized in that: the particle diameter of Nano cadmium sulphide is 80-200nm in the described step 1).
3. the preparation technology of the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium according to claim 1 is characterized in that: cats product is that rope Luo Ming A, handkerchief Sa Ming A, oleoyl are for aminoethyl diethylamide, A Keweier A, polyethylene polyamines salt, imidazoline surfactant, high fatty amine salt, quaternary ammonium salt cationic surfactant, N in the described step 1)
αThe mixture of one or more arbitrary proportions in-coconut acyl arginine ethyl ester, pyridine salt type cats product, quinolinium type cats product, double quaternary ammonium salt type cats product, the sulfonium salt type cats product, phosphonium salt type cats product, Arsenic salt type cats product;
Nonionogenic tenside is the mixture of one or more arbitrary proportions in polyoxyethylene-type surfactant, polyoxyethylene polyoxypropylene block type polyethers, EPE polyol EPE, triethanolamine monostearate, phosphorous nonionogenic tenside, the amino acid derivative nonionogenic tenside.
4. the preparation technology of the dual wavelength extinction aqueous anti-counterfeiting easer of Containing Sulfur cadmium according to claim 3 is characterized in that:
Described polyethylene polyamines salt is quaternized poly 4 vinyl pyridine, poly-sulfuric acid trimethylammonium polyethylene ammonium or polyvinyl lactam hydrochloride;
Described imidazoline surfactant is 1-hydroxyethyl-2-alkyl-tetrahydroglyoxaline, and wherein, the carbonatoms of alkyl is 5-20 in 1-hydroxyethyl-2-alkyl-tetrahydroglyoxaline;
Described high fatty amine salt is to utilize in hydrochloric acid, formic acid or the acetic acid and product that senior primary amine, senior secondary amine or senior tertiary amine obtain;
Described quaternary ammonium salt cationic surfactant is that alkyl trimethyl quaternary ammonium salt, alkyl dimethyl benzyl quaternary ammonium salt, alkyl dimethyl ethoxyl quaternary ammonium salt, fatty acyl are for the mixture of one or more arbitrary proportions in amino tri alkyl quaternary ammonium salt, the imidazoline type quaternary ammonium salt;
Described polyoxyethylene-type surfactant is the mixture of one or more arbitrary proportions in fatty acyl alkanolamine, Viscotrol C ethylene oxide adduct, long-chain fat polyoxyethylenated alcohol, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, the fatty acyl alkanolamine Soxylat A 25-7;
Described polyoxyethylene polyoxypropylene block type polyethers is the mixture of one or more arbitrary proportions in polyoxyethylene polyoxypropylene block type polyethers, polyoxyethylene polyoxypropylene polyoxyethylene blocks type polyethers, the polyoxyethylene polyoxypropylene polyoxypropylene block type polyethers;
Described EPE polyol EPE is the mixture of one or more arbitrary proportions in glyceryl ester type tensio-active agent, polyglycerol fatty acid ester, pentaerythritol fatty ester, dehydration Xylitol fatty acid ester, Span, sorbitan fatty acid ester, tween, sucrose fatty ester, alkyl glycoside, the Polyglycerine poly monoricinolein;
The acid amides of the nonionogenic tenside that described amino acid derivative nonionogenic tenside is glutamic acid derivatives, the ester class of N-acylamino acid, N-acylamino acid, the mixture of one or more arbitrary proportions in the urea groups methylene oleylamide.
5. according to the preparation technology of the dual wavelength extinction aqueous anti-counterfeiting easer of claim 1 or 3 described Containing Sulfur cadmiums, it is characterized in that: the anion surfactant in the described step 3) is sodium laurylsulfonate, benzene sulfonic acid sodium salt, sulfonated, alpha-sulfo monocarboxylic acid or Yi Jiebang A.
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