CN102477290B - Thermo-sensitive discoloration material microcapsule and preparation method thereof - Google Patents
Thermo-sensitive discoloration material microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermo-sensitive discoloration material microcapsule and a preparation method thereof. The microcapsule is composed of a core material and a wall material for covering the core material, wherein the core material comprises a thermo-sensitive discoloration compound composed of a chromogenic reagent, a color-developing agent and a solvent; the wall material is a melamine resin pre-polymer; the mass ratio of the thermo-sensitive discoloration compound to the melamine resin pre-polymer is 1:(1-2). The preparation method comprises the following steps of: mixing the chromogenic reagent, the color-developing agent and the solvent to form a thermo-sensitive discoloration solution under the heating condition; adding an emulsifying agent solution into the thermo-sensitive discoloration solution and emulsifying a commixed solution to obtain an emulsion; adjusting the pH value to 3-6 and adding the melamine resin pre-polymer into the emulsion; reacting at a temperature for 60-70 DEG C for 1-1.5 hours and then cooling to 30-40 DEG C; then adding a dispersant; and washing and drying to obtain the thermo-sensitive discoloration microcapsule. According to the method provided by the invention, the influences on human bodies and environments are greatly reduced; the operation is simple, the prepared microcapsule products can fast change color and fade and the effect is obvious, so that the thermo-sensitive discoloration material microcapsule can be widely applied in the fields of anti-counterfeiting textile and printing and the like.
Description
Technical field
The present invention relates to a kind of thermo-sensitive discoloration material microcapsule and preparation method thereof.
Background technology
Thermosensitive chromotropic material refers to the material with thermochromic properties.Thermal discoloration, Cucumber can be because colour-change occurs in structural changes at specific environment temperature, also referred to as " thermochromism " or " heat-sensitive variable colour ".The purposes of thermosensitive chromotropic material is many-sided, and its use range is mainly at aspects such as printing, coating, toy, false proof, textile garment and articles for daily use at present.
20 the end of the century thermo-sensitive material develop rapidly, conventional type thermo-sensitive material is that leuco dye and developer solid crystal particle are directly dispersed in binding agent, by heating, make xln reach molten state and cause color reaction, but two can reacted constituent direct contact make permanently effective preservation become a difficult problem.
The application of microencapsulation technology has solved this problem, and the thermo-sensitive material that temperature-sensitive microcapsulary not only can solve conventional type is difficult for the defect of preservation, easy rotten color development affected by environment, and has made up during preservation unsettled disadvantage of pressure-sensitive microcapsule.
Patent CN 128920A has proposed to use aminoresin or epoxy resin as the wall material of heat-sensitive variable colour microcapsule, but does not propose concrete working method.The preparation method of the heat-sensitive variable colour microcapsule that United States Patent (USP) 4028118 proposes uses cyclohexane give for the inadequate environmental protection of solvent and complicated operation.
Summary of the invention
The object of this invention is to provide a kind of thermo-sensitive discoloration material microcapsule and preparation method thereof.
Thermo-sensitive discoloration material microcapsule provided by the present invention, is comprised of core and the wall material of the described core of parcel; Wherein, described core comprises the heat-sensitive variable colour compound by chromogenic reagent, developer and solvent composition, and described wall material is melamine resin prepolymer; The mass ratio of described heat-sensitive variable colour compound and described melamine resin prepolymer is 1: (1-2).
In described heat-sensitive variable colour compound, the mass ratio of chromogenic reagent, developer and solvent can be followed successively by 1: (4-6): (40-60), preferred mass ratio is 1: 5: 50.
The method of the described thermo-sensitive discoloration material microcapsule of preparation provided by the present invention, comprises the steps:
1) preparation heat-sensitive variable colour compound: by chromogenic reagent, developer and solvent and be heated to 80 ℃-90 ℃, maintain described temperature 1-1.5 hour, obtain described heat-sensitive variable colour compound;
2) by step 1) heat-sensitive variable colour compound, emulsifier solution and the water prepared is mixed to get blend solution, described blend solution is placed under stirrer and carries out emulsification, obtains heat-sensitive variable colour compound emulsion;
3) under agitation condition, by step 2) with acidic solution, to regulate pH value be 3-6 for the heat-sensitive variable colour compound emulsion prepared, after adding melamine resin prepolymer solution, be warming up to 50-70 ℃, reaction 1-4 hour, stopped reaction is cooled to 30-40 ℃, add again dispersion agent, make heat-sensitive variable colour microcapsule solution;
4) to step 3) the heat-sensitive variable colour microcapsule solution suction filtration prepared with washed with de-ionized water, the dry thermo-sensitive discoloration material microcapsule that obtains.
Above-mentioned steps 1) in, the mass ratio of described chromogenic reagent, developer and solvent can be followed successively by 1: (4-6): (40-60), preferred mass ratio is 1: 5: 50.
Chromogenic reagent described in the present invention can be selected from following any one: crystal violet lactone, 3-diethylin-7,8-phenyl fluorane, chloro-6 anilinfluoranes of 3-and 3,3,3-tri-(to dimethylamino phenyl) phthalein;
Described developer can be selected from following any one: the two hydroxyl naphthalenes of dihydroxyphenyl propane, Bisphenol F, p-hydroxyphenylaceticacid phenethyl ester and 1,5-;
Described solvent be selected from following any one: lauryl alcohol, tetradecyl alcohol, hexadecanol and stearyl alcohol.
Above-mentioned steps 2) in, in described blend solution, the mass ratio of heat-sensitive variable colour compound and emulsifying agent can be (3-15): (3-10), be preferably 1: 1; In described blend solution, the concentration of heat-sensitive variable colour compound is (0.03-0.15) g/ml; The condition of described emulsification is: emulsification 5-90min under homogenizer 500-1500rpm rotating speed.
Above-mentioned steps 3) in the melamine resin prepolymer solution adding in, in melamine resin prepolymer and heat-sensitive variable colour compound emulsion, the mass ratio of heat-sensitive variable colour compound is (1-2): 1, be preferably 1: 1; The add-on of described dispersion agent is the 0.3-0.6% of reaction soln total mass.
In aforesaid method, described emulsifying agent be selected from following any one: styrene-maleic anhydride copolymer, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate; Described acidic solution be selected from following any one: acetum, citric acid solution and phosphoric acid solution; Described dispersion agent be selected from following any one: dispersion agent KET, dispersion agent NNO (methylene-bis bitter edible plant sodium sulfonate) and sodium lignosulfonate.
The present invention's melamine resin prepolymer used comprises different methylolation products.This melamine resin prepolymer can obtain by commercial sources, as is purchased from ShangHai WuJi Spinning Science Co., Ltd; Also can be prepared according to existing preparation method, as: make trimeric cyanamide and formaldehyde according to certain mol proportion (as 1: 2-3) mix, regulating pH value is 8-9, is heated to 60-70 ℃ and reacts under stirring, makes melmac performed polymer.
The present invention be take thermosetting resin as wall material, the organic solvent that contains thermosensitive chromotropic material is core, by adjusting the ratio of wall material and core, emulsification times and intensity, the pH value of polymerization temperature and soaking time and acidifying etc., under optimal condition, preparation has the heat-sensitive variable colour microcapsule of quick reversible color performance, makes it better be applied to weaving and the field such as false proof.Thermosensitive chromotropic material, through micro encapsulation, has improved thermostability, chemical stability, solvent resistance and mechanical stability, has overcome the dependency of Reversible Thermochromic Materials to environment, is with a wide range of applications.
In preparation method provided by the invention, volatile quantity and the residual volume of formaldehyde are less, have greatly reduced the harm of HUMAN HEALTH and the pollution to environment.The building-up process of microcapsule is to carry out in water, and this has further reduced environmental pollution and operation easier.By controlling emulsification condition, can make the microcapsule product of different-grain diameter to meet different requirements.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare thermo-sensitive discoloration material microcapsule
Preparation method is as follows:
1) by 50g tetradecyl alcohol (solvent) in flask after heat fused, add 1g crystal violet lactone (chromogenic reagent) and 5g dihydroxyphenyl propane (developer), slowly be warming up to 90 ℃, fully stir and be incubated 1 hour, naturally cool to 40 ℃ and obtain heat-sensitive variable colour compound solution.
2) 5g emulsifying agent styrene-maleic anhydride copolymer is joined in 30ml water, after it is dissolved completely, obtain emulsifier solution.In described emulsifier solution, adding 3g step 1) the heat-sensitive variable colour compound solution that makes and 50g water mixes.Blend solution is placed in to emulsification 30min under 1000rpm homogenizer, obtains heat-sensitive variable colour compound emulsion.
3) under the agitation condition of 500rpm rotating speed with acetum regulating step 2) ph value of emulsion prepared is 3, the melamine resin prepolymer solution that was 20% by 20ml mass concentration in 1.5 hours is slowly added dropwise in above-mentioned solution, be warming up to 50 ℃, be incubated 1.5 hours, stopped reaction is cooled to 30 ℃, add again dispersion agent NNO (methylene-bis bitter edible plant sodium sulfonate) 0.6g, obtain heat-sensitive variable colour microcapsule solution.The preparation method of above-mentioned melamine resin prepolymer used is as follows: trimeric cyanamide and formaldehyde mix for 1: 2 in molar ratio, with 2% NaOH solution, regulate pH value to 8～9, under stirring, be heated to 70 ℃, react to trimeric cyanamide and dissolve completely, continue the about 10min of reaction, obtain melamine resin prepolymer.
4) by step 3) microcapsule solution that makes carries out suction filtration and by washed with de-ionized water, the dry heat-sensitive variable colour microcapsule product that obtains at 40 ℃.Prepared microcapsule have quick reversible color performance, and its granularity is 7-15 μ m.
Embodiment 2, prepare thermo-sensitive discoloration material microcapsule
Preparation method is as follows:
1) by 40g hexadecanol in flask after heat fused, add 1g 3-diethylin-7,8-phenyl fluorane (chromogenic reagent) and 5g 1, the two hydroxyl naphthalenes (developer) of 5-, slowly be warming up to 90 ℃ of left and right, fully stir and be incubated 1 hour, naturally cooling to 50 ℃ and obtain heat-sensitive variable colour compound solution.
2) 3g emulsifier sodium lauryl sulfate is joined in 30ml water, after it is dissolved completely, obtain emulsifier solution.In described emulsifier solution, adding 4g step 1) the heat-sensitive variable colour compound solution that makes and 50g water mixes, and blend solution is placed in to emulsification 20min under 1200rpm homogenizer, obtains heat-sensitive variable colour compound emulsion.
3) under the agitation condition of 400rpm rotating speed with citric acid solution regulating step 2) ph value of emulsion prepared is 4, the melamine resin prepolymer solution that was 20% by 20ml mass concentration in 2 hours is slowly added dropwise in above-mentioned solution, be warming up to 60 ℃, be incubated 2 hours, stopped reaction is cooled to 40 ℃, add again dispersion agent NNO (methylene-bis bitter edible plant sodium sulfonate) 0.4g, obtain heat-sensitive variable colour microcapsule solution.The preparation method of above-mentioned melamine resin prepolymer used is as follows: trimeric cyanamide and formaldehyde mix for 1: 3 in molar ratio, with 30% trolamine, regulate pH value to 8～9, under stirring, be heated to 60 ℃, react to trimeric cyanamide and dissolve completely, continue the about 10min of reaction, obtain melamine resin prepolymer.
4) by step 3) microcapsule solution that makes carries out suction filtration and by washed with de-ionized water, the dry heat-sensitive variable colour microcapsule product that obtains at 40 ℃.
Embodiment 3, prepare thermo-sensitive discoloration material microcapsule
Preparation method is as follows:
1) by 50g lauryl alcohol (solvent) in flask after heat fused, add chloro-6 anilinfluoranes of 1g 3-(chromogenic reagent) and 6g p-hydroxyphenylaceticacid phenethyl ester (developer), slowly be warming up to 90 ℃, fully stir and be incubated 1 hour, naturally cooling to 40-50 ℃ and obtain heat-sensitive variable colour compound solution.
2) 2) 5g emulsifying agent Sodium dodecylbenzene sulfonate is joined in 30ml water, after it is dissolved completely, obtain emulsifier solution.In described emulsifier solution, adding 6g step 1) the heat-sensitive variable colour compound solution that makes and 60g water mixes, and blend solution is placed in to emulsification 40min under 1000rpm homogenizer, obtains heat-sensitive variable colour compound emulsion.
3) under the agitation condition of 400rpm rotating speed with phosphoric acid solution regulating step 2) ph value of emulsion prepared is 5, the melamine resin prepolymer that was 20% by 20ml mass concentration in 1.5 hours (embodiment 1 simultaneously) solution is slowly added dropwise in above-mentioned solution, be warming up to 70 ℃, be incubated 1.5 hours, stopped reaction is cooled to 35 ℃, add again dispersion agent K 0.4g, obtain heat-sensitive variable colour microcapsule solution.
4) by step 3) microcapsule solution that makes carries out suction filtration and with washed with de-ionized water, the dry heat-sensitive variable colour microcapsule product that obtains.
Embodiment 4, prepare thermo-sensitive discoloration material microcapsule
Preparation method is as follows:
1) in the ratio of 1: 5: 50, take respectively 3-diethylin-7,8-phenyl fluorane (chromogenic reagent), dihydroxyphenyl propane (developer) and tetradecyl alcohol, by solvent in flask after heat fused, add chromogenic reagent and developer, slowly be warming up to 90 ℃, fully stir and be incubated 1 hour, naturally cooling to 40-50 ℃ and obtain heat-sensitive variable colour compound solution.
2) 4g emulsifying agent styrene-maleic anhydride copolymer is joined in 30ml water, after it is dissolved completely, obtain emulsifier solution.In described emulsifier solution, adding 3g step 1) the heat-sensitive variable colour compound solution that makes and 50g water mixes, and blend solution is placed in to emulsification 25min under 1500rpm homogenizer, obtains heat-sensitive variable colour compound emulsion.
3) under the agitation condition of 600rpm rotating speed with acetum regulating step 2) ph value of emulsion prepared is 3, the melamine resin prepolymer that was 20% by 20ml mass concentration in 1.5 hours (embodiment 2 simultaneously) solution is slowly added dropwise in above-mentioned solution, be warming up to 60 ℃, be incubated 1.5 hours, stopped reaction is cooled to 40 ℃, add again the 0.6g of wooden sodium sulfonate, obtain heat-sensitive variable colour microcapsule solution.
4) by step 3) microcapsule solution that makes carries out suction filtration and with washed with de-ionized water, the dry heat-sensitive variable colour microcapsule product that obtains.
Embodiment 5, prepare thermo-sensitive discoloration material microcapsule
Preparation method is as follows:
1) in the ratio of 1: 4: 40, take respectively 3,3,3-tri-(to dimethylamino phenyl) phthalein (chromogenic reagent), Bisphenol F (developer) and stearyl alcohol.Stearyl alcohol after heat fused, is added to 3,3,3-tri-(to dimethylamino phenyl) phthalein and Bisphenol F in flask, be slowly warming up to 90 ℃, fully stir and be incubated 1 hour, naturally cool to 40-50 ℃ and obtain heat-sensitive variable colour compound solution.
2) 8g emulsifying agent styrene-maleic anhydride copolymer is joined in 30ml water, after it is dissolved completely, obtain emulsifier solution.In described emulsifier solution, adding 5g step 1) the heat-sensitive variable colour compound solution that makes and 50g water mixes, and blend solution is placed in to emulsification 50min under 800rpm homogenizer, obtains heat-sensitive variable colour compound emulsion.
3) under the agitation condition of 800rpm rotating speed with acetum regulating step 2) ph value of emulsion prepared is 5, the melamine resin prepolymer that was 20% by 20ml mass concentration in 2 hours (embodiment 2 simultaneously) solution is slowly added dropwise in above-mentioned solution, be warming up to 70 ℃, be incubated 2 hours, stopped reaction is cooled to 30 ℃, add again dispersion agent K 0.5g, obtain heat-sensitive variable colour microcapsule solution.
4) by step 3) microcapsule solution that makes carries out suction filtration and with washed with de-ionized water, the dry heat-sensitive variable colour microcapsule product that obtains.
Claims (3)
1. a method of preparing thermo-sensitive discoloration material microcapsule, comprises the steps:
1) preparation heat-sensitive variable colour compound: by chromogenic reagent, developer and solvent and be heated to 80-90 ℃, maintain described temperature 1-1.5 hour, obtain described heat-sensitive variable colour compound;
2) by step 1) heat-sensitive variable colour compound, emulsifier solution and the water prepared is mixed to get blend solution, described blend solution is placed under stirrer and carries out emulsification, obtains heat-sensitive variable colour compound emulsion;
3) under agitation condition, by step 2) with acidic solution, to regulate pH value be 3-6 for the heat-sensitive variable colour compound emulsion prepared, after adding melamine resin prepolymer solution, be warming up to 50-70 ℃, reaction 1-4 hour, stopped reaction is cooled to 30-40 ℃, add again dispersion agent, obtain heat-sensitive variable colour microcapsule solution;
4) to step 3) the heat-sensitive variable colour microcapsule solution that obtains carries out suction filtration and with washed with de-ionized water, the dry thermo-sensitive discoloration material microcapsule that obtains;
Described thermo-sensitive discoloration material microcapsule is comprised of the wall material of core and the described core of parcel; Wherein, described core comprises the heat-sensitive variable colour compound by chromogenic reagent, developer and solvent composition, and described wall material is melamine resin prepolymer;
Described step 1), in, the mass ratio of described chromogenic reagent, developer and solvent is followed successively by 1:(4-6): (40-60);
Described step 1) in, described chromogenic reagent be selected from following any one: 3---ethylamino-7,8-phenyl fluorane, chloro-6 anilinfluoranes of 3-and 3,3,3-tri-(to dimethylamino phenyl) phthalein;
Described developer be selected from following any one: the two hydroxyl naphthalenes of dihydroxyphenyl propane, Bisphenol F, p-hydroxyphenylaceticacid phenethyl ester and 1,5-;
Described solvent be selected from following any one: lauryl alcohol, tetradecyl alcohol, hexadecanol and stearyl alcohol;
Described step 2), in, in described blend solution, the mass ratio of heat-sensitive variable colour compound and emulsifying agent is (3-15): (3-10); In described blend solution, the concentration of heat-sensitive variable colour compound is (0.03-0.15) g/m1; The condition of described emulsification is: emulsification 5-90min under homogenizer 500-1500rpm rotating speed;
Described step 3) in the melamine resin prepolymer solution adding in, in melamine resin prepolymer and heat-sensitive variable colour compound emulsion, the mass ratio of heat-sensitive variable colour compound is (1-2): 1; The add-on of described dispersion agent is the 0.3-0.6% of reaction system total mass.
2. method according to claim 1, is characterized in that: described step 2), described emulsifying agent be selected from following any one: styrene-maleic anhydride copolymer, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate;
Described step 3) acidic solution described in be selected from following any one: acetum, citric acid solution and phosphoric acid solution;
Described step 3) dispersion agent described in be selected from following any one: dispersion agent KET, dispersion agent NNO and sodium lignosulfonate.
3. a thermo-sensitive discoloration material microcapsule, is characterized in that: described thermo-sensitive discoloration material microcapsule prepares according to the method described in claim 1 or 2.
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