CN112852402A - Durable thermochromic material, preparation method thereof and application thereof in textiles - Google Patents
Durable thermochromic material, preparation method thereof and application thereof in textiles Download PDFInfo
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- CN112852402A CN112852402A CN202011524720.XA CN202011524720A CN112852402A CN 112852402 A CN112852402 A CN 112852402A CN 202011524720 A CN202011524720 A CN 202011524720A CN 112852402 A CN112852402 A CN 112852402A
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- thermochromic
- polyvinyl alcohol
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
The invention provides a lasting thermochromic material, a preparation method thereof and application in textiles, wherein the thermochromic material has a microcapsule structure, takes a thermochromic organic dye as a core material of a microcapsule, and the core material is sequentially coated with a first capsule wall and a second capsule wall; the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting ultraviolet resistant agent, polyvinyl alcohol and n-butyl aldehyde. Compared with the existing products on the market, the durability of the thermochromic material is greatly improved. And because of the double-layer coating form, the invention can coat various color-changing system components and keep stable, does not influence color development, has better protection on the core material, ensures that the material is not easy to leak, and has good washing resistance and durability. The thermochromic material provided by the invention has higher reversible color change durability and is beneficial to long-term use of color-changing textiles.
Description
Technical Field
The invention relates to the technical field of textile fabrics, in particular to a durable thermochromic material, a preparation method thereof and application thereof in textiles.
Background
In modern life, consumers have stronger and stronger requirements on interesting clothes, and color-changeable clothes fabrics are one of the clothes. The color-changeable textile fabric is mainly realized by compounding functional materials with color-changing property. As one of the main categories of color-changing materials, thermochromic materials, also called as temperature-indicating materials (or thermochromic materials, abbreviated as temperature-changing materials), are materials that can change color with the change of external temperature, and the temperature at which the color changes is called as color-changing temperature. The textile is generally made of organic reversible thermochromic materials, and has the characteristics of sensitive color change, quick color change, large selectable color change temperature range, bright color and the like. The color change mechanism of the color change material is that the temperature is increased to cause the transfer of protons in the molecules of the thermochromic compound, so that the molecular structure is changed, and the reversible thermochromic phenomenon is generated.
The thermosensitive color-changing organic dye is composed of leuco dye, developer, temp regulator and sensitizer (or desensitizer), the leuco dye is a substance able to combine with proton to develop color, such as lactone compound, and is used as electron donor part in color-changing system to determine the change of color, and the developed color varies with different substituents. However, the conjugated system in the molecule is interrupted, and the color needs to react with a color developing agent under certain conditions to develop color. The color developing agent is an acid releasing compound which can release protons reversibly, namely an electron withdrawing compound, and determines the color shade. The temperature regulator mainly influences the temperature of thermochromism, and when the temperature regulator is molten, the color developing agent is separated from the leuco dye, so that the formation of a conjugated system is hindered, and the system is in a colorless state. For example, the leuco dye is crystal violet lactone, and when the leuco dye and a color changing system of a color developing agent bisphenol A are cooled to a certain temperature in a certain medium, the bisphenol A releases protons, so that electrons are obtained, the crystal violet lactone is subjected to ring opening, molecular rearrangement, the conjugated double bonds are communicated, and the bisphenol A ions are combined, so that the color is presented.
At present, the thermosensitive color-changing printing on the textile adopts thermosensitive color-changing paint, namely, after the thermosensitive color-changing organic dye is processed into microcapsules, the microcapsules are printed on the textile by adopting a paint printing process. In the market, most of the thermosensitive color-changing coating products are reversible single-layer temperature-changing microcapsules. The temperature-change material as the core material has relatively active chemical properties and is easily influenced by light. The existing temperature change microcapsule products on the market all have the problem of easy failure due to temperature change, particularly the microcapsule products can not be used for a long time under illumination, for example, color-changing printed textile fabrics under strong sunlight can not be used for a plurality of times outdoors.
Disclosure of Invention
In view of the above, the invention provides a durable thermochromic material, a preparation method thereof and application thereof in textiles.
The invention provides a durable thermochromic material which has a microcapsule structure, wherein a thermochromic organic dye is taken as a core material of a microcapsule, and the core material is sequentially coated with a first capsule wall and a second capsule wall; the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting ultraviolet resistant agent, polyvinyl alcohol and n-butyl aldehyde.
Preferably, the thermochromic organic dye includes crystal violet lactone and a color developer which is any one of phenol, bisphenol a, calcium chloride, stearic acid, lauric acid, and boric acid.
Preferably, the anti-ultraviolet agent is titanium dioxide and/or an ultraviolet absorbent.
The present invention provides a process for the preparation of a long-lasting thermochromic material as described hereinbefore, comprising the steps of:
s1, providing single-layer microcapsule powder; the single-layer microcapsule powder consists of a thermosensitive color-changing organic dye and a capsule wall coated by the thermosensitive color-changing organic dye; the capsule wall is formed by polymerizing polyvinyl alcohol and n-butyraldehyde;
s2, mixing the single-layer microcapsule powder, the ultraviolet resistant agent, the polyvinyl alcohol and the n-butyl aldehyde in a water-containing solvent, stirring to enable water to permeate into the single-layer microcapsule, and heating for reaction to obtain the durable thermochromic material with the double-layer capsule wall.
Preferably, the thermochromic organic dye comprises crystal violet lactone and a developer; the single-layer microcapsule powder is obtained according to the following steps:
mixing the crystal violet lactone and the color developing agent in a molten solvent, heating, carrying out heat preservation reaction, and cooling to obtain a dark blue solid; the solvent is preferably one or more of dodecanol, tetradecanol, hexadecanol, octadecanol, paraffin, lauric acid, glyceryl laurate, n-butyl stearate, glyceryl monostearate, phenyl salicylate and p-azoxyanisole;
preparing the dark blue solid, an emulsifier and water into a core material emulsion;
and adding a prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde into the core material emulsion under the stirring condition, reacting at constant temperature, and separating to obtain single-layer microcapsule powder.
Preferably, the mass ratio of the crystal violet lactone to the color developing agent is 2-3: 4-6; the mass ratio of the polyvinyl alcohol and the n-butyl aldehyde for forming the prepolymer solution is 20-30: 15-20.
Preferably, in the step S2, 20 to 30 parts by mass of the single-layer microcapsule powder, 5 to 10 parts by mass of the ultraviolet resistant agent, 10 to 20 parts by mass of polyvinyl alcohol, and 10 to 15 parts by mass of n-butyraldehyde are mixed in an aqueous solvent.
Preferably, in the step S2, the reaction temperature is 70-80 ℃, the pH value is 4-6, and the reaction time is 3-4 h.
The present invention provides a printing paste comprising a long-lasting thermochromic material as described hereinbefore.
The invention provides a printed fabric which is prepared by printing a fabric by using the printing paste.
Compared with the prior art, the invention provides the microcapsule color-changing material with the double-layer capsule wall, wherein the core material thermosensitive color-changing organic dye is coated by the first capsule wall and the second capsule wall in a double-layer mode, the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting an ultraviolet resistant agent, the polyvinyl alcohol and the n-butyl aldehyde. Compared with the existing products on the market, the durability of the thermochromic material is greatly improved. And because of the double-layer coating form, the invention can coat various color-changing system components and keep stable, does not influence color development, has better protection on the core material, ensures that the material is not easy to leak, and has good washing resistance and durability. Therefore, the thermochromic material provided by the invention has higher reversible color change durability and is beneficial to long-term use of color-changing textiles.
Drawings
FIG. 1 is a sample photograph of a size 2 printed fabric according to example 1 of the present invention;
FIG. 2 is a photograph showing a sample of paste 2 printed fabric in example 1 after being discolored;
FIG. 3 is a photograph showing a sample of paste 2 printed fabric in example 1 of the present invention after changing color for a long time at elevated temperature.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a durable thermochromic material which has a microcapsule structure, wherein a thermochromic organic dye is taken as a core material of a microcapsule, and the core material is sequentially coated with a first capsule wall and a second capsule wall; the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting ultraviolet resistant agent, polyvinyl alcohol and n-butyl aldehyde.
The thermochromic material provided by the invention has high reversible color change durability, can be used for obtaining color-changing textiles through processes such as printing and the like, can reversibly change color at a specific temperature, improves the light fastness, and can be used for a long time.
The thermochromic material is of a double-layer thermochromic microcapsule structure, namely, the thermochromic material is composed of a core material and two capsule walls, wherein the core material is thermochromic organic dye. The thermochromic organic dye is a thermochromic compound and mainly comprises a color former, a color developer and a solvent compound (also called as a temperature regulator).
In the preferred embodiment of the invention, a compound of a chromophoric agent crystal violet lactone and a color developing agent is adopted; crystal violet lactone (colorless) is selected as a leuco body, crystal violet lactone with a lactone structure is selected as an electron donor, electrons can be given, and structural change is generated under the action of a color developing agent, namely an electron donor, so that color change is caused. The color developer may be any one of phenol, bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), calcium chloride, stearic acid, lauric acid, boric acid, and the like, and preferably bisphenol a. The mass ratio of the crystal violet lactone to the color developer is preferably 2-3: 4-6.
In addition, the solvent compound can be one or more of dodecanol, tetradecanol, hexadecanol, octadecanol, paraffin, lauric acid, glyceryl laurate, n-butyl stearate, glyceryl monostearate, phenyl salicylate, p-azoxyanisole, and the like.
In the invention, the core material is sequentially coated with a first capsule wall and a second capsule wall; the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting ultraviolet resistant agent, polyvinyl alcohol and n-butyl aldehyde. The double-layer capsule wall has better sealing property and strength, can wrap various color-changing system components, and can more easily ensure that the contents are not lost; the outer layer of the temperature-sensitive color-changing system is protected by the ultraviolet-resistant agent, so that the stability of the color-changing material under the illumination condition is improved, the color-changing material is not easy to lose efficacy, and the effect of generating reversible thermochromism according to the temperature change is achieved.
Wherein, the anti-ultraviolet agent can be one or more of titanium dioxide and ultraviolet absorbent, such as benzotriazole, triazine, salicylate and benzophenone ultraviolet absorbent.
Accordingly, embodiments of the present invention provide a method for preparing a persistent thermochromic material as described above, comprising the steps of:
s1, providing single-layer microcapsule powder; the single-layer microcapsule powder consists of a thermosensitive color-changing organic dye and a capsule wall coated by the thermosensitive color-changing organic dye; the capsule wall is formed by polymerizing polyvinyl alcohol and n-butyraldehyde;
s2, mixing the single-layer microcapsule powder, the ultraviolet resistant agent, the polyvinyl alcohol and the n-butyl aldehyde in a water-containing solvent, stirring to enable water to permeate into the single-layer microcapsule, and heating for reaction to obtain the durable thermochromic material with the double-layer capsule wall.
Preferably, the thermochromic organic dye in the single-layer microcapsule powder of the present invention comprises: crystal violet lactone colour former and colour developing agent. The color developer may be any one of phenol, bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), calcium chloride, stearic acid, lauric acid, boric acid, and the like, and preferably bisphenol a. The mass ratio of the crystal violet lactone to the color developer is preferably 2-3: 4-6.
The embodiment of the invention firstly prepares the single-layer microcapsule powder (referred to as single-layer temperature change microcapsule) containing the color-changing functional material, and mainly comprises the steps of preparing a thermochromic compound and single-layer microencapsulation.
In the embodiment of the invention, 30-50 parts by mass of solvent is heated and melted, 2-3 parts of chromophoric agent crystal violet lactone and 4-6 parts of color developing agent are sequentially added after the solvent is completely melted, the temperature of the reaction kettle is raised to 90 ℃, the mixture is fully stirred and kept for 1-2 hours, and the mixture is naturally cooled to room temperature to obtain the dark blue solid.
The solvent for heating and melting is preferably one or a plurality of lauryl alcohol, tetradecanol, cetyl alcohol, stearyl alcohol, paraffin, lauric acid, glyceryl laurate, n-butyl stearate, glyceryl monostearate, phenyl salicylate and p-azoxyanisole; the temperature of the reaction kettle can be adjusted to be constant at 10 ℃ higher than the melting point of the corresponding solvent, and the stirring speed is 400 r/min. The reaction temperature for preparing the thermochromic compound can be 80-90 ℃, and the stirring speed is properly increased to 600 r/min; and transferring the fully reacted color-changing compound solution after the reaction is finished, naturally cooling to room temperature, and obtaining the dark blue solid for later use.
Then, the dark blue solid, an emulsifier and water are prepared into a core material emulsion; the emulsifier can be one or more of Arabic gum, sodium dodecyl benzene sulfonate, styrene-maleic anhydride copolymer, OP-10, Tween-80, Span-80 and Span-60. Specifically, 2-3 parts by mass of an emulsifier is selected and added into 40-50 parts of water to prepare an emulsifier solution; heating and stirring until the mixture is completely dissolved, and cooling to room temperature. Preferably, the emulsifier solution is slowly warmed up to 65 ℃ with stirring, and 40-50 parts of dark blue solid is slowly added and emulsified to form a core material emulsion. The emulsification process preferably comprises: firstly, emulsifying for 10min at 10000r/min by a high-speed shearing emulsifying machine under the water bath condition of 65 ℃, and then ultrasonically emulsifying for 10min at the frequency of 100HZ to obtain the core material emulsion.
The embodiment of the invention mainly adopts prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde to realize single-layer microencapsulation of the core material. The polyvinyl alcohol is white powder and is easy to dissolve in water, and linear polyvinyl alcohol with the average polymerization degree of 1500-2500 is specifically selected; the mass ratio of the polyvinyl alcohol to the n-butyraldehyde in the prepolymer solution is preferably 20-30: 15-20. According to the mass parts, preferably weighing 20-30 parts of polyvinyl alcohol, adding 20-30 parts of water, heating to 40 ℃, stirring at a rotation speed of 400r/min, heating to 95 ℃, and rotating at a rotation speed of 1000r/min until the polyvinyl alcohol is completely dissolved; the temperature can be reduced to 40 ℃, 15-20 parts by mass of n-butyl aldehyde is slowly dropped into the mixture under the stirring of 500r/min, the mixture is mixed for 1h-1.5h, the pH value is preferably adjusted to 4-6 by hydrochloric acid or acetic acid, the temperature is slowly increased to 40 ℃, and the temperature is kept for 3-4h, so that the prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde is obtained.
Under the condition of room temperature, the embodiment of the invention preferably weighs a prepolymer solution consisting of 50 parts by mass of polyvinyl alcohol and n-butyl aldehyde, can slowly drop the core material emulsion into the prepolymer solution under the stirring of 400r/min, slowly raises the temperature to 70-80 ℃, reacts at constant temperature for 3-4h, then slowly lowers the temperature to room temperature, is washed by water and is filtered by suction, and single-layer microcapsule powder is obtained by separation. The single-layer microcapsule prepared by the embodiment of the invention has simple auxiliary components, cannot influence stability due to phase separation, is easy to separate, and is convenient for the subsequent synthesis of the second layer of capsule wall.
The embodiment of the invention takes the prepared single-layer microcapsule as a core and coats the capsule wall again, thereby preparing the double-layer microcapsule. According to the mass parts, in the preferred embodiment of the invention, 20-30 parts of the single-layer microcapsule powder, 5-10 parts of the ultraviolet resistant agent, 10-20 parts of polyvinyl alcohol and 10-15 parts of n-butyl aldehyde are mixed in the aqueous solvent, stirred to enable water to permeate into the single-layer microcapsule, and heated for reaction to obtain the durable thermochromic material with the double-layer capsule wall.
Wherein, 5 to 10 parts of the anti-ultraviolet agent and 10 to 20 parts of the polyvinyl alcohol are dissolved in 20 to 30 parts of the water-ethylene glycol mixed solution, preferably, the temperature is increased to 40 ℃, the rotation speed is 400r/min, the stirring is carried out, the temperature is increased to 95 ℃, and the rotation speed is 1000r/min until the polyvinyl alcohol is completely dissolved. In the embodiment of the invention, preferably, the temperature is reduced to 30 ℃, 10 to 15 parts of n-butyl aldehyde is slowly dropped into the mixture under the stirring of 500r/min, and then the polyvinyl alcohol-n-butyl aldehyde solution containing the anti-ultraviolet agent is obtained; the ultraviolet resistant agent can be titanium dioxide or ultraviolet absorbent, such as benzotriazole, triazine, salicylate, and benzophenone ultraviolet absorbent.
Finally, 20-30 parts of reversible thermochromic single-layer microcapsule powder is weighed and added into the polyvinyl alcohol-n-butyl aldehyde solution, and the mixture is stirred for 1-2 hours, so that the aqueous solution is fully permeated into the microcapsules; preferably, hydrochloric acid or acetic acid is used for adjusting the pH value to 4-6, the temperature can be slowly raised to 70-80 ℃, the reaction is carried out for 3-4h at constant temperature, and then the temperature is slowly reduced to the room temperature. According to the embodiment of the invention, the cooled microcapsule solution is cleaned by a large amount of distilled water and is filtered, and then the microcapsule solution is placed in a vacuum oven for drying, so that the reversible thermochromic double-layer microcapsule powder is obtained. The specific operation of the embodiment of the invention is uniform and sufficient in dispersion, which is beneficial to improving the uniformity of the particle size of the microcapsule particles, otherwise, the uniformity and the fastness of color development are easily influenced.
In the embodiment of the invention, the reversible thermochromic double-layer microcapsule powder is a temperature-sensitive color-changing material or a thermochromic material, has a high reversible color-changing durability and good color rendering property, can be applied to a fabric in a printing process, and has a micron and nanometer grade particle size.
The embodiment of the invention provides printing paste which comprises the durable thermochromic material. Specifically, the printing paste comprises the following components in parts by mass: 10-20 parts of lasting thermochromic material, 10-20 parts of printing adhesive, 1-3 parts of penetrating agent, 0.5-1 part of thickening agent and 30-40 parts of water. Wherein, the adhesive and the thickening agent are independently preferably aqueous auxiliary agents; the penetrating agent can be JFC, and in addition, the penetrating agent can also comprise 2-3 parts of additives such as a hydrophilic agent and the like.
In a specific embodiment of the present invention, the printing paste is: 10 parts of the double-layer microcapsule powder, 10 parts of a water-based polyacrylate adhesive, 2.5 parts of a penetrating agent JFC, 0.5 part of a water-based thickening agent and 30 parts of water, and adding acetic acid to adjust the pH value to 4-6; the viscosity of the printing paste is 2050mpa · s (20 ℃).
The embodiment of the invention provides a printed fabric, which is prepared by printing a fabric by using the printing paste. The fabric is not particularly limited by the embodiment of the invention, and any type of fabric can be adopted to carry out the conventional printing process. Specifically, drying at 80-100 ℃ for 3-5min after printing, and drying at 140-160 ℃ for 3-5 min; preferably, the fabric is dried at 80 ℃ for 3min and at 140 ℃ for 5min after printing.
The printed fabric obtained by the embodiment of the invention has a color change phenomenon after temperature change, can be recovered after color change, has improved light fastness and washing fastness, and can be used for a long time.
For further understanding of the present application, the permanent thermochromic materials provided herein, their method of preparation and use in textiles are specifically described below in connection with the examples. It should be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is defined by the following examples.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products available on the market.
In the following examples, linear polyvinyl alcohol was selected, and the average degree of polymerization was 1500-.
Example 1
1) Preparation of Single-layer temperature-Change microcapsules
Preparing a color-changing compound: the temperature of the reaction kettle is adjusted to be 50 ℃ which is 10 ℃ higher than the melting point of corresponding solvent tetradecanol, the stirring speed is 400r/min, and 40 parts of tetradecanol is heated and melted. And after the solvent is completely changed into a molten state, sequentially adding 3 parts of color former crystal violet lactone and 6 parts of color developing agent bisphenol A, simultaneously raising the temperature of the reaction kettle to 90 ℃, properly increasing the stirring speed to 600r/min, fully stirring and preserving heat for 2 hours, after the reaction is finished, transferring the color changing compound solution obtained by full reaction, and naturally cooling to room temperature to obtain a dark blue solid for later use.
Selecting 2 parts of emulsifier Tween-80, and adding 40 parts of water to prepare an emulsifier solution; during preparation, the mixture is heated and stirred until the mixture is completely dissolved, and is cooled to room temperature. Slowly heating the emulsifier solution to 65 ℃ under stirring, slowly adding 40 parts of the color-changing compound, emulsifying by a high-speed shearing emulsifying machine at 10000r/min under the condition of water bath at 65 ℃, and ultrasonically emulsifying for 10min at 100HZ frequency after 10min to form core material emulsion (emulsion).
Weighing 20 parts of polyvinyl alcohol, adding 30 parts of water, heating to 40 ℃, stirring at the rotating speed of 400r/min, heating to 95 ℃, and rotating at the rotating speed of 1000r/min until the polyvinyl alcohol is completely dissolved; cooling to 40 ℃, slowly dripping 20 parts of n-butyraldehyde into the mixture under stirring at 500r/min, and mixing for 1.5 hours; adjusting the pH value to 4-6 by using hydrochloric acid or acetic acid, slowly heating to 40 ℃, and preserving heat for 4 hours to obtain a prepolymer solution.
Weighing 50 parts of prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde at room temperature, slowly dripping the core material emulsion into the prepolymer solution under the stirring of 400r/min, slowly heating to 80 ℃, reacting at constant temperature for 4 hours, then slowly cooling to room temperature, washing with water and carrying out suction filtration to obtain single-layer microcapsule powder, and marking as microcapsule 1.
2) Preparation of double-layer microcapsules
Dissolving 10 parts of benzotriazole ultraviolet absorbent Tinuvin 1130 (Passion company) and 15 parts of polyvinyl alcohol in 25 parts of water-ethylene glycol mixed solution (the volume ratio of the solvent is 3:2), heating to 40 ℃, stirring at the rotating speed of 400r/min, heating to 95 ℃, and rotating speed of 1000r/min until the polyvinyl alcohol and the like are completely dissolved; and cooling to 30 ℃, and slowly dripping 15 parts of n-butyl aldehyde while stirring at 500r/min to obtain the polyvinyl alcohol-n-butyl aldehyde solution.
Weighing 30 parts of single-layer microcapsule powder prepared in the step 1), adding the single-layer microcapsule powder into the polyvinyl alcohol-n-butyraldehyde solution, and stirring for 2 hours to enable the water solution to permeate into the microcapsules; adjusting the pH value to 4-6 by using hydrochloric acid or acetic acid, slowly heating to 80 ℃, reacting at constant temperature for 3.5 hours, and then slowly cooling to room temperature.
Washing and filtering the obtained microcapsule solution by using a large amount of distilled water, and then placing the microcapsule solution in a vacuum oven for drying to obtain reversible thermochromic double-layer microcapsule powder (called double-layer thermochromic capsule powder for short) which is marked as microcapsule 2; the particles were of uniform size and the particle size parameters are given in the table below.
Table 1 particle size of double-layer microcapsules prepared in examples of the present invention
The test method comprises the following steps: after the microcapsules were diluted 1000 times with distilled water, the emulsion particle size and distribution were measured using a Nano-ZS type Nano particle size and potential analyzer.
3) Printing technology
Selecting 180g/gsm bleached all-cotton plain cloth as a fabric body, and then printing a printing functional layer on the outer layer of the fabric body to obtain the printing fabric.
Printing paste 1: 10 parts of the single-layer temperature change microcapsule powder, 10 parts of an aqueous polyacrylate adhesive, Hitachi Chailin UDT LIQ (Ongo Co.), 2.5 parts of a penetrating agent JFC (Hensmai Co.), 0.5 part of an aqueous thickening agent PTF (Hensmai Co.), and 30 parts of water; adding acetic acid to adjust pH to about 6. The printing paste is used as a comparison group, and other processes are the same except that the color-changing functional materials are different.
Printing paste 2: 10 parts of the double-layer temperature-change capsule powder, 10 parts of a water-based polyacrylate adhesive, 2.5 parts of a penetrating agent JFC, 0.5 part of a water-based thickener PTF and 30 parts of water; and adding acetic acid to adjust the pH value to about 6, wherein the viscosity of the printing paste is 2050mpa & s (20 ℃).
The printing process comprises the following steps: and (3) drying 20 parts of the obtained printing paste for flat screen printing at 80 ℃ for 3min and at 140 ℃ for 5 min.
Example 2
1) Preparation of Single-layer temperature-Change microcapsules
Preparing a color-changing compound: the temperature of the reaction kettle is adjusted to be constant at 40 ℃ which is 10 ℃ higher than the melting point of the corresponding solvent n-butyl stearate, the stirring speed is 400r/min, and 50 parts of n-butyl stearate is heated and melted. After the solvent is completely changed into a molten state, sequentially adding 2.5 parts of color former crystal violet lactone and 5.5 parts of color developing agent phenol, simultaneously raising the temperature of the reaction kettle to 90 ℃, properly increasing the stirring rotating speed to 600r/min, fully stirring and preserving heat for 2 hours, after the reaction is finished, transferring the color changing compound solution obtained by full reaction, and naturally cooling to room temperature to obtain a dark blue solid for later use.
2 parts of emulsifier styrene-maleic anhydride copolymer is selected and added into 40 parts of water to prepare emulsifier solution; during preparation, the mixture is heated and stirred until the mixture is completely dissolved, and is cooled to room temperature. Slowly heating the emulsifier solution to 65 ℃ under stirring, slowly adding 40 parts of the color-changing compound, emulsifying by a high-speed shearing emulsifying machine at 10000r/min under the condition of water bath at 65 ℃, and ultrasonically emulsifying for 10min at 100HZ frequency after 10min to form core material emulsion.
Weighing 20 parts of polyvinyl alcohol, adding 25 parts of water, heating to 40 ℃, stirring at the rotating speed of 400r/min, heating to 95 ℃, and rotating at the rotating speed of 1000r/min until the polyvinyl alcohol is completely dissolved; cooling to 40 ℃, slowly dripping 20 parts of n-butyl aldehyde while stirring at 500r/min, and mixing for 1 h; adjusting the pH value to 4-6 by using hydrochloric acid or acetic acid, slowly heating to 40 ℃, and preserving heat for 4 hours to obtain a prepolymer solution.
Weighing 50 parts of prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde at room temperature, slowly dripping the core material emulsion into the prepolymer solution under the stirring of 400r/min, slowly heating to 80 ℃, reacting at constant temperature for 4 hours, then slowly cooling to room temperature, washing with water and carrying out suction filtration to obtain single-layer microcapsule powder.
2) Preparation of double-layer microcapsules
Dissolving 4 parts of titanium dioxide, 4 parts of benzophenone ultraviolet absorbent Chimassorb 81 (Pasteur company) and 15 parts of polyvinyl alcohol in 20 parts of water-glycol mixed solution (the volume ratio of the solvent is 3:2), heating to 40 ℃, stirring at the rotating speed of 400r/min, heating to 95 ℃, and rotating at the rotating speed of 1000r/min until the polyvinyl alcohol and the like are completely dissolved; and cooling to 30 ℃, and slowly dripping 15 parts of n-butyl aldehyde while stirring at 500r/min to obtain the polyvinyl alcohol-n-butyl aldehyde solution.
Weighing 30 parts of single-layer microcapsule powder prepared in the step 1), adding the single-layer microcapsule powder into the polyvinyl alcohol-n-butyraldehyde solution, and stirring for 2 hours to enable the water solution to permeate into the microcapsules; adjusting the pH value to 4-6 by using hydrochloric acid or acetic acid, slowly heating to 80 ℃, reacting at constant temperature for 3.5 hours, and then slowly cooling to room temperature.
Washing and filtering the obtained microcapsule solution by using a large amount of distilled water, and then placing the microcapsule solution in a vacuum oven for drying to obtain reversible thermochromic double-layer microcapsule powder which is marked as microcapsule 3; the particle size was uniform, and the particle size parameters are shown in table 1.
3) Printing technology
Selecting 180g/gsm bleached all-cotton plain cloth as a fabric body, and then printing a printing functional layer on the outer layer of the fabric body to obtain the printing fabric.
Printing paste 3: 10 parts of the double-layer temperature-change capsule powder, 10 parts of a water-based polyacrylate adhesive, 2.5 parts of a penetrating agent JFC, 0.5 part of a water-based thickener PTF and 30 parts of water; adding acetic acid to adjust pH to about 6.
The printing process comprises the following steps: after printing (the process is the same as that of example 1), drying is carried out for 3min at 80 ℃ and baking is carried out for 5min at 140 ℃.
The performance of the printed fabric obtained in the embodiment of the invention is shown as follows; the conditions before and after the color of the size 2 printed fabric sample is changed are shown in figures 1-3, and it can be found that the blue color on the fabric gradually disappears and becomes colorless after the temperature is increased, the temperature increasing time of figures 2 and 3 is different, the temperature increasing time of figure 3 is longer, and the color change is more obvious.
According to tables 2 and 3, the printed fabric of size 1 and the printed fabric of size 2 in the embodiment of the application are compared, and the printing color uniformity of the double-layer microcapsule is improved and the light fastness is greatly improved due to the fact that the printing K/S value of the double-layer microcapsule is slightly reduced. Compared with the size 2 printed fabric, the size 3 printed fabric has the advantages that the used color-changing dye amount is reduced, the microcapsule particle size is reduced, the printing color depth is reduced, the uniformity is further improved, the fastness is approximately equivalent, and the condition that the double-layer microcapsule protection is the main reason for improving the fastness is shown.
Table 2 color change performance of printed fabric obtained in the embodiment of the present invention
TABLE 3 light fastness of printed fabrics obtained in the examples of the invention
The fabric performance detection method comprises the following steps:
1. apparent color yield: the apparent color yield of the printed fabric was tested on a Datacolor650 color measuring and matching machine. Expressed by K/S value, the larger the K/S value, the higher the apparent color yield.
2. Uniformity: selecting a certain point as a reference point, measuring the color difference delta E of the fabric by using a color measuring and matching instrument at n different positions on the fabric, and then carrying out average color difference calculation according to the following formula to obtain the average color difference as the measurement standard of uniformity. The smaller the numerical value is, the smaller the color difference between the fabric point and the point is, the better the coloring uniformity is;
3. thermochromic behavior: using an ironing sublimation fastness instrument to ensure that the temperature of a heating plate is 3 ℃ higher than the color change temperature of the sample; and (3) placing the sample on a heating plate, heating for five minutes, comparing with the original sample, and observing whether the surface printing of the sample is changed.
4. Washing and drying procedures: washing for 5 times according to GB/T8629 and 2017: procedure 4N (type a), ECE detergent 98(20g, a: B: C: 77:20:3), hung to dry.
5. Light fastness test: the color fastness to light and sweat is conformed according to the color fastness test of GB/T14576-.
6. Light-resistant shot-light method: and (3) irradiating the material for 72 hours at room temperature by adopting a light source of an LED spotlight of the rail-mounted spotlight.
7. Sunlight yellowing resistance: according to the phenomenon that the fabric is easy to turn yellow under the long-time irradiation of sunlight, under the environment of simulating the irradiation of the sunlight by a solar bulb and a heating temperature control device, a sample is placed for a period of time, and then the color change grade of the sample is evaluated, specifically under a D65 light source, by using a gray sample card for evaluation.
From the above examples, it is clear that the durability of the thermochromic material of the present invention is greatly improved compared to the existing commercial products. In addition, the invention can coat various color-changing system components and keep stable, does not influence color development, and has good washing resistance and durability. The thermochromic material provided by the invention has higher reversible color change durability and is beneficial to long-term use of color-changing textiles.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. A persistent thermochromic material has a microcapsule structure and is characterized in that a thermochromic organic dye is taken as a core material of a microcapsule, and the core material is sequentially coated with a first capsule wall and a second capsule wall; the first capsule wall is formed by polymerizing polyvinyl alcohol and n-butyl aldehyde, and the second capsule wall is formed by reacting ultraviolet resistant agent, polyvinyl alcohol and n-butyl aldehyde.
2. The persistent thermochromic material of claim 1, wherein the thermochromic organic dye includes crystal violet lactone and a color developer that is any one of phenol, bisphenol a, calcium chloride, stearic acid, lauric acid, and boric acid.
3. A persistent thermochromic material according to claim 1 or 2, wherein the uv-resistant agent is titanium dioxide and/or a uv-absorber.
4. A method of preparing a long-lasting thermochromic material as claimed in any of claims 1 to 3, comprising the steps of:
s1, providing single-layer microcapsule powder; the single-layer microcapsule powder consists of a thermosensitive color-changing organic dye and a capsule wall coated by the thermosensitive color-changing organic dye; the capsule wall is formed by polymerizing polyvinyl alcohol and n-butyraldehyde;
s2, mixing the single-layer microcapsule powder, the ultraviolet resistant agent, the polyvinyl alcohol and the n-butyl aldehyde in a water-containing solvent, stirring to enable water to permeate into the single-layer microcapsule, and heating for reaction to obtain the durable thermochromic material with the double-layer capsule wall.
5. The method of claim 4, wherein the thermochromic organic dye includes crystal violet lactone and a developer; the single-layer microcapsule powder is obtained according to the following steps:
mixing the crystal violet lactone and the color developing agent in a molten solvent, heating, carrying out heat preservation reaction, and cooling to obtain a dark blue solid; the solvent is preferably one or more of dodecanol, tetradecanol, hexadecanol, octadecanol, paraffin, lauric acid, glyceryl laurate, n-butyl stearate, glyceryl monostearate, phenyl salicylate and p-azoxyanisole;
preparing the dark blue solid, an emulsifier and water into a core material emulsion;
and adding a prepolymer solution formed by polyvinyl alcohol and n-butyl aldehyde into the core material emulsion under the stirring condition, reacting at constant temperature, and separating to obtain single-layer microcapsule powder.
6. A preparation method according to claim 5, wherein the mass ratio of the crystal violet lactone to the color developer is 2-3: 4-6; the mass ratio of the polyvinyl alcohol and the n-butyl aldehyde for forming the prepolymer solution is 20-30: 15-20.
7. The production method according to claim 6, wherein in the step S2, 20 to 30 parts by mass of the single-layer microcapsule powder, 5 to 10 parts by mass of an ultraviolet inhibitor, 10 to 20 parts by mass of polyvinyl alcohol, and 10 to 15 parts by mass of n-butyraldehyde are mixed in an aqueous solvent.
8. The method according to claim 7, wherein in step S2, the reaction temperature is 70-80 ℃, the pH value is 4-6, and the reaction time is 3-4 h.
9. Printing paste, characterized in that it comprises a long-lasting thermochromic material according to any of claims 1 to 3.
10. A printed fabric, which is characterized in that the printed fabric is obtained by printing a fabric with the printing paste according to claim 9.
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