CN115679708A - Microcapsule coating fabric with photo-initiation self-warning or self-repairing function and preparation method thereof - Google Patents
Microcapsule coating fabric with photo-initiation self-warning or self-repairing function and preparation method thereof Download PDFInfo
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- CN115679708A CN115679708A CN202211263554.1A CN202211263554A CN115679708A CN 115679708 A CN115679708 A CN 115679708A CN 202211263554 A CN202211263554 A CN 202211263554A CN 115679708 A CN115679708 A CN 115679708A
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Abstract
The invention relates to a photo-initiated self-warning or self-repairing microcapsule coated fabric and a preparation method thereof. The coating fabric is damaged and the microcapsules at the position are broken, the light responsive material flows out, the specific UV light or visible light irradiates the coating fabric, the optical fiber coating fabric can also introduce the specific UV light or visible light into the fabric through the optical fiber, and the light responsive material generates light response according to the received light signal to perform self-warning or self-repairing on the coating fabric. The method has the advantages of simple process, regular microcapsule appearance and good stability, and once the coated fabric has micro cracks, the method can report the cracks in the fabric in an early warning manner, reduce loss, realize automatic repair of the micro cracks of the material through specific light, and prolong the service life of the fabric.
Description
Technical Field
The invention relates to the field of functional fabrics, in particular to a microcapsule coating fabric with photo-initiation self-warning or self-repairing function and a preparation method thereof.
Background
In the process of processing, forming and using of the polymer composite material, the polymer composite material is influenced by environment, external force and the like, and micro cracks are inevitably generated on the surface and inside of the polymer composite material. If the microcracks cannot be detected and repaired in time, the microcracks continue to expand to cause cracking of a matrix of the composite material or interlayer degumming, so that the mechanical property of the composite material is reduced, macroscopic cracks can be caused, brittle fracture can occur, the composite material is finally failed, and major accidents are caused.
The polymer composite material can automatically repair internal or external microcracks, so that the mechanical property of the material is enhanced, the service life is prolonged, the polymer composite material is widely applied to the fields of automobiles, aerospace, aviation manufacturing and the like, and has very important significance in reducing equipment maintenance cost, reducing equipment maintenance time, prolonging the service life of the equipment and the like.
The self-repairing system can be divided into an intrinsic self-repairing system and an embedded self-repairing system; the buried self-repairing system has simple structure and good repairing effect and is widely regarded. The embedded self-repairing system takes microcapsule, glass fiber or repairing agent wrapped by vessel as a unit and is embedded into a polymer matrix for repairing; the repairing process of the microcapsule self-repairing material comprises the steps that cracks in a matrix expand to the microcapsules to cause the microcapsules to break, repairing agents in the microcapsules flow to the cracks under the capillary action, and the repairing agents generate polymerization reaction under the action of catalysts to repair the cracks. The microcapsule composite material has simple preparation process and wide repairable matrixes, can repair various damages to the material and becomes a hot spot and a key point of the self-repairing material.
At room temperature, if the crack contains a photosensitive group capable of forming a new chemical bond, the polymer can be self-repaired under illumination to obtain a large number of photosensitive groups on the surface of the crack, which is important for the self-repairing behavior of the polymer. These photosensitive groups are part of the polymer structure and do not affect other properties of the polymer. The use of UV light or visible light as a stimulus to external conditions can effect re-crosslinking of the polymer structure, completing the self-healing process.
The textile material is used as a substrate, the light responsive material microcapsule and the coating adhesive are loaded on the substrate in a mixed manner, and the UV light or visible light is used for inducing the light responsive material to realize self-warning or self-repairing, so that the functional textile which can perform self-warning or self-repairing through light initiation is prepared.
Disclosure of Invention
The invention aims to solve the technical problem of a microcapsule coating fabric with photoinitiation self-warning or self-repairing function and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the microcapsule coated fabric capable of self-warning or self-repairing through light initiation comprises a fabric base fabric and a coating loaded with self-warning or self-repairing photoresponse microcapsules, wherein the coating loaded with the microcapsules is attached to one surface or two surfaces of the fabric base fabric.
Further, the fabric base cloth is a common base cloth or an optical fiber fabric, and the common base cloth is woven by any one or more of polyester, nylon, polypropylene, spandex, acrylon, polylactic acid, viscose, cotton, hemp or wool through weaving, knitting or non-weaving process; the optical fiber fabric is woven by adopting a side light-emitting optical fiber through a weaving process or is woven by adopting a side light-emitting optical fiber and common yarns according to a required interval weaving method.
Further, the side emitting optical fiber may be a finished side emitting optical fiber or a side emitting optical fiber obtained by laser processing, mechanical polishing or chemical etching of the end emitting optical fiber.
Further, the light source is 280-400 nm UV light or 400-780 nm visible light, and for a common fabric, an external specific light source is adopted to irradiate the surface of the fabric to realize self-warning or self-repairing; for the optical fiber fabric, an external specific light source is adopted to irradiate the surface of the fabric or required specific light is introduced into the side light-emitting optical fiber, so that the self-warning or self-repairing of the fabric is realized.
Further, the coating loaded with the self-warning or self-repairing light-responsive microcapsules comprises a coating adhesive and the light-responsive microcapsules, wherein the light-responsive microcapsules can be self-warning microcapsules or self-repairing microcapsules and are dispersed in the coating, and the average particle size of the light-responsive microcapsules is less than or equal to 80 microns. Wherein the coating adhesive is one or more of PVC, epoxy resin, polyurethane, polyamide, polydimethylsiloxane and polyethylene, the photoresponse microcapsule consists of a wall material and a core material, and the mass percentage of the coating adhesive to the photoresponse microcapsule is (10).
Further, the wall material of the light-responsive microcapsule comprises SiO 2 One or more of urea-formaldehyde resin, polyurea formaldehyde or melamine-formaldehyde prepolymer.
Further, when the light response microcapsule is a self-warning light response microcapsule, the core material comprises one or more of ultraviolet response photochromic dye, fluorescent liquid OIL-GLO44-P, rhodamine-based fluorescent molecule, 2',7' -dichlorophenol fluorescein, tetrachlorofluorescein, crystal violet lactone or aggregation induced emission effect (AIE effect) molecule as a self-warning material.
Further, when the light response microcapsule is a self-repairing light response microcapsule, the core material comprises one or more of light-cured resin aliphatic polyurethane acrylate, epoxy resin, vinyl silicone oil, paraffin, methyl methacrylate, polyurethane prepolymer and dicyclopentadiene and one or more of photoinitiator, cinnamoyl, coumarinyl or anthracene polymer material.
The preparation method of the microcapsule coating fabric with photo-initiation self-warning or self-repairing function comprises the following steps:
After the technical scheme is adopted, compared with the prior art, the invention has the following advantages:
(1) By utilizing the excellent light conduction function and the side light emitting characteristic of the optical fiber, the light-responsive material can efficiently absorb light to play a light-triggered self-warning or self-repairing function, and is particularly suitable for self-repairing of fabrics in a dark environment; (2) The invention processes the end face light-emitting optical fiber into the side face light-emitting optical fiber (12), which is beneficial to improving the illumination efficiency; (3) The invention provides a coated fabric which can achieve self-warning or self-repairing effect by introducing UV light into the fabric, wherein microcapsules can load different types of self-repairing materials and photo-responsive materials, when microcracks appear on the surface or in the composite material, the UV light is introduced, and a repairing agent and a photoinitiator are dissolved out from the cracks to repair the microcracks. The optical fibers are respectively connected with light sources of different types or wavelengths, so that the corresponding light-responsive materials are activated, more efficient and synergistic self-repairing can be realized, and the optical fiber has wider practical application prospect.
The invention is described in detail below with reference to the figures and examples.
Drawings
FIG. 1 is a schematic cross-sectional view of a photo-initiated self-warning or self-repairing microcapsule coated fabric;
FIG. 2 is a schematic cross-sectional view of a light-responsive microcapsule;
FIG. 3 is a schematic cross-sectional view of a photo-initiated self-warning microcapsule coated fabric;
FIG. 4 is a schematic cross-sectional view of a photo-initiated self-healing microcapsule coated fabric;
fig. 5 is a graph of the strength of a PVC coated fabric with embedded microcapsules, where the a-curve is: fabric strength before scratching; the curve b is: after scratching, ultraviolet irradiation is carried out for 0h to obtain the fabric strength; the curve c is: after scratching, ultraviolet irradiation is carried out for 12h to obtain the fabric strength; the d curve is: after scratching, ultraviolet irradiation is carried out for 36h to obtain the fabric strength;
fig. 6 is a graph of the self-healing effect of a PVC coated fabric embedding microcapsules, wherein a is: SEM image of coating scratch; the b picture is as follows: a self-repairing SEM image after 12 hours of ultraviolet illumination; the c picture is as follows: a self-repairing SEM image after 24h of ultraviolet illumination; d is as follows: self-repairing SEM images after ultraviolet illumination for 36 h;
FIG. 7 is a fluorescence view of PVC coated fabric: PVC coating fluorescence without embedded microcapsules panel b: and after ultraviolet irradiation, the microcapsule-embedded PVC coating can automatically early warn a fluorescence image.
The list of parts represented by the various reference numbers in the drawings is as follows:
1. a fabric base fabric; 2. coating slurry; 3. self-warning or self-repairing photoresponsive microcapsules; 11. a plain yarn; 12. side-emitting optical fiber
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The first embodiment is as follows: the photoresponse microcapsule is SiO 2 Coated epoxy resin microcapsule
(1) Weaving of fabric
And designing the fabric texture into a plain weave on a weaving machine, drafting by using cotton yarns, and weaving polyester yarns to obtain the polyester plain weave fabric.
(2)SiO 2 Preparation of coated epoxy resin microcapsules
Adopting the method of interfacial polymerization and in-situ polymerization, firstly, according to the following steps of 10:10:6:5, respectively weighing epoxy resin (E-51), adipic acid diester, cationic photoinitiator and tetraethyl orthosilicate (TEOS), placing the epoxy resin, the adipic acid diester, the cationic photoinitiator and the TEOS in a beaker, manually stirring in an ultrasonic environment, preliminarily mixing, and uniformly stirring to obtain an oil phase; then, a proper amount of polyether P123 is weighed and placed in a certain amount of deionized water, and the polyether P123 is fully dissolved on a magnetic stirrer to be used as a water phase. Subsequently, the aqueous phase was added dropwise to the oil phase while stirring in an ultrasonic environment to perform preliminary emulsification. Then, the mixture is placed under a high-speed homogenizer until the mixture is stirred into uniform and stable O/W emulsion. Next, transferring the emulsion into a flat-bottomed flask, placing the flat-bottomed flask in a water bath kettle, simultaneously mechanically stirring the emulsion, and dropwise adding prepared dilute hydrochloric acid; after 4h, adding a proper amount of TEOS and a diluted hydrochloric acid solution for the first time; after 4 hours, continuously replenishing a proper amount of dilute hydrochloric acid, and totally replenishing twice; continuing to react for 12h, and ending the experiment; suspending the microcapsule in liquid, centrifuging under the action of a centrifuge, washing with deionized water for multiple times until the supernatant is neutral, taking out the microcapsule at the bottom, and drying to obtain the self-repairing photoresponse microcapsule 3 with the diameter of about 1.5 microns.
(3) Embedded SiO 2 Preparation of PVC coated fabric coated with epoxy resin microcapsules
A PVC coating fabric coated with microcapsules is prepared by a scraper coating method, EPVC (100 parts), DOP (70 parts), DOA (5 parts), a stabilizer (2.3 parts) and the microcapsules (10 parts) are uniformly mixed to prepare coating slurry 2, and the microcapsules are uniformly dispersed in the coating slurry by ultrasonic stirring. And uniformly coating the prepared coating agent on two sides of the polyester woven fabric by using a scraper, and then placing the polyester woven fabric in an oven for curing to obtain the PVC coating fabric embedded with the photoresponse microcapsules.
(4) UV light irradiation self-repair
As shown in figures 1-4, the fabric structure and action principle of the invention, a scratch with the width of about 20 μm is scratched on a coated microcapsule PVC coated fabric by a blade, the scratch is deep until the coating substrate, the coated microcapsule PVC coated fabric is taken out after being irradiated by UV light for a period of time, crack changes before and after repair are observed, and the self-repairing effect of the crack is better along with the extension of the UV light illumination time. As shown in fig. 2-3, after the coated fabric is scratched, the microcapsules at the scratched position are cracked, the repairing agent flows into the scratched position due to the capillary action, under the irradiation of an ultraviolet lamp, the photoinitiator can absorb ultraviolet light in the range of 250-300 nm, proton acid with strong chemical activity is generated under the photolysis, the ring-opening polymerization reaction of epoxy groups can be triggered, a highly cross-linked network structure is finally formed, and the adhesive cracks achieve the self-repairing effect. From the a-diagram of fig. 6, a scratch having a width of about 20 μm can be seen; the graphs b, c and d in fig. 6 are respectively the self-repairing effect graphs of the microcapsule-embedded PVC coated fabric at the coating scratch position after the ultraviolet illumination time is 12h, 24h and 36h, and it can be obviously seen from the graphs that the self-repairing effect at the crack position is better along with the increase of the ultraviolet illumination time, and the scratch is basically and completely bonded after the illumination time reaches 36h, which indicates that the microcapsule-embedded PVC coated fabric has a good self-repairing function.
Fig. 5 is a graph comparing the strengths of the PVC coated fabrics embedded with the microcapsules, wherein the strength of the coated fabric measured before scratching is 732N, the strength of the coated fabric measured after scratching by ultraviolet light for 0h is 662N, the strength of the coated fabric measured after 12h of light is 683N, and the strength of the coated fabric measured after 36h of light is 720N, which is not much different from the strength of the fabric before scratching, and thus it can be seen that the scratched part of the fabric is basically and completely self-repaired. Therefore, the strength of the PVC coated fabric embedded with the microcapsules is gradually increased along with the increase of the ultraviolet light irradiation time, and the strength of the fabric is maximum when the light irradiation time reaches 36h, so that the fabric is basically and completely healed.
The second embodiment: the light response microcapsule is urea-formaldehyde resin coated light-cured resin aliphatic polyurethane acrylate microcapsule
(1) Weaving of fabric
The fabric tissue is designed to be plain woven on a weaving machine, cotton yarn is used for drafting, the finished side light-emitting optical fiber 12 and nylon yarn, namely common yarn 11 are woven in at intervals, a certain length of the optical fiber needs to be reserved on one side of the fabric to extend out of the fabric, and the side light-emitting optical fiber 12 fabric base cloth 1 is obtained.
(2) Preparation of urea-formaldehyde resin coated photocuring resin aliphatic polyurethane acrylate microcapsule
Adding urea and formaldehyde solution into a three-neck flask by adopting an in-situ polymerization two-step method, regulating the pH value to be 8-9 by using triethanolamine, magnetically stirring for 1h at a constant temperature of 70 ℃ to obtain a transparent prepolymer solution, adding polyurethane acrylate RJ423, HDDA and a photoinitiator (the mass ratio is 4.9: 0.2) which are uniformly ultrasonically mixed into a polyurea-formaldehyde prepolymer, emulsifying for 30min at a certain rotating speed, regulating the pH value of a system to be 3-4 by using dilute hydrochloric acid, slowly heating to 60 ℃, reacting for 2-3 h, washing, filtering and drying a precipitate at the bottom of the flask to obtain white microcapsule powder.
(3) Preparation of epoxy resin coating fabric coated with urea-formaldehyde resin-coated photocuring resin aliphatic polyurethane acrylate microcapsules
Uniformly mixing epoxy resin E51, a diluent TMPEG and a photoinitiator 6992 (the mass ratio is 6.9: 2.9: 0.2) by ultrasonic, uniformly dispersing 5% of microcapsules in the microcapsules by mechanical stirring, coating the coating slurry on the surface of an optical fiber fabric by a scraper coating method, and then irradiating the optical fiber fabric by ultraviolet light with the wavelength of 365nm and the power of 500W for 5min in a photochemical reaction device under the condition of room temperature to cure the epoxy resin. And obtaining the microcapsule-embedded epoxy resin coating fabric.
(4) UV light irradiation self-repair
And (3) scratching a scratch with the width of about 20 micrometers on the microcapsule epoxy resin coating fabric by using a blade, wherein the scratch is as deep as the coating substrate, introducing ultraviolet light into optical fibers at two ends of the coating fabric, taking out the optical fibers after a period of time, observing crack changes before and after repair, and having a good self-repairing effect at the crack along with the extension of the UV light illumination time.
Example three: the photoresponse microcapsule is a polyurea formaldehyde coated vinyl silicone oil microcapsule
(1) Treatment of optical fibers
The end face light-emitting optical fiber is polished in a physical and mechanical mode, so that the end face light-emitting optical fiber is changed into a side face light-emitting optical fiber (12).
(2) Weaving of fabric
The fabric weave is designed to be plain weave on a weaving machine, nylon yarn is used for drafting, the side light-emitting optical fiber 12 and the nylon yarn, namely the common yarn 11 are woven in at intervals, and the optical fiber needs to be left at two sides of the fabric for a certain length to extend out of the fabric, so that the side light-emitting optical fiber (12) fabric is obtained.
(3) Preparation of polyurea formaldehyde coated vinyl silicone oil microcapsule
Adding a proper amount of distilled water, 2.0g of urea and 0.1g of resorcinol into a solution containing a dispersing agent, and stirring for dissolving; then, when the pH is adjusted to be =3.0 and 1 000r/min, a certain amount of vinyl silicone oil is added, and after dispersion is stable, 0.5% ammonium chloride aqueous solution is added; then, 2.0g of 38% formaldehyde aqueous solution is added while slowly stirring, and the mixture reacts for 2 hours at the constant temperature of 60 ℃; and after the reaction is finished, carrying out suction filtration, cleaning the product by using distilled water, dimethylbenzene and ethanol, and drying to obtain a microcapsule product.
(3) Preparation of epoxy modified organic silicon resin coating fabric coated with polyurea formaldehyde and vinyl silicone oil microcapsules
Adding a certain amount of epoxy modified organic silicon resin into a size mixing kettle, adjusting the viscosity of the coating by using toluene and butanol, adding ground ZnO and talcum powder at 800r/min, and uniformly stirring. And dispersing the self-made microcapsules into the epoxy modified organic silicon resin at the rotating speed of 300r/min, adding 650 parts of polyamide resin in a certain proportion, and stirring for 30min to obtain the self-repairing organic silicon coating. Coating the coating on the optical fiber fabric by using a scraper coating method, and obtaining the microcapsule-embedded epoxy modified organic silicon resin coated fabric after the coating is dried and cured at high temperature.
(4) UV light irradiation self-repair
And (3) scribing a transverse crack on the microcapsule epoxy modified organic silicon resin coating fabric by using a blade, introducing ultraviolet light into optical fibers at two ends of the coating fabric until the depth of the transverse crack reaches a coating substrate, taking out the optical fibers after a period of time, observing crack changes before and after repair, and ensuring that the self-repairing performance of the crack is better along with the extension of the UV light illumination time.
Example four: the light response microcapsule is a polyurethane prepolymer microcapsule coated by polyurea
(1) Weaving of fabric
And weaving the common yarn 11 and the finished side light-emitting optical fiber 12. The fabric weave is designed to be plain weave on a weaving machine, cotton yarn is used for drafting, optical fibers and common yarn 11 are woven in at intervals, and the optical fibers need to be left at two sides of the fabric for a certain length to extend out of the fabric, so that the finished product of the side-surface luminous optical fiber fabric is obtained.
(2) Preparation of coated urea-formaldehyde-coated polyurethane prepolymer microcapsule
A monomer mixture of urea (10 g) and formaldehyde solution (26 g) was added to a 100mL four-necked flask equipped with a condenser, stirrer and thermometer by in situ polymerization in an oil-in-water (O/W) emulsion. The pH of the solution was adjusted to around 8 by adding a certain amount of triethanolamine. The solution was stored at 70 ℃ for 1 hour to form methylol ureas. Double the volume of water was then added to the system. A predetermined amount of the above reaction solution was mixed with 70mL of an aqueous solution containing SDBS (0.1 g), ammonium chloride (0.25 g) and resorcinol (0.25 g), and EB270 (4 g), HDDA (6 g) and photoinitiator 1173 (0.4 g) were added with mechanical stirring to form an O/W emulsion.
One or two drops of 1-octanol were added at a certain stirring speed to eliminate surface bubbles. After the emulsifier was stirred at 25 ℃ for 1 hour, the temperature was increased to 60 ℃ at a rate of 0.5 ℃/min. Simultaneously, the pH of the reaction mixture was adjusted to 4 within 90min by dropwise addition of dilute hydrochloric acid. After the reaction was continued for 3 hours, the mixture was cooled to room temperature. And collecting the product, performing vacuum filtration, washing with water and acetone for three times, and performing vacuum drying at 45 ℃ for 24 hours to obtain the polyurea-formaldehyde microcapsule coated with the polyurethane prepolymer.
(3) Preparation of polyurethane coating fabric coated with polyurea-formaldehyde-coated polyurethane prepolymer microcapsules
The prepared polyurethane prepolymer-coated polyurea microcapsules are prepared into a polyurethane coating for embedding the microcapsules by a direct mixed coating method, the polyurethane coating is coated on the surface of an optical fiber fabric by a scraper coating method, and the polyurethane coated fabric coated with the photoresponse microcapsules is obtained by curing treatment.
(4) UV light irradiation self-repair
Scratching the polyurethane coating embedded with the polyurethane prepolymer/polyurea-formaldehyde microcapsules by using a blade, wherein the depth of the scratch is up to the substrate, and the width of the scratch is about 20 mu m so as to simulate micro-cracks formed by the epoxy resin coating under the action of external force; then introducing ultraviolet light into the optical fibers at the two ends of the coated fabric, observing and contrasting the change of scratches before and after ultraviolet illumination after a certain time, wherein the scratches are basically filled in the part with narrow scratches; at the wider part, the bottom of the scratch is filled.
Example five: the photoresponse microcapsule is SiO 2 Epoxy resin microcapsule coated with fluorescent agent
(1) Weaving of fabric
And designing the fabric weave as a plain weave on a weaving machine, drafting with polyester yarns, and weaving the polyester yarns into the common fabric base fabric.
(2)SiO 2 Preparation of epoxy resin microcapsule coated with fluorescent agent
The microcapsules are synthesized by two steps, namely interfacial polymerization and in-situ polymerization. The specific experimental procedure is that firstly, a small amount of diphenylamino-4-benzaldehyde is dissolved in 1mL of DFM solution to be used as fluorescent agent. Weighing 1g of epoxy resin (E-51), lg of adipic acid ester, 0.5g of cationic photoinitiator and 0.5g of tetraethyl orthosilicate (TEOS) in a beaker, then weighing 50uL of fluorescent agent in the beaker, manually stirring in an ultrasonic environment, preliminarily mixing, and uniformly stirring to obtain an oil phase; then 0.7g of surfactant (polyether P123) is weighed and placed in 40ml of deionized water, and the surfactant is fully dissolved for 5min as a water phase under high-speed stirring at the temperature of 40 ℃. Subsequently, the aqueous phase was added dropwise to the oil phase while stirring in an ultrasonic environment to perform preliminary emulsification. Then, the mixture is placed under a high-speed homogenizer, and the speed is gradually increased to 8000rmp until the mixture is stirred into uniform and stable O/W emulsion. Next, the emulsion is transferred into a flat-bottomed flask, placed in a water bath, mechanically stirred to 300rpm, and added with 900 μ L of 2mol L of dilute hydrochloric acid prepared in advance, and the temperature is raised to 50 ℃ to start reaction; after 4 hours, adding a proper amount of TEOS 2.3mL and 2mol L of dilute hydrochloric acid solution 300uL; after 4 times, continuously adding 600 mu L of 2mol L of dilute hydrochloric acid, and adding twice in total; continuing to react for 12h, and ending the experiment; suspending the microcapsule in liquid, centrifuging under the action of a centrifuge, washing with deionized water for multiple times until the supernatant is neutral, taking out the microcapsule at the bottom, and drying in an oven at 60 ℃ to obtain the microcapsule.
(3) Embedded SiO 2 Preparation of fluorescent agent epoxy resin microcapsule coated PVC coating fabric
A PVC coating fabric coated with microcapsules is prepared by a scraper coating method, EPVC (100 parts), DOP (70 parts), DOA (5 parts), a stabilizer (2.3 parts) and the microcapsules (10 parts) are uniformly mixed to prepare coating slurry, and the microcapsules are uniformly dispersed in the coating slurry by ultrasonic stirring. And uniformly coating the prepared coating agent on two sides of the polyester woven fabric by using a scraper, and then placing the polyester woven fabric in an oven for curing to obtain the PVC coating fabric embedded with the photoresponse microcapsules.
(4) UV light irradiation self-warning
Scratching a scratch with the width of about 20 micrometers on the coated microcapsule PVC coated fabric by using a blade, wherein the scratch is deep until the coating substrate, placing the coated fabric under UV light for a period of time, taking out, observing the change of the crack before and after repairing, and having better self-warning effect at the crack along with the extension of the illumination time of the UV light. After the coated fabric is scratched, the microcapsules at the scratched positions are cracked, a solvent in the microcapsules flows into the scratched positions under the action of capillary tubes, and under the irradiation of an ultraviolet lamp, a photoinitiator can absorb ultraviolet light within the range of 250-300 nm, so that cracks achieve a self-warning effect.
Fig. 7 is a fluorescence image of PVC coated fabric with microcapsules embedded, and the fluorescer flowed into the scratch after the microcapsules broke. The PVC coating in FIG. 7 (a) without embedded microcapsules showed substantially no fluorescence at the scratch. Fig. 7 (b) is a fluorescence image of the scratch of the coating of the microcapsule-embedded PVC coated fabric under ultraviolet illumination, in which the scratch can be clearly seen to have an obvious yellow fluorescence effect, which illustrates that the self-warning behavior of the microcapsule-embedded PVC coated fabric can be detected by fluorescence.
Example six: the photoresponse microcapsule is a polyurea aldehyde coated blue AIE fluorescent dye microcapsule
(1) Weaving of fabric
And designing the fabric weave as a plain weave on a weaving machine, drafting with polyester yarns, and weaving the polyester yarns into the common fabric base fabric.
(2) Preparation of polyurea-formaldehyde coated healing agent, blue AIE fluorescent dye and photoinitiator microcapsule
A2.5 wt% aqueous solution (5 mL) of Ethylene Methyl Acrylate (EMA) was added to distilled water (20 mL), and urea (0.504 g), resorcinol (0.050 g), and ammonium chloride (0.050 g) were added with stirring. The pH of the synthesis solution was adjusted to 3.5 using 10% NaOH solution.
A drop of 1-octanol was then added to the solution to eliminate surface bubbles. The resulting mixture was stirred at 800, 1000, 1200, 1400, 1600rpm, and 10mL of a core material, consisting of TPE (1,1,2,2-tetraphenylethylene), which is a representative fluorescent dye having the phenomenon of AIE, was added to the stirred solution, with a mass of 0.2g. To the stirred emulsion was added a 37wt% solution of formaldehyde (1.456 g, 0.0179mol), the temperature of the resulting mixture was raised to 60 ℃ and heated at that temperature for 5.5h. The reaction mixture was cooled to room temperature and the microcapsules were isolated by vacuum filtration. The microcapsules were washed with water and acetone and then air dried.
(3) Preparation of epoxy resin coating fabric embedded with polyurea formaldehyde coated blue AIE fluorescent dye microcapsule
Epoxy resin and diethylenetriamine are mixed according to the mass ratio of 100:20, adding a microcapsule with a certain mass of 15wt%, uniformly mixing, putting into a vacuum drying oven, and vacuumizing for 15min. The mixed solution was coated on a general fabric and left at room temperature for 72 hours.
(4) UV light irradiation self-warning
And (3) scratching a scratch with the width of about 20 micrometers on the microcapsule epoxy resin coating fabric by using a blade until the scratch reaches the coating substrate, and placing the coating fabric under UV light to ensure that the self-warning effect at the crack is good.
Example seven: the capsule coated with the photoresponsive material is urea-formaldehyde resin coated 2,7-dichlorophenol fluorescein (DCF) microcapsule
(1) Weaving of fabric
The fabric tissue is designed to be plain weave on a weaving machine, cotton yarn is used for drafting, the side light-emitting optical fiber and the nylon yarn of the finished product are woven in at intervals, and a certain length of the optical fiber needs to be left on one side of the fabric to extend out of the fabric, so that the side light-emitting optical fiber fabric base fabric is obtained.
(2) Preparation of urea-formaldehyde resin coated 2,7-dichlorophenol fluorescein (DCF) microcapsule
Adding urea and formaldehyde solution into a three-neck flask by adopting an in-situ polymerization two-step method, regulating the pH value to be 8-9 by using triethanolamine, magnetically stirring for 1h at the constant temperature of 70 ℃ to obtain a transparent prepolymer solution, adding 0.12g of DCF at a certain rotating speed, emulsifying for 30min, regulating the pH value of a system to be 3-4 by using dilute hydrochloric acid, slowly heating to 60 ℃, reacting for 2-3 h, washing, filtering and drying precipitates at the bottom of the flask to obtain white microcapsule powder.
(3) Preparation of urea-formaldehyde resin coated 2,7-dichlorophenol fluorescein (DCF) microcapsule-embedded epoxy resin coated fabric
Epoxy resin E51, diluent TMPEG and photoinitiator 6992 (mass ratio 6.9: 2.9: 0.2) are mixed evenly by ultrasound. Uniformly dispersing microcapsules with the mass percent of 20% in the microcapsules by mechanical stirring, coating the coating slurry on the surface of the optical fiber fabric by a scraper coating method, and then irradiating the optical fiber fabric by using ultraviolet light with the wavelength of 365nm and the power of 500W in a photochemical reaction device at room temperature for 5min to cure the epoxy resin. And obtaining the microcapsule-embedded epoxy resin coating fabric.
(5) UV light irradiation self-warning
And (3) scratching a scratch with the width of about 20 micrometers on the microcapsule epoxy resin coating fabric by using a blade, wherein the scratch is as deep as the coating substrate, and introducing ultraviolet light into optical fibers at two ends of the coating fabric to find that the scratch shows red fluorescence, so that the self-warning effect is good.
Example four: the photoresponse microcapsule is urea-formaldehyde resin coated tetrachlorofluorescein microcapsule
(1) Weaving of fabric
And designing the fabric weave as a plain weave on a weaving machine, drafting with polyester yarns, and weaving the polyester yarns into the common fabric base fabric.
(2) Preparation of urea-formaldehyde resin coated tetrachlorofluorescein, photocuring resin aliphatic polyurethane acrylate microcapsule
Adding urea and formaldehyde solution into a three-neck flask by adopting an in-situ polymerization two-step method, regulating the pH value to be 8-9 by using triethanolamine, magnetically stirring for 1h at the constant temperature of 70 ℃ to obtain a transparent prepolymer solution, adding 0.12g of tetrachlorofluorescein at a certain rotating speed, emulsifying for 30min, regulating the pH value of a system to be 3-4 by using dilute hydrochloric acid, slowly heating to 60 ℃, reacting for 2-3 h, washing, filtering and drying precipitates at the bottom of the flask to obtain microcapsule powder.
(3) Preparation of epoxy resin coating fabric with urea-formaldehyde resin-coated tetrachlorofluorescein microcapsule embedded
Uniformly mixing epoxy resin E51, a diluent TMPEG and a photoinitiator 6992 (the mass ratio is 6.9: 2.9: 0.2) by ultrasonic, uniformly dispersing microcapsules with the mass percentage of 20% in the microcapsules by mechanical stirring, coating the coating slurry on the surface of an optical fiber fabric by a scraper coating method, and then irradiating the optical fiber fabric by ultraviolet light with the wavelength of 365nm and the power of 500W for 5min in a photochemical reaction device under the condition of room temperature to cure the epoxy resin. And obtaining the microcapsule-embedded epoxy resin coating fabric.
(4) The UV light irradiation is from the scratch of drawing width about 20 mu m on cladding microcapsule epoxy coating fabric with the blade for the early warning, and the scratch degree of depth is until the coating base, lets in the ultraviolet ray with the optic fibre at coating fabric both ends, finds that scratch department presents orange fluorescence, and is from early warning respond well.
Example five: the photoresponse microcapsule is a polyurea formaldehyde coated fluorescent liquid OIL-GLO44-P microcapsule
(1) Weaving of fabric
And designing the fabric weave as a plain weave on a weaving machine, drafting with polyester yarns, and weaving the polyester yarns into the common fabric base fabric.
(2) Preparation of OIL-GLO44-P microcapsule of polyurea-formaldehyde coated fluorescent liquid
A2.5 wt% aqueous solution (5 mL) of Ethylene Methyl Acrylate (EMA) was added to distilled water (20 mL), and urea (0.504 g), resorcinol (0.050 g), and ammonium chloride (0.050 g) were added with stirring. The pH of the synthesis solution was adjusted to 3.5 using 10% NaOH solution.
A drop of 1-octanol was then added to the solution to eliminate surface bubbles. The resulting mixture was stirred at 1400rpm, and 10mL of a core material consisting of the fluorescent liquid OIL-GLO44-P, having a mass of 0.2g, was added to the stirred solution. To the stirred emulsion was added a 37wt% solution of formaldehyde (1.456 g, 0.0179mol), the temperature of the resulting mixture was raised to 60 ℃ and heated at that temperature for 5.5h. The reaction mixture was cooled to room temperature and the microcapsules were isolated by vacuum filtration. The microcapsules were washed with water and acetone and then air dried.
(3) Preparation of epoxy resin coating fabric embedded with polyurea-formaldehyde-coated fluorescent liquid OIL-GLO44-P microcapsule
Uniformly mixing epoxy resin E51 and a diluent TMPEG (polyethylene glycol) (mass ratio of 6.9: 2.9) by ultrasonic waves, uniformly dispersing 20% of microcapsules by mechanical stirring, coating the coating slurry on the surface of an optical fiber fabric by a scraper coating method, and then irradiating the optical fiber fabric by using ultraviolet light with the wavelength of 365nm and the power of 500W for 5min in a photochemical reaction device under room temperature condition to cure the epoxy resin. And obtaining the microcapsule-embedded epoxy resin coating fabric.
(4) Visible light irradiation self-warning
The coated fabric is placed under the sunlight to show orange at the coating scratch position, and the self-early warning effect is good.
The foregoing is illustrative of the best mode of the invention and details not described herein are within the common general knowledge of a person of ordinary skill in the art. The protection scope of the present invention is subject to the content of the claims, and any equivalent changes based on the technical teaching of the present invention are also within the protection scope of the present invention.
Claims (9)
1. The microcapsule coated fabric capable of self-warning or self-repairing through light initiation is characterized by comprising a fabric base fabric (1) and a coating loaded with self-warning or self-repairing photoresponse microcapsules, wherein the coating loaded with the microcapsules is attached to one surface or two surfaces of the fabric base fabric (1).
2. The photo-induced self-warning or self-repairing microcapsule coated fabric as claimed in claim 1, wherein the fabric base cloth (1) is a common base cloth or an optical fiber fabric, and the common base cloth is woven by any one or more blended fibers of polyester, nylon, polypropylene, spandex, acrylon, polylactic acid, viscose, cotton, hemp or wool through a weaving, knitting or non-weaving process; the optical fiber fabric is woven by adopting a lateral luminous fiber (12) through a weaving process or weaving the lateral luminous fiber (12) and common yarns (11) according to a required interval weaving method.
3. The photo-initiated self-warning or self-healing microcapsule coated fabric according to claim 2, wherein the side emitting optical fiber (12) is a finished side emitting optical fiber (12) or a side emitting optical fiber (12) obtained by laser processing, mechanical polishing or chemical etching of an end emitting optical fiber.
4. The photo-initiated self-warning or self-repairing microcapsule coated fabric as claimed in claim 2, wherein the light source is 280-400 nm of UV light or 400-780 nm of visible light, and for a common fabric, an external specific light source is adopted to irradiate the surface of the fabric to realize self-warning or self-repairing; for the optical fiber fabric, an external specific light source is adopted to irradiate the surface of the fabric or required specific light is introduced into the side light-emitting optical fiber (12) to realize self-warning or self-repairing of the fabric.
5. The photo-initiated self-warning or self-repairing microcapsule coated fabric according to claim 2, wherein the self-warning or self-repairing photo-responsive microcapsule loaded coating comprises a coating adhesive (2) and a photo-responsive microcapsule (3), the photo-responsive microcapsule (3) can be a self-warning microcapsule or a self-repairing microcapsule and is dispersed in the coating, and the average particle size is less than or equal to 80 μm; wherein the coating adhesive (2) is one or more of PVC, epoxy resin, polyurethane, polyamide, polydimethylsiloxane and polyethylene, the photoresponse microcapsule (3) is composed of a wall material and a core material, and the mass percentage of the coating adhesive to the photoresponse microcapsule is 10-20.
6. The photo-initiated self-warning or self-repairing microcapsule coated fabric according to claim 5, wherein the photo-responsive microcapsule (3) wall material comprises SiO 2 One or more of urea-formaldehyde resin, polyurea formaldehyde or melamine-formaldehyde prepolymer.
7. The photo-initiated self-warning or self-repairing microcapsule coated fabric according to claim 5, wherein when the photo-responsive microcapsule (3) is a self-warning photo-responsive microcapsule, the core material comprises one or more of an ultraviolet-responsive photochromic dye, a fluorescent liquid OIL-GLO44-P, a rhodamine-based fluorescent molecule, 2',7' -dichlorophenol fluorescein, tetrachlorofluorescein, crystal violet lactone or an aggregation induced emission effect (AIE effect) molecule as a self-warning material.
8. The photo-initiated self-warning or self-repairing microcapsule coated fabric as claimed in claim 5, wherein the core material of the photo-responsive microcapsule (3) is a self-repairing photo-responsive microcapsule, and the core material comprises one or more of a photo-curing resin aliphatic urethane acrylate, an epoxy resin, vinyl silicone oil, paraffin, methyl methacrylate, a polyurethane prepolymer and dicyclopentadiene, and one or more of a photoinitiator, a cinnamoyl group, a coumarin group or an anthracene group polymer material.
9. The preparation method of the microcapsule coating fabric with the photoinitiation self-warning or self-repairing function is characterized by comprising the following steps of:
step 1, weighing a coating adhesive, a photoresponse microcapsule and other additives according to a certain proportion, and carrying out ultrasonic dispersion and full mixing for a period of time to prepare coating slurry for coating the photoresponse microcapsule;
step 2, after the fabric base cloth (1) is subjected to pretreatment such as unwinding, ironing, plasma treatment/laser etching/chemical treatment and the like, the coated photoresponse microcapsule coating slurry is uniformly coated on the surface of the pretreated fabric base cloth through a roller coating or a scraper coating, coating is carried out on the surface of the fabric base cloth once or for many times according to requirements, drying and curing are carried out at the temperature of 90-120 ℃, one or more layers of photoresponse microcapsule coating films are formed on the surface of the fabric, and the coated fabric with the self-warning and self-repairing photoinitiation microcapsules is prepared through winding.
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