CN114164661A - Large-area preparation method of high-stability high-saturation photonic crystal structure color-generating fabric - Google Patents
Large-area preparation method of high-stability high-saturation photonic crystal structure color-generating fabric Download PDFInfo
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- CN114164661A CN114164661A CN202111437620.8A CN202111437620A CN114164661A CN 114164661 A CN114164661 A CN 114164661A CN 202111437620 A CN202111437620 A CN 202111437620A CN 114164661 A CN114164661 A CN 114164661A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a large-area preparation method of a high-stability high-saturation photonic crystal structure color-generating fabric, which comprises the following steps: s1, surface modification of the textile substrate: coating a special high molecular polymer on the surface of a textile substrate, heating and curing to form a film, and obtaining a fabric with a high molecular layer; s2, preparing a nano microsphere dispersion liquid containing an activating agent, and enabling the nano microsphere dispersion liquid to be uniformly distributed on the surface of the fabric with the polymer layer obtained in S1 under the action of external force induction; s3, heating the compound obtained in the step S2 to obtain the large-area color-developing fabric with the photonic crystal structure. The method can solve the problem that the color saturation and the structural stability of the photonic crystal structure chromogenic fabric are difficult to combine, and solve the difficulties in developing the photonic crystal structure chromogenic textiles, such as large-area crack-free and large-area rapid assembly and the like.
Description
Technical Field
The invention relates to a preparation method of a structural color-producing fabric, in particular to a large-area preparation method of a high-stability high-saturation photonic crystal structural color-producing fabric, and belongs to the field of textile structural color production.
Background
A photonic crystal is a nanomaterial with a periodic dielectric structure, and its most basic feature is to have a photonic band gap. Due to the existence of the photon forbidden band, visible light equivalent to the forbidden band can be prevented from passing through the photonic crystal so as to be selectively reflected, constructive interference is formed on the surface of the photonic crystal, and therefore, colorful structural colors are formed, and the color generation principle can be explained according to a Bragg diffraction formula. The reflection wavelength can be correspondingly changed along with the change of the effective refractive index, the lattice spacing and the incident angle (equal to the observation angle) of the photonic crystal, the structural color of the photonic crystal also has a flexible and changeable visual effect, and the conventional chemical coloring agents (dyes and pigments) cannot achieve the effect, so that the photonic crystal structure is one of the advantages of color generation and market attraction; the second advantage is that the preparation process of the photonic crystal structure chromogenic material has no wastewater discharge, does not need to apply chemical colorants such as dye and pigment, is a physical chromogenic process, and has the characteristics of green and sustainable development; and the color-generating material with the photonic crystal structure has a visual sensing characteristic, is a novel intelligent optical material, and has potential application prospects in the fields of intelligent sensing, intelligent anti-counterfeiting, intelligent display and the like. However, the application of the current photonic crystal structure color generation technology in the textile field has the following difficult problems.
The first problem is as follows: the nano-microsphere for preparing the photonic crystal is usually selected from Polystyrene (PS) and silicon dioxide (SiO)2) And polymethyl methacrylate (PMMA) and other hard nanometer microspheres. Because the prepared photonic crystal is supported only by weak bonding forces such as hydrogen bonds, Van der Waals forces and the like among the nano microspheres, the structure of the photonic crystal is easy to damage under external force (washing, friction and bending), so that the structural color disappears, which is the most urgent and difficult problem to solve when the practical application of the color generation technology of the photonic crystal structure is carried out in the textile field. However, the physical encapsulation method adopted at present to improve the structural stability of the photonic crystal, such as the photo-curing method (CN201810127322.0), has an irreversible negative effect on the optical properties of the photonic crystal (the refractive index difference of the photonic crystal is reduced). To solve this problem, there is a research work on hollow SiO2The nanometer microspheres construct a photonic crystal array, and then the photonic crystal array is packaged, so that the stability of the photonic crystal structure is improved, and the difference of the refractive index of the photonic crystal is also kept, namely the gorgeous structural color (Li Y, Wang X, Hu M, et al2/Polyurethane Acrylate Inverse Opal Photonic Crystals with High Color Saturation and Tough Mechanical Strength[J].Langmuir,2019,35(44):14282-14290；CN201811006303.9). But hollow SiO2The preparation process of the nano-microsphere is complicated, and the large-scale industrial application of the method in the textile field is limited. To reconcile the contradictory problems between photonic crystal structural stability and optical properties, there are reports in the literature of co-deposition methods for preparing composite photonic crystals to improve the structural stability of photonic crystals (LI Y C, ZHOU L, LIU G J, et al].Applied Surface Science,2018,444:145-153.MENG Y,TANG B T,XIU J H,et al.Simple fabrication of colloidal crystal structural color films with good mechanical stability and high hydrophobicity[J]Dyes and Pigments,2015,123: 420-426). However, the method also has certain disadvantages that if too many soft particles are added, the self-assembly of the nano microspheres is interfered, and meanwhile, the refractive index difference of the photonic crystals is reduced, so that the optical properties of the photonic crystals are influenced. Researchers have also used surface-supported solidification to improve the structural stability of photonic crystals (WANG X H, LI Y C, ZHAO Q, et al. high structural stability of photonic crystal on structures, prepared via a surface-supported solidification method [ J ]].ACS Applied Materials&Interfaces,13(16): 19221-19229), although the method can coordinate the matching problem between the structural stability and color vividness of photonic crystals to some extent, it is still insufficient for practical application. In summary, no technical means for improving the structural stability of the photonic crystal to meet the requirement of practical application and retaining the attractive structural color of the photonic crystal is reported at present.
The second problem is that: the preparation method of the photonic crystal is usually a nano microsphere self-assembly method, the process is usually carried out in a water phase, and the water is the substance with the largest surface tension in the liquid, so the shrinkage generated by the water in the assembly process usually causes cracks to be generated in the finally assembled photonic crystal structure, and the appearance of the photonic crystal structure is influenced, and the practical application of the photonic crystal structure is also influenced. In order to solve the problem, research works have adopted a concentration method to prepare high-concentration PS nano microsphere emulsion so as to form liquid photonic crystals (metastable photonic crystals) (CN201910350271.2), and at the moment, the self-assembly is induced by external force so as to prepare a large-area crack-free photonic crystal coating (CN 201910349806.4). However, the method is also repellent to the difficulty, and the PS photonic crystal obtained by assembly has no firm accumulation structure and is easy to be damaged by external force. The aqueous polyurethane emulsion is added into the colloidal microsphere dispersion, and the dispersion is applied to a substrate in a silk rod coating mode, so that a crack-free photonic crystal structure (CN201710225398.2) can be obtained through assembly. The method has the following defects: generally, the nano-microspheres and the waterborne polyurethane have relatively close refractive indexes, and the saturation of structural color is reduced.
The problem three is: as is well known, textile dyeing is a continuous processing process, but the current photonics crystal structure color generation technology (such as gravity settling self-assembly method and vertical deposition self-assembly method) is also prepared in laboratory samples. In order to realize the continuous preparation of large-area photonic crystals, relevant researchers at home and abroad also carry out corresponding research work in recent years. If researchers try to prepare soft nano microspheres as structural elements for assembling photonic crystals and continuously prepare the flexible photonic crystal structure color-generating film by an external force shearing-induced self-assembly technology, the preparation process of the flexible nano microspheres is complex, and the external force shearing-induced self-assembly requires higher processing temperature and more complex special equipment, so that the defects of high energy consumption and high equipment investment are caused (Zhao Q, Finlayson C E, snonwell D E, et al, large-scale ordering of nanoparticles using a video elastic skin processing [ J ]. Nature communications,2016,7(1):1-10.CN 201610329842.0). A recent research work reported a technique for continuously preparing a cellulose nanocrystal structure color film: a photonic crystal structure color generation film is formed by self-assembly by utilizing plant-based cellulose nanocrystalline colloidal particles, and a large-area photonic crystal structure color generation film (DROGUET B E, LIANG H L, FRKA P B, et al large-scale interference of structural colorful crystalline porous crystal films ms and impact pigments [ J ] Nature Materials,2021. DOI: 10.1038/s41563-021 01135-8.) is obtained by processing on roll-to-roll continuous pilot plant equipment. However, the photonic crystal prepared by using the cellulose nanocrystal as an assembly element is usually a fragile structure and has poor matching with a flexible textile substrate.
Combining the practical application-limiting viewpoint of the photonic crystal, it can be found that the three difficult problems are related to thread, and when one property of the photonic crystal is improved, the other two points are discarded to a certain extent. At present, there is a fresh report of a technical means for continuously preparing a large-area photonic crystal structure chromogenic fabric with high structural stability and color saturation. Therefore, the development of a fast and economic method for preparing the large-area high-stability high-saturation structure chromogenic fabric has important significance in the practical application of the bionic coloring field of textiles.
Disclosure of Invention
The invention aims to provide a large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric, which can continuously, quickly and massively construct photonic crystals, and the constructed photonic crystals have the advantages of high structural stability, good structural color durability, bright and bright color, iridescence effect and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a large-area preparation method of a high-stability high-saturation photonic crystal structure color-generating fabric comprises the following steps:
s1, surface modification of the textile substrate: coating a special high molecular polymer on the surface of a textile substrate, heating and curing to form a film, and obtaining a fabric with a high molecular layer;
the special high molecular polymer is a soft segment hard segment copolymerization polyurethane high molecular polymer or a soft segment hard segment copolymerization polyacrylic acid high molecular polymer;
s2, preparing a nano microsphere dispersion liquid containing an activating agent, and enabling the nano microsphere dispersion liquid to be uniformly distributed on the surface of the fabric with the polymer layer obtained in S1 under the action of external force induction;
the nanometer microsphere dispersion liquid containing the activating agent comprises the following components in percentage by weight: 15-55 wt% of nano microspheres, 0.02-0.1 wt% of carbon black, 1-10 wt% of activating agent and the balance of water;
s3, carrying out heating treatment on the compound obtained in the step S2, completing the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the compound, and finally obtaining the large-area photonic crystal structure chromogenic fabric.
The invention can continuously prepare the photonic crystal structure chromogenic fabric with iridescence effect and stable structure in a large area by using the continuous heating device. The method can solve the problem that the color saturation and the structural stability of the photonic crystal structure chromogenic fabric are difficult to combine, and solve the difficulties in developing the photonic crystal structure chromogenic textiles, such as large-area crack-free and large-area rapid assembly.
Preferably, the hard segment of the soft segment and hard segment copolymerization type polyurethane high molecular polymer is one of toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate; the soft segment is a long carbon chain soft substance with crystallization performance, the length of a carbon chain in a repeating unit is more than 4C, and the soft segment is selected from one of poly adipic acid-1, 4 butanediol ester, poly adipic acid-1, 6 hexanediol ester and poly-1, 6-hexamethylene-carbonate;
the soft segment hard segment copolymerization type polyacrylic acid high molecular polymer has the hard segment selected from one of methyl methacrylate, hydroxyethyl methacrylate or methyl acrylate, the soft segment is a long straight chain monomer with more than 4C, and the soft segment is selected from one of butyl acrylate, n-pentyl acrylate, n-hexyl acrylate and isooctyl acrylate.
Preferably, the nano-microsphere is an organic high-molecular polymer Polystyrene (PS) nano-microsphere, a polymethyl methacrylate (PMMA) nano-microsphere, polystyrene @ polydopamine (PS @ PDA), polystyrene @ silicon dioxide (PS @ SiO)2) Poly (styrene-hydroxyethyl acrylate) (P (St-HEA)), poly (styrene-methyl methacrylate) (P (St-MMA)), poly (styrene-methyl methacrylate-methacrylic acid) (P (St-MMA-MAA)), poly (styrene-methyl methacrylate-acrylic acid) (P (St-MMA-AA)), poly (styrene-butyl acrylate-methyl methacrylate) (P (St-BA-MMA)), poly (styrene-methacrylic acid) (P (St-MAA)), and inorganic Silica (SiO)2) One or more of the nano microspheres.
Preferably, the activating agent is one or a mixture of several of amphiphilic fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate and ethylene oxide adduct of polypropylene glycol.
Preferably, in S3, the heat treatment conditions are: the temperature is 50-80 deg.C, humidity is 50-70%, and the time is 2-10 min. Under certain temperature and humidity conditions, the surfactant molecules contained in the assembling liquid can activate the interface molecules of the special polymer layer and enhance the chain segment/molecular motion of the surface layer of the special polymer, and in the self-assembling process of the nano microspheres, the capillary force generated in the water evaporation and microsphere assembling process induces the chain segment of the special polymer to move to the space between the nano microspheres and the surface of the photonic crystal. After the photonic crystal is assembled, the polymer chain segment is re-cured inside the photonic crystal to generate a local adhesion effect, and the bottom of the photonic crystal is in surface adhesion with the polymer layer on the surface of the fabric. In addition, activated molecules are directionally arranged on a water-solid/air interface at a certain temperature, so that the interfacial tension between the assembly liquid and the substrate and between the assembly liquid and the air is reduced, the cohesive force generated by hydrogen bonds between water molecules on the liquid surface is further reduced, the surface of the fabric with the special macromolecules of the nano microsphere dispersion liquid is in a thermodynamically stable state, the three-phase line does not slide in the heating assembly process, and the large-area photonic crystal structure chromogenic fabric can be continuously prepared in an external force induction mode. The special polymer which passes through extension exists in the photonic crystal structure color-generating fabric prepared by the project, and the special polymer plays a role of a ligament in front of the nano-microsphere. In the photonic crystal structure, more air phases still exist, so that the photonic crystal structure has excellent structural stability and can also show bright structural color.
Preferably, the coating amount of the special high molecular polymer is 8 to 30 g/m (dry weight).
Preferably, the diameter of the nano-microsphere is 150-350 nm, the sphericity is good, and the monodispersion index is less than 0.08.
Preferably, the external force inducing means is one of a wire rod, a scraper, a magnetic rod and a glass rod.
Preferably, in S1, the special high molecular polymer coating method is one of a direct blade coating method and a film transfer method; when the direct blade coating method is adopted, the film forming conditions are as follows: the temperature is 80-140 ℃, and the time is 1-5 min; in the case of the film transfer method, the film formation conditions are as follows: the temperature is 80-120 ℃, and the time is 10-90 s.
Preferably, the textile substrate is selected from one of cotton fabric, polyester fabric, real silk fabric, polyester-cotton blended fabric, polyester-polyurethane blended fabric and the like.
Preferably, the heating device used for assembling and stabilizing the photonic crystal is a static heating device (oven) or a continuous heating device (hot air heating or infrared heating).
The invention has the beneficial effects that:
1. the invention provides a complete set of special polymer structure types and adaptive activator molecular structure types on the basis of researching the structure-activity relationship between activator molecules and special polymers for fabric surface modification. Under the condition of specific temperature and humidity, the molecules of the activating agent can activate the interface molecules of the special polymer layer on the surface of the fabric, and creep relaxation gradually occurs. In the self-assembly process of the nano-microspheres, the capillary force generated after the regular photonic crystal structure is formed by the upward driving force of water molecule evaporation and the gradual assembly of the microspheres induces the creep-relaxed special polymer chain segment and even partial polymer main chain to migrate to the space between the nano-microspheres and the surface of the photonic crystal. After the photonic crystal is assembled, the temperature is reduced, the high molecular chain segments/molecules are cured secondarily in the photonic crystal, and a ligament effect is realized among the photonic crystal structural element nano microspheres, so that the photonic crystal structure trunk has good flexibility. Meanwhile, the creep-relaxed interface polymer can also play a role in integral fusion and connection between the photonic crystal layer and the fabric surface modification layer, so that the photonic crystal structure 'trunk' stands on a firm 'ground'. The ligament to the body to the ground are integrated, so that the stability of the photonic crystal is obviously improved, the difference of refractive index in the photonic crystal can be reserved, the brilliant structural color is presented, and the consistency of high stability and high saturation of the color-generating fabric with the photonic crystal structure is realized.
2. According to the invention, activator molecules are introduced into the nano microsphere emulsion, and in the self-assembly process of the nano microsphere, the activator molecules can form ordered directional arrangement on a liquid-solid interface, so that the cohesive force generated by water molecules on the liquid-solid/gas interface is reduced, the nano microsphere dispersion can be wetted and spread on the solid interface, and the large-area continuous preparation of photonic crystals is facilitated.
3. The method for preparing the large-area crack-free photonic crystal coating can effectively replace part of the existing chemical pigments of paint and dye, can reduce environmental pollution, and meets the clean production requirement of sustainable development.
Drawings
FIG. 1 is a digital photograph of an assembled photonic crystal prepared by adding and not adding alkylphenol ethoxylates (1 wt%) to the PS nanosphere dispersion prepared in example 1;
FIG. 2 is a digital photograph of a photonic crystal structure color-producing fabric prepared in example 2;
FIG. 3 is a reflectance curve of a photonic crystal structure color-producing fabric prepared in example 3;
FIG. 4 is an SEM image of a photonic crystal structure color-producing fabric prepared in example 4;
FIG. 5 is an SEM image of the surface of a special polymer migration photonic crystal of the color-producing fabric with a photonic crystal structure prepared in example 5;
FIG. 6 is a digital photograph of large area photonic crystal structure color-producing fabrics prepared in examples 6 and 7, wherein the upper is example 6 and the lower is example 7;
FIG. 7 is an illustration of the iridescence effect of the large area photonic crystal structure color-generating fabric prepared in examples 7, 8 and 9, wherein a, b and c correspond to the large area photonic crystal structure color-generating fabric prepared in examples 7, 8 and 9 in sequence;
FIG. 8 is a graph showing the structural stability of the photonic crystal structure color-producing fabric prepared in example 5;
fig. 9 is a digital photograph of the photonic crystal structure color-producing fabrics prepared in comparative examples 1, 2, 3, wherein a, b, c correspond to comparative examples 1, 2, 3 in order.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
A special polymer (i), type PUE-2013, type PUE1401, type PUE1650 and the like, shanghai si sheng polymer materials ltd); model P1907, model P3904, model P3902s, and the like, zhejiang department of agriculture, ltd (some are listed, but not limited to the above products);
special polymer II, which is prepared by a laboratory, and takes one preparation method as an example: 100g of deionized water was charged into a 250mL four-necked round bottom flask with mechanical stirring and condensing means, followed by 5g of Methyl Methacrylate (MMA) and 5g of Butyl Acrylate (BA) and 0.5g of Sodium Dodecyl Sulfate (SDS) with a stirring speed of 350rpm, and 0.3g of potassium persulfate was dissolved in 10mL of deionized water and added to the four-necked flask when the temperature was raised to 80 ℃. The whole reaction system is carried out in a nitrogen atmosphere for 10 hours;
example 1
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: coating 8 g/square meter of special polymer (PUE1401) on the surface of the polyester fabric, and heating and curing the polyester fabric in a heating device at 80 ℃ for 5min to form a film;
(2) preparing 150nm PS nano microsphere dispersion (15 wt% of nano microsphere, 0.02 wt% of carbon black, 1 wt% of fatty alcohol-polyoxyethylene ether as an activating agent and the balance of water), and uniformly distributing the dispersion on the surface of the fabric with the special polymer layer obtained in the step (1) through a silk rod induction effect;
(3) and (3) placing the compound obtained in the step (2) in a standing heating device (with the temperature of 50 ℃ and the humidity of 50%) for 10min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 2
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: preparing 12 g/square meter special polymer (PUE-2013) on the surface of a polyester fabric by adopting a film transfer method, and placing the polyester fabric in a heating device for heating and curing for 90s at 80 ℃ to form a film;
(2) preparing 200nm PMMA nano microsphere dispersion (20 wt% of nano microspheres, 0.03 wt% of carbon black and 2 wt% of activating agent: polyoxyethylene sorbitan fatty acid ester), and uniformly distributing the dispersion on the surface of the fabric with the special polymer layer obtained in the step (1) under the induction action of a scraper;
(3) and (3) placing the compound obtained in the step (2) in a continuous hot air heating device (with the temperature of 60 ℃ and the humidity of 60%) for 7min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable curing of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 3
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: coating 16 g/square meter special polymer (PUE1650) on the surface of cotton fabric, and heating and curing in a heating device at 100 ℃ for 3min to form a film;
(2) preparing 250nm P (St-MMA) nano microsphere dispersion liquid (30 wt% of nano microsphere, 0.05 wt% of carbon black, 3 wt% of activator alkylphenol polyoxyethylene, and the balance of water), and uniformly distributing the dispersion liquid on the surface of the fabric with the special polymer layer obtained in the step (1) through the induction action of a magnetic bar;
(3) and (3) placing the compound obtained in the step (2) in a standing heating device (with the temperature of 70 ℃ and the humidity of 70%) for 5min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 4
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: preparing 20 g/square meter special polymer (P1907) on the surface film of real silk fabric by adopting a film transfer method, and placing the prepared special polymer in a heating device for heating and curing for 60s to form a film at 100 ℃;
(2) configuration of 220nm PS @ SiO2The nano microsphere dispersion (35 wt% of nano microsphere, 0.06 wt% of carbon black, 4 wt% of fatty acid polyoxyethylene ester as an activating agent and the balance of water) is uniformly distributed on the surface of the fabric with the special macromolecule layer obtained in the step (1) through the glass rod induction;
(3) and (3) placing the compound obtained in the step (2) in a standing heating device (the temperature is 80 ℃, and the humidity is 70%) for 5min, completing the assembly of the nano microspheres, the activation and migration of the interface layer, and the stable solidification of the whole compound, and obtaining the large-area high-stability photonic crystal structure color-developing fabric.
Example 5
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: coating 24 g/square meter of special polymer (P3904) on the surface of the polyester-cotton blended fabric in a scraping way, and heating and curing the polyester-cotton blended fabric in a heating device at 120 ℃ for 2min to form a film;
(2) preparing 350nm P (St-HEA) nano microsphere dispersion (40 wt% of nano microspheres, 0.07 wt% of carbon black, 5 wt% of fatty acid methyl ester ethoxylate as an activator and the balance of water), and uniformly distributing the dispersion on the surface of the fabric with the special high molecular layer obtained in the step (1) through the induction action of a silk rod;
(3) and (3) placing the compound obtained in the step (2) in a standing heating device (the temperature is 80 ℃, and the humidity is 70%) for 5min, completing the assembly of the nano microspheres, the activation and migration of the interface layer, and the stable solidification of the whole compound, and obtaining the large-area high-stability photonic crystal structure color-developing fabric.
Example 6
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: preparing 28 g/square meter special polymer (P3902s) on the surface of the polyester-cotton blended fabric by adopting a film transfer method, and heating and curing the prepared polymer in a heating device at 110 ℃ for 30 seconds to form a film;
(2) preparing 270nm P (St-MMA-MAA) nano microsphere dispersion (45 wt% of nano microsphere, 0.08 wt% of carbon black, 6 wt% of activator, ethylene oxide adduct of polypropylene glycol and the balance of water), and uniformly distributing the dispersion on the surface of the fabric with the special high molecular layer obtained in the step (1) through a scraper induction effect;
(3) and (3) placing the compound obtained in the step (2) in a continuous infrared heating device (with the temperature of 50 ℃ and the humidity of 70%) for 8min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 7
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: coating 30 g/square meter of special polymer (hard segment: methyl methacrylate; soft segment: butyl acrylate) on the surface of the polyester-polyurethane blended fabric, heating and curing at 140 ℃ in a heating device for 1min to form a film;
(2) preparing 280nm P (St-MMA-AA) nanoparticle dispersion liquid (50 wt% of nanoparticles, 0.09 wt% of carbon black, 7 wt% of fatty alcohol-polyoxyethylene ether as an activator, and the balance of water), and uniformly distributing the dispersion liquid on the surface of the fabric with the special polymer layer obtained in the step (1) under the induction action of a magnetic bar;
(3) and (3) placing the compound obtained in the step (2) in a continuous infrared heating device (with the temperature of 60 ℃ and the humidity of 70%) for 7min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 8
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: preparing 18 g/square meter special polymer (hard segment: hydroxyethyl methacrylate; soft segment: n-amyl acrylate) on the surface of the polyester-polyurethane blended fabric by adopting a film transfer method, and heating and curing the polymer in a heating device at 120 ℃ for 10s to form a film;
(2) preparing 290nm P (St-BA-MMA) nano microsphere dispersion liquid (55 wt% of nano microsphere, 0.1 wt% of carbon black, 8 wt% of alkylphenol polyoxyethylene ether as an activating agent and the balance of water), and enabling the dispersion liquid to be uniformly distributed on the surface of the fabric with the special polymer layer obtained in the step (1) under the induction action of a glass rod;
(3) and (3) placing the compound obtained in the step (2) in a continuous hot air heating device of a standing device (with the temperature of 60 ℃ and the humidity of 60%) for 7min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Example 9
A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric comprises the following steps in sequence:
(1) surface modification of textile substrates: preparing 18 g/square meter special polymer (hard segment: methyl acrylate; soft segment: isooctyl acrylate) on the surface of the polyester-polyurethane blended fabric by adopting a film transfer method, and heating and curing for 10s in a heating device at 120 ℃ to form a film;
(2) preparing 300nm P (St-MAA) nano microsphere dispersion (55 wt% of nano microspheres, 0.1 wt% of carbon black, 10 wt% of fatty alcohol-polyoxyethylene ether as an activating agent and the balance of water), and uniformly distributing the dispersion on the surface of the fabric with the special polymer layer obtained in the step (1) under the induction action of a glass rod;
(3) and (3) placing the compound obtained in the step (2) in a continuous hot air heating device of a standing device (with the temperature of 60 ℃ and the humidity of 60%) for 7min to finish the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the whole compound, so as to obtain the large-area high-stability photonic crystal structure chromogenic fabric.
Comparative example 1
A preparation method of a color-producing fabric with a photonic crystal structure comprises the following steps:
(1) preparing 300nm P (St-MAA) nano microsphere dispersion (55 wt% of nano microspheres, 0.1 wt% of carbon black, 10 wt% of fatty alcohol-polyoxyethylene ether as an activating agent and the balance of water), and uniformly distributing the dispersion on the surface of the polyester fabric under the induction action of a glass rod;
(2) and (3) placing the compound obtained in the step (1) in a continuous hot air heating device of a standing device (with the temperature of 50 ℃ and the humidity of 50%) for 10min, and finishing the assembly of the nano microspheres to obtain the photonic crystal structure chromogenic fabric.
Comparative example 2
A preparation method of a color-producing fabric with a photonic crystal structure comprises the following steps:
(1) surface modification of textile substrates: preparing 25 g/square meter special polymer (hard segment: hydroxyethyl methacrylate; soft segment: n-amyl acrylate) on the surface of the cotton fabric by adopting a film transfer method, and heating and curing the prepared polymer in a heating device at 120 ℃ for 10s to form a film;
(2) preparing 250nm PS nano microsphere dispersion (55 wt% of nano microspheres, 0.1 wt% of carbon black and the balance of water), and uniformly distributing the dispersion on the surface of the polyester fabric under the induction action of a silk rod;
(3) and (3) placing the compound obtained in the step (1) in a continuous hot air heating device of a standing device (with the temperature of 50 ℃ and the humidity of 50%) for 10min, and finishing the assembly of the nano microspheres to obtain the photonic crystal structure chromogenic fabric.
Comparative example 3
A preparation method of a color-producing fabric with a photonic crystal structure comprises the following steps:
(1) surface modification of textile substrates: preparing 2 g/square meter of special polymer (PUE1650) on the surface of the polyester fabric by adopting a blade coating method, and heating and curing the polyester fabric in a heating device at 100 ℃ for 2min to form a film;
(2) preparing 250nm PS nano microsphere dispersion (55 wt% of nano microsphere, 0.1 wt% of carbon black, 0.5 wt% of fatty alcohol-polyoxyethylene ether and the balance of water), and uniformly distributing the dispersion on the surface of the polyester fabric under the induction action of a silk rod;
(3) and (3) placing the compound obtained in the step (1) in a continuous hot air heating device of a standing device (the temperature is 70 ℃, and the humidity is 50%) for 5min, and finishing the assembly of the nano microspheres to obtain the photonic crystal structure chromogenic fabric.
In example 1, the digital photograph of the assembled photonic crystal film is shown in fig. 1, under the same experimental conditions, without adding an activator (1 wt%) and without adding the PS nanosphere dispersion. According to the observation of the figure, when the activating agent is not added, the liquid of the nano microsphere dispersion liquid shrinks in the assembly process, and finally a continuous photonic crystal structure color generation film cannot be formed, so that large-area continuous preparation is not easy.
A digital photograph of the photonic crystal structure color-producing fabric prepared in example 2 is shown in fig. 2. The prepared photonic crystal fabric is bright and bright in color and has no cracks.
The reflectance curve of the photonic crystal structure color-producing fabric prepared in example 3 is shown in fig. 3. As shown in the figure, the reflectance peak is high and narrow, demonstrating that the structured color has high brightness and saturation.
An SEM picture of the photonic crystal coating prepared in example 4 is shown in fig. 4. As shown in the figure, the photonic crystal assembled by the nano microspheres has excellent structural regularity.
The SEM picture of the surface of the special polymer migration photonic crystal of the color-producing fabric with the photonic crystal structure prepared in example 5 is shown in figure 5. As shown in the figure, the polyurethane chain segment which moves upwards in the assembling process can be observed to form petal-like local bonding in the nanometer microsphere under a higher multiple, the function of a ligament is realized in the photonic crystal, and simultaneously more air phase is reserved, so that the structural stability of the photonic crystal is improved.
The digital photos of the large-area photonic crystal structure color-generating fabrics prepared in examples 6 and 7 are shown in FIG. 6. As shown in the figure, the method can continuously prepare the large-area photonic crystal structure color-generating fabric with uniform color and no defects.
The pictures showing the iridescence effect of the large area photonic crystal structure color-generating fabric prepared in examples 7, 8 and 9 are shown in FIG. 7. As shown in the figure, the prepared photonic crystal has the inherent property of the crystal, namely anisotropy, and presents different structural colors under different angles, thereby showing an attractive iridescence effect.
The structural stability display picture of the photonic crystal structure color-producing fabric prepared in example 5 is shown in fig. 8. As shown in the figure, the prepared photonic crystal structure color-producing fabric has excellent structure stability, the photonic crystal coating is not damaged at all after being bent, and the color of the bent part is not changed.
Fig. 9 is a digital photograph of the photonic crystal structure color-producing fabrics prepared in comparative examples 1, 2, 3, wherein a, b, c correspond to comparative examples 1, 2, 3 in order. As shown in the figure, the special high molecular polymer is not added on the surface of the fabric in the comparative example 1, the structural stability of the finally prepared photonic crystal structure color-developing fabric is poor, and the activating agent is not added in the comparative example 2, so that a large number of obvious cracks are generated in the finally prepared photonic crystal structure color-developing fabric. In comparative example 3, the consumption of the special polymer and the activator is too small, and the structural stability of the finally prepared photonic crystal structure color-producing fabric is poor.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The large-area preparation method of the high-stability and high-saturation photonic crystal structure color-generating fabric provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A large-area preparation method of a high-stability high-saturation photonic crystal structure color-producing fabric is characterized by comprising the following steps:
s1, surface modification of the textile substrate: coating a special high molecular polymer on the surface of a textile substrate, heating and curing to form a film, and obtaining a fabric with a high molecular layer;
the special high molecular polymer is a soft segment hard segment copolymerization polyurethane high molecular polymer or a soft segment hard segment copolymerization polyacrylic acid high molecular polymer;
s2, preparing a nano microsphere dispersion liquid containing an activating agent, and enabling the nano microsphere dispersion liquid to be uniformly distributed on the surface of the fabric with the polymer layer obtained in S1 under the action of external force induction;
the nanometer microsphere dispersion liquid containing the activating agent comprises the following components in percentage by weight: 15-55 wt% of nano microspheres, 0.02-0.1 wt% of carbon black, 1-10 wt% of activating agent and the balance of water;
s3, carrying out heating treatment on the compound obtained in the step S2, completing the assembly of the nano microspheres, the activation and migration of the interface layer and the stable solidification of the compound, and finally obtaining the large-area photonic crystal structure chromogenic fabric.
2. The large area fabrication method according to claim 1, wherein: the soft segment and hard segment copolymerization type polyurethane high molecular polymer has a hard segment selected from one of toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate; the soft segment is a long carbon chain soft substance with crystallization performance, the length of a carbon chain in a repeating unit is more than 4C, and the soft segment is selected from one of poly adipic acid-1, 4 butanediol ester, poly adipic acid-1, 6 hexanediol ester and poly-1, 6-hexamethylene-carbonate;
the soft segment hard segment copolymerization type polyacrylic acid high molecular polymer has the hard segment selected from one of methyl methacrylate, hydroxyethyl methacrylate or methyl acrylate, the soft segment is a long straight chain monomer with more than 4C, and the soft segment is selected from one of butyl acrylate, n-pentyl acrylate, n-hexyl acrylate and isooctyl acrylate.
3. The large area fabrication method according to claim 1, wherein: the nano-microsphere is organic high-molecular polymer polyphenylEthylene (PS) nano-microsphere, polymethyl methacrylate (PMMA) nano-microsphere, polystyrene @ polydopamine (PS @ PDA), polystyrene @ silicon dioxide (PS @ SiO)2) Poly (styrene-hydroxyethyl acrylate) (P (St-HEA)), poly (styrene-methyl methacrylate) (P (St-MMA)), poly (styrene-methyl methacrylate-methacrylic acid) (P (St-MMA-MAA)), poly (styrene-methyl methacrylate-acrylic acid) (P (St-MMA-AA)), poly (styrene-butyl acrylate-methyl methacrylate) (P (St-BA-MMA)), poly (styrene-methacrylic acid) (P (St-MAA)), and inorganic Silica (SiO)2) One or more of the nano microspheres.
4. The large area fabrication method according to claim 1, wherein: the activating agent is one or a mixture of several of amphiphilic fatty alcohol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate and ethylene oxide addition product of polypropylene glycol.
5. The large area fabrication method according to claim 1, wherein: in S3, the heat treatment conditions were: the temperature is 50-80 deg.C, humidity is 50-70%, and the time is 2-10 min.
6. The large area fabrication method according to claim 1, wherein: the coating amount of the special high molecular polymer is 8-30 g/sq m (dry weight).
7. The large area fabrication method according to claim 1, wherein: the diameter of the nano microsphere is 150-350 nm, the sphericity is good, and the monodispersion index is less than 0.08.
8. The large area fabrication method according to claim 1, wherein: the external force induction mode is one of a wire rod, a scraper, a magnetic rod and a glass rod scraping and shearing mode.
9. The large area fabrication method according to claim 1, wherein: in S1, the special high molecular polymer coating mode is one of a direct blade coating method and a film transfer method; when the direct blade coating method is adopted, the film forming conditions are as follows: the temperature is 80-140 ℃, and the time is 1-5 min; in the case of the film transfer method, the film formation conditions are as follows: the temperature is 80-120 ℃, and the time is 10-90 s.
10. The large area fabrication method according to claim 1, wherein: the textile base material is selected from one of cotton fabric, polyester fabric, real silk fabric, polyester-cotton blended fabric, polyester-polyurethane blended fabric and the like.
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