Nonwoven fabric with ecological sensing function and production process thereof

Abstract

The present application relates to the technical field of facial non-woven fabric materials, and discloses a non-woven fabric with ecological sensing function and a production process thereof. The non-woven fabric is printed on the surface with an anthocyanin quaternization microcapsule-containing sensing printing liquid, the anthocyanin quaternization microcapsule contains copper-based MOF limited encapsulated anthocyanin chelate in the inside, the copper-based MOF limited effect and the entrapping effect of the gelatin capsule wall form a double-layer protection structure, the porous framework of the copper-based MOF can isolate oxygen, enzymes and impurity ions from degrading anthocyanin, and the gelatin capsule wall provides a macroscopic mechanical barrier and a controlled release channel, and the two cooperate to improve the storage stability of anthocyanin.

Description

Technical Field

[0001] This invention relates to the field of facial cleansing nonwoven fabric materials technology, specifically to a nonwoven fabric with eco-sensing function and its production process. Background Technology

[0002] With the continuous improvement of residents' skincare awareness and the rapid development of the disposable hygiene products industry, non-woven fabric facial cleansing wipes and washcloths have gradually become one of the core consumables for daily skincare, with both market demand and industry scale showing a stable growth trend. Traditional non-woven facial cleansing wipes mainly rely on the physical friction of the fibers themselves to achieve cleaning, with a single function, and cannot provide intuitive and visual feedback on the degree of residual oil and dirt on the skin surface. Consumers find it difficult to accurately judge the cleansing endpoint during use. On the one hand, insufficient cleansing can easily lead to clogged pores and acne, and on the other hand, over-cleansing may damage the skin's slightly acidic barrier, causing secondary problems such as skin sensitivity, dryness, degreasing, and even inflammatory reactions. It is no longer able to meet consumers' dual upgrade needs for skincare experience and product functionality.

[0003] Against this backdrop, eco-friendly nonwoven fabrics with intelligent skin cleanliness sensing capabilities have emerged and rapidly become an important development direction in the disposable care products field. The core design concept of this type of material lies in utilizing pH-sensitive color-changing materials to respond to local pH fluctuations on the skin surface caused by oil and dirt residue. The material's own color change visually reflects the degree of cleanliness, providing users with a visual basis for determining the cleanliness endpoint. Ideally, pH-sensitive color-changing materials should possess characteristics such as high color-changing sensitivity, fast response speed, good biocompatibility, and good compatibility with nonwoven fabric substrates. However, existing technologies typically involve directly loading pH-sensitive pigments such as natural anthocyanins and synthetic acid-base indicators onto the nonwoven fabric surface through methods such as dyeing and physical coating. While this theoretically achieves a preliminary pH-responsive color-changing function, practical applications reveal numerous insurmountable technical defects, severely restricting the industrialization and long-term reliability of such products.

[0004] Chinese patent application CN121496764A discloses a nonwoven fabric with eco-sensing function and its production process. The anthocyanins in the pH-sensitive color-changing nanomaterials in this solution display different colors due to changes in pH value. That is, the cleanliness of facial skin can be known by the color change of the nonwoven fabric surface. However, anthocyanins are natural polyphenol pigments that are highly sensitive to heat, light, oxygen and metal ions. When the finished product is stored at room temperature and exposed to sunlight, the anthocyanins are easily degraded and lost, and the color-changing function is lost. Summary of the Invention

[0005] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a nonwoven fabric with eco-sensing functions and its production process. By printing an inductive printing liquid containing anthocyanin quaternized microcapsules onto the surface of the nonwoven fabric, the anthocyanin quaternized microcapsules contain anthocyanin chelates encapsulated in a copper-based MOF. The confinement effect of the copper-based MOF and the encapsulation effect of the capsule wall form a dual-layer protective structure. The porous framework of the copper-based MOF can isolate the degradation of anthocyanins by oxygen, enzymes and impurity ions, while the capsule wall provides a macroscopic mechanical barrier and a controlled-release channel. The two work together to improve the storage stability of anthocyanins.

[0006] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: A production process for a nonwoven fabric with eco-sensing capabilities includes the following steps: Step 1: Treating with NaOH disrupts the hydrogen bond network between cellulose molecules, reducing its crystallinity and exposing more surface hydroxyl active sites, resulting in activated microcrystalline cellulose particles.

[0007] Step 2: Based on the etherification reaction, the activated microcrystalline cellulose particles are deprotonated to form oxygen anion active centers, which attack the active sites of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, and the quaternary ammonium salt cationic groups are covalently grafted onto the activated microcrystalline cellulose particles to obtain quaternized microcrystalline cellulose.

[0008] Step 3: Dimethylimidazole is used as a ligand to coordinate with copper ions and self-assemble rapidly to form a porous framework. Anthocyanins, as guest molecules, are encapsulated in situ in the porous framework, and the surface anthocyanins form coordination chelates with the unsaturated copper ions on the surface of the porous framework to obtain anthocyanin chelates.

[0009] Step 4: Using negatively charged gelatin as the wall material, electrostatic complexation occurs between it and positively charged quaternized microcrystalline cellulose. The mixture spontaneously condenses and deposits on the surface of the anthocyanin chelate to form a capsule wall. The capsule wall structure is initially solidified by low-temperature setting to obtain anthocyanin quaternized microcapsules.

[0010] Step 5: Using water-based acrylic emulsion as a film-forming binder, anthocyanin quaternized microcapsules are uniformly dispersed in deionized water to prepare an inductive printing liquid. The inductive printing liquid is then uniformly printed onto the surface of the nonwoven fabric using a printing roller. After low-temperature drying, a nonwoven fabric with eco-sensing function is obtained.

[0011] Furthermore, the ratio of aqueous acrylate emulsion, deionized water, and anthocyanin quaternized microcapsules is 5-8g: 90-92g: 5-6g.

[0012] Furthermore, the specific preparation steps for activated microcrystalline cellulose particles are as follows: Mix microcrystalline cellulose particles with NaOH, grind for 2-4 min, then place in a reaction vessel containing deionized water, stir and react for 2-4 h at 100-110℃ and 500-600 r / min, filter, wash the precipitate 2-4 times with deionized water and anhydrous ethanol, and vacuum dry at 60-80℃ for 1-2 h to obtain activated microcrystalline cellulose particles.

[0013] Furthermore, the ratio of microcrystalline cellulose particles, NaOH, and deionized water is 40-50g: 3-5g: 180-190mL.

[0014] Furthermore, the microcrystalline cellulose particles are obtained by drying microcrystalline cellulose at 105-110℃ for 3-4 hours and then grinding and pulverizing it for 2-4 minutes.

[0015] Furthermore, the specific preparation steps of quaternized microcrystalline cellulose are as follows: Activated microcrystalline cellulose particles and deionized water were added to a reaction vessel and stirred for 20-30 min at 20-25℃ and 500-600 r / min. Then, NaOH was added and mixed, and the mixture was stirred and swollen at room temperature for 30-40 min. Next, (3-chloro-2-hydroxypropyl)trimethylammonium chloride was added, and the mixture was heated to 45-50℃ and stirred for 20-22 h. The pH was neutralized to 8 by adding glacial acetic acid solution dropwise. The mixture was centrifuged at 5000-6000 r / min for 3-5 min, filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then vacuum dried at 60-80℃ for 1-2 h to obtain quaternized microcrystalline cellulose.

[0016] Furthermore, the ratio of activated microcrystalline cellulose particles, deionized water, NaOH, and (3-chloro-2-hydroxypropyl)trimethylammonium chloride is 1-2g: 20-30mL: 3-5g: 1.8-3.6g.

[0017] Furthermore, the specific preparation steps for anthocyanin chelates are as follows: Under light-protected conditions, a 0.16 mol / L copper nitrate solution was added dropwise to solution A at a rate of 50-60 drops / min. The mixture was stirred at 20-25℃ and 500-600 r / min for 20-30 min, centrifuged at 5000-6000 r / min for 3-5 min, filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then vacuum dried at 40-50℃ for 1-2 h to obtain anthocyanin chelates.

[0018] Furthermore, the specific preparation steps for solution A are as follows: Dimethylimidazole, deionized water, and anthocyanins were added to a reaction vessel and stirred and dispersed for 20-30 minutes under conditions of darkness, 20-25℃, and 500-600 r / min. Then, 0.2 mol / L sodium hydroxide solution was added to adjust the pH value to 6.0-6.5 to obtain solution A.

[0019] Furthermore, the ratio of dimethylimidazole, deionized water, and anthocyanin is 2-3g: 80-100mL: 0.3-0.45g.

[0020] Furthermore, the specific preparation steps of the anthocyanin quaternized microcapsules are as follows: The emulsion and a gelatin solution with a mass fraction of 5-7% were stirred and mixed. The pH of the system was adjusted to 5.2 with a 5-7% NaOH solution. The system was subjected to a re-coagulation reaction at 45-55℃ and 300-400 r / min for 30-40 min. The temperature was then lowered to 1-2℃, and genipin was added. The pH of the system was then adjusted to 5.0-5.2 with a 5% NaOH solution. The system was then further cross-linked and cured for 2-4 h to obtain anthocyanin quaternized microcapsules.

[0021] Furthermore, the ratio of emulsion, gelatin solution, and genipin is 50-60 mL: 100-120 mL: 0.8-1 g.

[0022] Furthermore, the specific preparation steps of the emulsion are as follows: Quaternized microcrystalline cellulose, deionized water, Tween-80, anthocyanin chelate, anhydrous ethanol and Span-80 were stirred and mixed, and sheared and emulsified at 2000-3000 r / min for 5 min to obtain an emulsion.

[0023] Furthermore, the ratio of quaternized microcrystalline cellulose, deionized water, Tween-80, anthocyanin chelate, anhydrous ethanol and Span-80 is 0.5-0.8g: 80-90mL: 0.7-0.9g: 1.5-1.9g: 1-3mL: 0.5-0.8g.

[0024] (III) Beneficial Effects Compared with the prior art, the present invention provides a nonwoven fabric with ecological sensing function and its production process, which has the following beneficial effects: 1. This invention involves printing an inductive printing liquid containing anthocyanin quaternized microcapsules onto the surface of a nonwoven fabric. The anthocyanin quaternized microcapsules contain anthocyanin chelates encapsulated by a copper-based MOF. The confinement effect of the copper-based MOF and the encapsulation effect of the capsule wall form a dual-layer protective structure. The porous framework of the copper-based MOF can isolate the degradation of anthocyanins by oxygen, enzymes and impurity ions, while the capsule wall provides a macroscopic mechanical barrier and a controlled-release channel. The two work together to improve the storage stability of anthocyanins.

[0025] 2. This invention constructs anthocyanin quaternized microcapsules that integrate quaternized microcrystalline cellulose as the synergistic wall-forming agent, copper-based MOF-confined anthocyanins, and genipin crosslinking with the capsule wall. The quaternized microcrystalline cellulose possesses both antibacterial and cationic properties. Its positively charged surface undergoes strong electrostatic complexation with negatively charged gelatin molecules, directly participating in the interfacial construction of the capsule wall. This significantly enhances the mechanical strength and structural stability of the microcapsules, preventing sudden leakage of functional components caused by capsule wall rupture during wiping.

[0026] 3. This invention relies on the cationic antibacterial properties of quaternized microcrystalline cellulose, the metal ion antibacterial properties of copper-based MOF, and the polyphenolic antibacterial properties of anthocyanins to form a synergistic antibacterial system. It has a significant antibacterial effect on common skin pathogens, proving that the capsule wall has hydrophilicity and the water-based acrylic ester printing system has excellent interfacial compatibility. After printing and forming a film, it can be firmly anchored to the surface of nonwoven fabric, which not only ensures the resistance to dry and wet friction, but also does not damage the breathable and skin-friendly properties of nonwoven fabric.

[0027] 4. In this invention, the gelatin is alkaline type B gelatin with an isoelectric point of approximately 4.7-5.2. After forming the capsule wall of the anthocyanin quaternized microcapsules, the gelatin carries a weak negative charge, and most of the negative charge has been neutralized by the positive charge of the quaternized microcrystalline cellulose. The net charge inside is minimal, and the ion concentration inside and outside the capsule wall is basically balanced. Therefore, in the initial state, the capsule wall structure is the most compact and the porosity is the lowest, and the contact between anthocyanins and the outside world is limited. When the skin pH increases with the presence of dirt residue, the degree of dissociation of the carboxyl groups on the gelatin molecular chain intensifies, the negative charge density increases significantly, and the charge balance is broken. In order to maintain the electroneutrality of the system, cations in the external solution will spontaneously permeate into the network, resulting in an ion concentration inside the network that is much higher than that in the external solution. This causes the anthocyanin quaternized microcapsules to macroscopically exhibit water absorption and expansion of the capsule wall, increased volume, and significantly increased porosity. This significantly enhances the color development and response amplitude of anthocyanins, effectively solving the problem of weak color change of anthocyanins and insufficient visual recognition, and greatly improving the intuitiveness and accuracy of cleanliness. Detailed Implementation

[0028] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0030] Example 1: A production process for a nonwoven fabric with eco-sensing function, comprising the following steps: S1: Dry 50g of microcrystalline cellulose at 105℃ for 3h, grind and pulverize for 2min to obtain microcrystalline cellulose particles with a particle size of 20μm; then mix 40g of microcrystalline cellulose particles with 3g of NaOH, grind for 2min, and then place in a reaction vessel containing 180mL of deionized water. Stir and react for 2h at 100℃ and 500r / min. Filter, wash the precipitate twice with deionized water and anhydrous ethanol, and vacuum dry at 60℃ for 1h to obtain activated microcrystalline cellulose particles.

[0031] S2: Add 1g of activated microcrystalline cellulose particles and 20mL of deionized water to a reaction vessel, stir and react for 20min at 20℃ and 500r / min, then add 3g of NaOH and mix, stir and swell at room temperature for 30min, then add 1.8g of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, heat to 45℃, continue stirring and react for 20h, add glacial acetic acid solution to neutralize the pH to 8, centrifuge at 5000r / min for 3min, filter, wash the precipitate twice with deionized water and anhydrous ethanol, and vacuum dry at 60℃ for 1h to obtain quaternized microcrystalline cellulose.

[0032] S3: 2g of dimethylimidazole, 80mL of deionized water and 0.3g of anthocyanin were added to a reaction vessel and stirred and dispersed for 20min at 20℃ and 500r / min in the dark. Then, 0.2mol / L sodium hydroxide solution was added to adjust the pH to 6.0 to obtain solution A. Under the dark, 40mL of 0.16mol / L copper nitrate solution was added dropwise to solution A at a rate of 50 drops / min. The reaction was stirred and reacted for 20min at 20℃ and 500r / min, centrifuged at 5000r / min for 3min, filtered, and the precipitate was washed twice with deionized water and anhydrous ethanol and dried under vacuum at 40℃ for 1h to obtain an anthocyanin chelate with a copper-based MOF confined encapsulation structure.

[0033] S4: Mix 0.5g of quaternized microcrystalline cellulose, 80mL of deionized water, 0.7g of Tween-80, 1.5g of anthocyanin chelate, 1mL of anhydrous ethanol and 0.5g of Span-80, and shear emulsify at 2000r / min for 5min to obtain an emulsion.

[0034] S5: Mix 50 mL of emulsion and 100 mL of 5% gelatin solution by stirring. Adjust the pH of the system to 5.2 with 5% NaOH solution. Perform a re-coagulation reaction at 45℃ and 300 r / min for 30 min. Cool down to 1℃, then add 0.8 g of genipin. Adjust the pH of the system to 5.0 with 5% NaOH solution and continue cross-linking and curing for 2 h to obtain anthocyanin quaternized microcapsules.

[0035] S6: Mix 5g of water-based acrylic emulsion, 90g of deionized water, and 5g of anthocyanin quaternized microcapsules to obtain an inductive printing liquid; print the inductive printing liquid onto the surface of nonwoven fabric using a printing roller, and dry at 40℃ for 30min to obtain a nonwoven fabric with eco-sensing function.

[0036] Example 2: A production process for a nonwoven fabric with eco-sensing function, comprising the following steps: S1: 55g of microcrystalline cellulose was dried at 107.5℃ for 3.5h and ground for 3min to obtain microcrystalline cellulose particles with a particle size of 25μm; then 45g of microcrystalline cellulose particles and 4g of NaOH were mixed and ground for 3min, and then placed in a reaction vessel containing 185mL of deionized water. The mixture was stirred and reacted at 105℃ and 550r / min for 3h. After filtration, the precipitate was washed three times with deionized water and anhydrous ethanol and dried under vacuum at 70℃ for 1.5h to obtain activated microcrystalline cellulose particles.

[0037] S2: Add 1.5g of activated microcrystalline cellulose particles and 25mL of deionized water to a reaction vessel, stir and react for 25min at 22.5℃ and 550r / min, then add 4g of NaOH and mix, stir and swell at room temperature for 35min, then add 2.7g of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, heat to 47.5℃, continue stirring and react for 21h, add glacial acetic acid solution to neutralize the pH to 8, centrifuge at 5500r / min for 4min, filter, wash the precipitate three times with deionized water and anhydrous ethanol, and vacuum dry at 70℃ for 1.5h to obtain quaternized microcrystalline cellulose.

[0038] S3: 2.5 g of dimethylimidazole, 90 mL of deionized water and 0.375 g of anthocyanin were added to a reaction vessel and stirred and dispersed for 25 min under light-protected conditions at 22.5 °C and 550 r / min. Then, 0.2 mol / L sodium hydroxide solution was added to adjust the pH to 6.25 to obtain solution A. Under light-protected conditions, 50 mL of 0.16 mol / L copper nitrate solution was added dropwise to solution A at a rate of 55 drops / min. The reaction was stirred and reacted for 25 min at 22.5 °C and 550 r / min, centrifuged at 5500 r / min for 4 min, filtered, and the precipitate was washed three times with deionized water and anhydrous ethanol. It was then vacuum dried at 45 °C for 1.5 h to obtain an anthocyanin chelate with a copper-based MOF confined encapsulation structure.

[0039] S4: Mix 0.65g of quaternized microcrystalline cellulose, 85mL of deionized water, 0.8g of Tween-80, 1.7g of anthocyanin chelate, 2mL of anhydrous ethanol and 0.65g of Span-80, and shear emulsify at 2500r / min for 5min to obtain an emulsion.

[0040] S5: Mix 55 mL of emulsion and 110 mL of 6% gelatin solution by stirring. Adjust the pH of the system to 5.2 with 5% NaOH solution. Perform a re-coagulation reaction at 50℃ and 350 r / min for 35 min. Cool down to 1.5℃, then add 0.9 g of genipin. Adjust the pH of the system to 5.1 with 5% NaOH solution and continue cross-linking and curing for 3 h to obtain anthocyanin quaternized microcapsules.

[0041] S6: Mix 6.5g of water-based acrylic emulsion, 91g of deionized water, and 5.5g of anthocyanin quaternized microcapsules to obtain an inductive printing liquid; print the inductive printing liquid onto the surface of nonwoven fabric using a printing roller, and dry at 45℃ for 35min to obtain a nonwoven fabric with eco-sensing function.

[0042] Example 3: A production process for a nonwoven fabric with eco-sensing function, comprising the following steps: S1: 60g of microcrystalline cellulose was dried at 110℃ for 4h and ground for 4min to obtain microcrystalline cellulose particles with a particle size of 30μm; then 50g of microcrystalline cellulose particles and 5g of NaOH were mixed and ground for 4min, and then placed in a reaction vessel containing 190mL of deionized water. The mixture was stirred and reacted at 110℃ and 600r / min for 4h. After filtration, the precipitate was washed 4 times with deionized water and anhydrous ethanol and dried under vacuum at 80℃ for 2h to obtain activated microcrystalline cellulose particles.

[0043] S2: Add 2g of activated microcrystalline cellulose particles and 30mL of deionized water to a reaction vessel, stir and react for 30min at 25℃ and 600r / min, then add 5g of NaOH and mix, stir and swell at room temperature for 40min, then add 3.6g of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, heat to 50℃, continue stirring and react for 22h, add glacial acetic acid solution to neutralize the pH to 8, centrifuge at 6000r / min for 5min, filter, wash the precipitate 4 times with deionized water and anhydrous ethanol, and vacuum dry at 80℃ for 2h to obtain quaternized microcrystalline cellulose.

[0044] S3: Add 3g of dimethylimidazole, 100mL of deionized water and 0.45g of anthocyanin to a reaction vessel. Stir and disperse for 30min at 25℃ and 600r / min in the dark. Then add 0.2mol / L sodium hydroxide solution to adjust the pH to 6.5 to obtain solution A. Under the dark, add 60mL of 0.16mol / L copper nitrate solution at a rate of 60 drops / min to solution A. Stir and react for 30min at 25℃ and 600r / min. Centrifuge at 6000r / min for 5min. Filter and wash the precipitate four times with deionized water and anhydrous ethanol. Dry under vacuum at 50℃ for 2h to obtain an anthocyanin chelate with a copper-based MOF confined encapsulation structure.

[0045] S4: Mix 0.8g of quaternized microcrystalline cellulose, 90mL of deionized water, 0.9g of Tween-80, 1.9g of anthocyanin chelate, 3mL of anhydrous ethanol and 0.8g of Span-80, and shear emulsify at 3000r / min for 5min to obtain an emulsion.

[0046] S5: Mix 60 mL of emulsion and 120 mL of 7% gelatin solution by stirring. Adjust the pH of the system to 5.2 with 5% NaOH solution. Perform a re-coagulation reaction at 55℃ and 400 r / min for 40 min. Cool down to 2℃, then add 1 g of genipin. Adjust the pH of the system to 5.2 with 5% NaOH solution and continue cross-linking and curing for 4 h to obtain anthocyanin quaternized microcapsules.

[0047] S6: Mix 8g of water-based acrylic emulsion, 92g of deionized water, and 6g of anthocyanin quaternized microcapsules to obtain an inductive printing liquid; print the inductive printing liquid onto the surface of nonwoven fabric using a printing roller, and dry at 50℃ for 40min to obtain a nonwoven fabric with eco-sensing function.

[0048] Comparative Example 1: Based on Example 3, the quaternized microcrystalline cellulose in step S4 was replaced with the activated microcrystalline cellulose particles prepared in step S1, while the other steps remained unchanged, and a nonwoven fabric with eco-sensing function was prepared.

[0049] Comparative Example 2: Based on Example 3, the anthocyanin chelate in step S4 was replaced with the raw anthocyanin in step S3, while the other steps remained unchanged, to prepare a nonwoven fabric with eco-sensing function.

[0050] Comparative Example 3: Based on Example 3, the anthocyanin quaternized microcapsules in step S6 were replaced with the raw anthocyanin in step S3, while the other steps remained unchanged, to prepare a nonwoven fabric with eco-sensing function.

[0051] Performance tests were conducted on Examples 1-3 and Comparative Examples 1-3. Simulated fats were prepared by heating and mixing 20% ​​squalane, 30% triglyceride, 15% palmitic acid, 10% stearic acid, 10% cholesterol, and 15% petrolatum according to the specified mass ratio. Fresh pigskin was fixed on the test bench and uniformly coated with a solution of 2 mg / cm³. 2 Simulated grease and oily skin surfaces were used to fix eco-sensitive nonwoven fabric to the friction head of a fabric friction tester. Standardized parameters were set: pressure 12 kPa, 10 rubs, simulating manual wiping. The total wet weight of the nonwoven fabric after wiping was weighed, and the wet weight of the blank nonwoven fabric was tested simultaneously, along with the swelling rate. The inhibition rates of Staphylococcus aureus and Escherichia coli were tested according to GB / T 20944.2-2007 "Evaluation of Antimicrobial Properties of Textiles - Part 2: Absorption Method" and GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles - Part 3: Shaking Method". The eco-sensitive nonwoven fabric was placed in a constant temperature and humidity test chamber with pre-set conditions of 40℃ and 75%RH, and the anthocyanin retention rate was tested after 6 months. The staining grade was tested according to the standard of GB / T 3920-2024 "Color Fastness Tests - Color Fastness to Rubbing". The results are shown in Table 1. Table 1

[0052] As shown in Table 1, the activated microcrystalline cellulose in Comparative Example 1 has no strong positive charge on its surface, and cannot form an electrostatic complex with the negatively charged gelatin to participate in the construction of the capsule wall. The complex condensed phase separation effect is poor, and the resulting pure gelatin capsule wall has insufficient density and few physical cross-linking points, resulting in a significant decrease in mechanical strength. It is easy to break when wiping, leading to sudden leakage of internal functional components. It lacks a fixed amount of cationic quaternary ammonium groups, and cannot form an initial charge balance with the negative charge of gelatin. The swelling range of the capsule wall is greatly reduced when the pH increases, and it cannot amplify the color change signal of anthocyanins through structural changes. The cleanliness recognition is significantly reduced, and the core sensing enhancement function is lost. It lacks the cationic antibacterial effect of quaternary ammonium salts, and only the binary antibacterial effect of copper-based MOF and anthocyanins remains. The triple synergistic effect mechanism disappears, and the antibacterial rate against common skin pathogens is significantly reduced. The capsule wall has high porosity and poor density, and anthocyanins can easily migrate and dissolve out through the gaps in the capsule wall, increasing the risk of staining when wiping. The rate of pigment leakage accelerates during storage, and the anthocyanin retention rate decreases after aging.

[0053] In Comparative Example 2, the free anthocyanins were not protected by the physical barrier of the MOF porous framework, nor did they have the coordination stabilizing effect of unsaturated copper sites. They were easily oxidized and degraded by oxygen, light, and temperature. After aging, the pigment retention rate decreased significantly, and the product shelf life was significantly shortened. The free anthocyanins had a small molecular weight and easily diffused and migrated outward through the micropores of the capsule wall. When wiped with water, the dissolution rate was fast and the dissolution amount was high. They easily stained the skin and towels. They lacked the metal ion sustained-release antibacterial effect of copper-based MOFs and only had a binary antibacterial system of quaternized cellulose and anthocyanins. The antibacterial broad spectrum and long-term effect were reduced.

[0054] In Comparative Example 3, anthocyanins were directly exposed to the printing system and the external environment. Light, heat, and oxygen could directly act on the pigment molecules, and significant degradation occurred during the production and drying process. After aging, the pigment retention rate was extremely low, and the pigments completely faded and became ineffective within a short period of time when stored at room temperature, failing to meet shelf-life requirements. Anthocyanins were only physically adsorbed onto the surface of nonwoven fibers, and a large amount dissolved immediately upon contact with water. When wiped, they severely stained the skin and clothing, making them completely unusable. The synergistic antibacterial effect of quaternized cellulose and copper-based MOF was lacking, and the antibacterial rate was extremely low due to the weak antibacterial activity of anthocyanins themselves, making it impossible to achieve antibacterial and skin-care effects.

[0055] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0056] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A production process for nonwoven fabrics with ecological sensing functions, characterized in that, Includes the following steps: Step 1: Disrupt the hydrogen bond network between cellulose molecules by treating with NaOH, exposing more hydroxyl active sites to obtain activated microcrystalline cellulose particles; Step 2: Based on the etherification reaction, the activated microcrystalline cellulose particles undergo deprotonation to form oxygen anion active centers, which attack the active sites of (3-chloro-2-hydroxypropyl)trimethylammonium chloride, and the quaternary ammonium salt cationic groups are covalently grafted onto the activated microcrystalline cellulose particles to obtain quaternized microcrystalline cellulose. Step 3: Coordinate self-assembly of copper ions with dimethylimidazole as a ligand rapidly forms a porous framework, and anthocyanins as guest molecules are in situ encapsulated in the porous framework to obtain anthocyanin chelates. Step 4: Using negatively charged gelatin as the wall material, electrostatic complexation occurs between it and positively charged quaternized microcrystalline cellulose, which spontaneously condenses and deposits on the surface of anthocyanin chelates to form capsule walls. The capsule wall structure is initially solidified by low-temperature setting to obtain anthocyanin quaternized microcapsules. Step 5: Using water-based acrylic emulsion as a film-forming binder, anthocyanin quaternized microcapsules are uniformly dispersed in deionized water to prepare an inductive printing liquid. The inductive printing liquid is then uniformly printed onto the surface of the nonwoven fabric using a printing roller. After low-temperature drying, a nonwoven fabric with eco-sensing function is obtained. The ratio of the aqueous acrylate emulsion, deionized water, and anthocyanin quaternized microcapsules is 5-8g: 90-92g: 5-6g.

2. The production process of a nonwoven fabric with ecological sensing function according to claim 1, characterized in that, The specific preparation steps for the activated microcrystalline cellulose particles are as follows: Mix microcrystalline cellulose particles with NaOH, grind for 2-4 min, then place in a reaction vessel containing deionized water, stir and react for 2-4 h at 100-110℃ and 500-600 r / min, filter, wash the precipitate 2-4 times with deionized water and anhydrous ethanol, and vacuum dry at 60-80℃ for 1-2 h to obtain activated microcrystalline cellulose particles.

3. The production process of a nonwoven fabric with ecological sensing function according to claim 2, characterized in that, The ratio of microcrystalline cellulose particles, NaOH, and deionized water is 40-50g: 3-5g: 180-190mL; The microcrystalline cellulose particles are obtained by drying microcrystalline cellulose at 105-110℃ for 3-4 hours and then grinding and pulverizing it for 2-4 minutes.

4. The production process of a nonwoven fabric with ecological sensing function according to claim 1, characterized in that, The specific preparation steps for the quaternized microcrystalline cellulose are as follows: Activated microcrystalline cellulose particles and deionized water were added to a reaction vessel and stirred for 20-30 min at 20-25℃ and 500-600 r / min. Then, NaOH was added and mixed, and the mixture was stirred and swollen at room temperature for 30-40 min. Then, (3-chloro-2-hydroxypropyl)trimethylammonium chloride was added, and the mixture was heated to 45-50℃ and stirred for 20-22 h. The pH was neutralized to 8 by adding glacial acetic acid solution dropwise. The mixture was centrifuged at 5000-6000 r / min for 3-5 min, filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then vacuum dried at 60-80℃ for 1-2 h to obtain quaternized microcrystalline cellulose. The ratio of activated microcrystalline cellulose particles, deionized water, NaOH and (3-chloro-2-hydroxypropyl)trimethylammonium chloride is 1-2g: 20-30mL: 3-5g: 1.8-3.6g.

5. The production process of a nonwoven fabric with ecological sensing function according to claim 1, characterized in that, The specific preparation steps for the anthocyanin chelate are as follows: Under light-protected conditions, a 0.16 mol / L copper nitrate solution was added dropwise to solution A at a rate of 50-60 drops / min. The mixture was stirred at 20-25℃ and 500-600 r / min for 20-30 min, centrifuged at 5000-6000 r / min for 3-5 min, filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then vacuum dried at 40-50℃ for 1-2 h to obtain anthocyanin chelates.

6. The production process of a nonwoven fabric with ecological sensing function according to claim 5, characterized in that, The specific preparation steps for solution A are as follows: Dimethylimidazole, deionized water and anthocyanins were added to a reaction vessel and stirred and dispersed for 20-30 min under the conditions of light protection, 20-25℃ and 500-600 r / min. Then, 0.2 mol / L sodium hydroxide solution was added to adjust the pH value to 6.0-6.5 to obtain solution A. The ratio of dimethylimidazole, deionized water and anthocyanin is 2-3g: 80-100mL: 0.3-0.45g.

7. The production process of a nonwoven fabric with ecological sensing function according to claim 1, characterized in that, The specific preparation steps of the anthocyanin quaternized microcapsules are as follows: The emulsion and a gelatin solution with a mass fraction of 5-7% were stirred and mixed. The pH of the system was adjusted to 5.2 with a 5-7% NaOH solution. The system was subjected to a re-coagulation reaction at 45-55℃ and 300-400 r / min for 30-40 min. The temperature was then lowered to 1-2℃, and genipin was added. The pH of the system was then adjusted to 5.0-5.2 with a 5% NaOH solution. The system was then further cross-linked and cured for 2-4 h to obtain anthocyanin quaternized microcapsules. The ratio of the emulsion, gelatin solution, and genipin used is 50-60 mL: 100-120 mL: 0.8-1 g.

8. The production process of a nonwoven fabric with ecological sensing function according to claim 7, characterized in that, The specific preparation steps of the emulsion are as follows: Quaternized microcrystalline cellulose, deionized water, Tween-80, anthocyanin chelate, anhydrous ethanol and Span-80 were stirred and mixed, and sheared and emulsified at 2000-3000 r / min for 5 min to obtain an emulsion.

9. The production process of a nonwoven fabric with ecological sensing function according to claim 8, characterized in that, The ratio of the amount of quaternized microcrystalline cellulose, deionized water, Tween-80, anthocyanin chelate, anhydrous ethanol and Span-80 is 0.5-0.8g: 80-90mL: 0.7-0.9g: 1.5-1.9g: 1-3mL: 0.5-0.8g.

10. A nonwoven fabric with ecological sensing function, characterized in that, It is produced by the manufacturing process described in any one of claims 1-9.

Images