A kind of formaldehyde-removing composite functional fiber cotton and its preparation method and application

Abstract

The present invention belongs to the technical field of functional fiber materials, and discloses a formaldehyde-removing composite functional fiber cotton and its preparation method and application. The preparation method is: the formaldehyde-removing composite inorganic functional particles and the fiber substrate are mixed and granulated to obtain a functional masterbatch, and then the functional masterbatch and the fiber substrate are blended and spun and then post-finished with a self-emulsifying amino silicone oil emulsion, and the obtained fiber is processed by opening and other processes to obtain the formaldehyde-removing composite functional fiber cotton. The self-emulsifying amino silicone oil emulsion is obtained by reacting cyclopentasiloxane cross-linked amino silicone oil modified by epoxy-terminated polyether. The present invention adopts a blending method to introduce inorganic functional particles, and post-finishes with a specific self-emulsifying amino silicone oil emulsion, which can give the fiber cotton product the functions of formaldehyde removal, deodorization, antibacterial, antiviral, mildew prevention, mite prevention, far infrared, negative ion, light absorption and heat generation, heat insulation, flame retardancy, etc., and has a soft and fluffy feel that is durable and washable, and can be used for the manufacture of high-end fiber products.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional fiber materials, and in particular relates to a formaldehyde-removing composite functional fiber cotton and a preparation method and application thereof. Background Art

[0002] With the improvement of textile technology and quality of life, single-function fiber fabrics can no longer meet people's living needs. Multifunctionalization is an inevitable trend in the development of fiber fabrics. The development of functional fibers is a symbol of the progress of modern fiber science. Functional fibers refer to new fibers that have some special functions in addition to the physical and mechanical properties of general fibers. For example, fibers with health care functions, such as fibers with functions such as formaldehyde removal, deodorization, antibacterial, antiviral, mildew prevention, anti-mite, far infrared, and negative ion, have attracted people's attention, and their market prospects are becoming more and more broad, and corresponding research is also increasing.

[0003] At present, the preparation methods of multifunctional fiber materials mainly include blending and finishing. The blending method generally involves mixing materials with functions such as formaldehyde removal, deodorization, mildew prevention, mite prevention, antibacterial, antiviral, far infrared, and negative ion with a fiber matrix before fiber formation, and then spinning to form. It has the advantages of lasting efficacy and water resistance, and is mainly used for high-end fabrics. For example, in our previous patents CN116288768A and CN116575187A, a method for preparing far-infrared negative ion antibacterial and anti-mite health care multifunctional fibers and formaldehyde removal, deodorization, antibacterial, mildew prevention, and antiviral multifunctional fiber cotton by blending is disclosed. The finishing method is mainly a method of post-treating the formed fiber material with a finishing agent containing functional ingredients to give the fiber material the corresponding functions. The finishing method has little effect on the fiber matrix material, a simple process, and low cost. It has a good cost-effectiveness advantage for products such as mattresses and cushions that are not often washed. For example, in our previous patent CN117005204A, a far-infrared antiviral and formaldehyde-removing multifunctional fiber cotton finishing liquid is disclosed, which is used for post-finishing applications on fibers, fiber blocks, and fiber fabrics, and imparts corresponding far-infrared antiviral and formaldehyde-removing functions.

[0004] Inorganic functional materials introduced by blending and finishing methods generally have an adverse effect on the softness, air permeability and other properties of fiber materials. Soft finishing can improve the above defects. Existing fiber softening finishing agents generally use softening finishing agents with organic silicon components, such as amino silicone oil softening finishing agents. They generally have the problem of poor water dispersion performance. Before use, they need to be emulsified with a high content of emulsifier in advance. The addition of emulsifiers will have an adverse effect on the softening effect and water washability of fiber materials.

[0005] Patent CN 116239778A discloses a softening finishing agent that can improve the soap resistance of fabrics, which is composed of an epoxy-terminated polyether with a mass ratio of (0.5-1):30 and a block polyether amino silicone oil emulsion with a solid content of 30-40%. One end of the epoxy group is chemically bonded to the group (amino, hydroxyl) on the block polyether amino silicone oil to form a cross-linked structure, and the other end is bonded to the hydroxyl group on the fiber, thereby increasing the binding force between the silicone oil and the fiber and improving the soap fastness. However, it requires the block polyether amino silicone oil synthesized by the ternary copolymerization method as the main raw material, and its preparation process is relatively complicated and the cost is relatively high. Patent CN109988313A discloses a polyether amino silicone oil copolymer softening finishing agent, which is prepared by the reaction of epoxy-terminated polysiloxane, polyether amine, cross-linking monomer, etc., wherein the cross-linking monomer adopts multifunctional octaamino cage-shaped silsesquioxane, so that the obtained polyether amino silicone oil copolymer has a body cross-linking structure, and the softening finishing agent prepared by the above polyether amino silicone oil copolymer can give the fabric a thick, crisp, and smooth feel style. However, the water solubility of its polyether block structure is limited, and the cross-linking network density of the body cross-linking structure is large, resulting in poor hydrophilicity, and it still needs to be emulsified with a low molecular weight emulsifier for fabric finishing, which has an adverse effect on the softening finishing effect and water washability. In addition, the source of its preparation raw materials is narrow and the cost is high. Summary of the invention

[0006] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a method for preparing formaldehyde-removing composite functional fiber cotton. The formaldehyde-removing composite functional fiber cotton of the present invention obtains functional masterbatch by mixing formaldehyde-removing composite inorganic functional particles with fiber substrates, and then the functional masterbatch and fiber substrates are blended and spun, and post-finished with a specific self-emulsifying amino silicone oil emulsion, which can give the product the functions of formaldehyde removal, deodorization, antibacterial, antiviral, mildew prevention, anti-mite, far infrared, negative ion, light absorption and heat generation, heat insulation, flame retardancy, etc., and has a soft and fluffy feel that is durable and washable, and can be used for the manufacture of high-end fiber products.

[0007] Another object of the present invention is to provide a formaldehyde-removing composite functional fiber cotton prepared by the above method.

[0008] Another object of the present invention is to provide the application of the above-mentioned formaldehyde-removing composite functional fiber cotton in the manufacture of furniture, home textiles, clothing, filtration, automobiles, toys, textiles and other products.

[0009] The purpose of the present invention is achieved through the following technical solutions:

[0010] A method for preparing formaldehyde-removing composite functional fiber cotton comprises the following preparation steps:

[0011] (1) mixing and granulating the formaldehyde-removing composite inorganic functional particles and the fiber substrate to obtain a functional masterbatch, then blending and spinning the functional masterbatch and the fiber substrate, and then finishing with a self-emulsifying amino silicone oil emulsion to obtain a formaldehyde-removing composite functional fiber;

[0012] (2) subjecting the obtained formaldehyde-removing composite functional fiber to an opening treatment, or to a plurality of processes such as opening, combing, web laying, glue spraying, shaping, and winding in sequence, to obtain a formaldehyde-removing composite functional fiber cotton;

[0013] The self-emulsifying amino silicone oil emulsion is prepared by the following method:

[0014] 2,4,6,8,10-cyclopentasiloxane and allyl epoxy-terminated polyether are added to anhydrous solvent and stirred to dissolve uniformly. The temperature is raised to 60-90°C under the protection of inert gas. Chloroplatinic acid catalyst is added and stirred to react until the olefinic reaction is complete. Then amino silicone oil is added for cross-linking reaction. After the reaction is completed, the solvent is removed by vacuum distillation. The obtained product is mixed with glacial acetic acid and water and homogenized and emulsified uniformly to obtain a self-emulsifying amino silicone oil emulsion.

[0015] Furthermore, the formaldehyde-removing composite inorganic functional particles in step (1) are a mixture of an inorganic formaldehyde-removing powder with a particle size of 0.5 to 5 μm and at least one inorganic functional particle selected from inorganic deodorizing powder, inorganic antibacterial powder, inorganic antiviral powder, inorganic antimildew powder, inorganic antimite powder, inorganic far-infrared powder, inorganic negative ion powder, inorganic light-absorbing heat-generating powder, inorganic aerogel, and inorganic flame retardant.

[0016] Further preferably, the inorganic formaldehyde removal powder and inorganic deodorizing powder are at least one of titanium dioxide powder, bamboo charcoal powder, activated carbon powder, diatomaceous earth powder, nano mineral crystal powder, silicon dioxide powder, and negative ion powder; the inorganic antibacterial powder, inorganic antiviral powder, inorganic mildew-proof powder, and inorganic anti-mite powder are at least one of silver oxide powder, zinc oxide powder, copper oxide powder, graphene powder, aluminum oxide powder, sodium oxide powder, magnesium oxide powder, calcium oxide powder, manganese oxide powder, iron oxide powder, and ceramic powder containing silver, copper or zinc ions; the inorganic far-infrared powder is far-infrared ceramic powder, tourmaline The inorganic negative ion powder is at least one of tourmaline negative ion powder, tourmaline powder and graphene powder; the inorganic light-absorbing heat-generating powder is at least one of heat-storage heat-generating powder, graphene powder and far-infrared ceramic powder; the inorganic aerogel powder is at least one of silica aerogel, alumina aerogel, titanium dioxide aerogel, graphene oxide aerogel, zirconium oxide aerogel and carbon aerogel; the inorganic flame retardant is at least one of inorganic red phosphorus, sulfate, magnesium hydroxide and aluminum hydroxide.

[0017] Furthermore, the fiber substrate in step (1) includes at least one of polyester fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polyaramid fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber and cellulose fiber.

[0018] Furthermore, the co-spinning in step (1) includes solution co-spinning or melt co-spinning; the mass ratio of the formaldehyde-removing composite inorganic functional particles and the fiber substrate after mixed granulation is 6-45:55-94; the mass ratio of the functional masterbatch and the fiber substrate after co-spinning is 2-30:70-98.

[0019] Furthermore, the post-finishing step in step (2) is: adding the fibers obtained by spinning into a diluted self-emulsifying amino silicone oil emulsion for immersion treatment, and then drying and shaping at a temperature of 150 to 180°C; or spraying the diluted self-emulsifying amino silicone oil emulsion on the fiber surface, and then drying and shaping at a temperature of 150 to 180°C to obtain formaldehyde-removing composite functional fibers.

[0020] Furthermore, the molecular formula of the allyl epoxy terminated polyether is as follows:

[0021] Wherein, a is an integer of 1 to 40, and b is an integer of 0 to 20.

[0022] Preferably, the average molecular weight of the allyl epoxy-terminated polyether is 500 to 1200 g / mol. The present application has verified that the average molecular weight of the allyl epoxy-terminated polyether is lower than 500 g / mol, which easily leads to gelation of the product and reduces the self-emulsification ability.

[0023] Furthermore, the molar ratio of the 2,4,6,8,10-cyclopentasiloxane to the allyl epoxy-terminated polyether is 1:2 to 4. The present application has verified that when the molar ratio of the allyl epoxy-terminated polyether is lower than the above range, the stability of the emulsion is significantly reduced; when the molar ratio of the allyl epoxy-terminated polyether is higher than the above range, the product gels easily and the self-emulsification ability is reduced.

[0024] Under the above-mentioned preparation process conditions, the reaction product obtained by 2,4,6,8,10-cyclopentasiloxane and allyl epoxy-terminated polyether has one of the following structural formulas (the molar ratio of 2,4,6,8,10-cyclopentasiloxane to allyl epoxy-terminated polyether is 1:3):

[0025]

[0026] The amino silicone oil is cross-linked and modified by using the hydrophilic macromolecule, and the obtained modified amino silicone oil has a suitable cross-linking density and hydrophilic self-emulsification properties. The obtained amino silicone oil emulsion has good stability and good softening finishing effect.

[0027] Furthermore, the anhydrous solvent is ethanol, propanol or isopropanol.

[0028] Furthermore, the amino silicone oil has a viscosity of 500 to 4000 mPa·s at 25° C. and an ammonia value (the number of milliliters of 1 mol / L hydrochloric acid required to neutralize 1 g of the amino silicone oil) of 0.3 to 1.2.

[0029] Furthermore, the mass ratio of the total mass of the 2,4,6,8,10-cyclopentasiloxane and the allyl epoxy-terminated polyether to the amino silicone oil is 0.5 to 1:1.

[0030] Furthermore, the amount of glacial acetic acid added is used to adjust the pH value of the emulsion to 5.5-6.5; the amount of water added is used to adjust the solid content of the emulsion to 20%-60%.

[0031] A formaldehyde-removing composite functional fiber cotton is prepared by the method.

[0032] The above-mentioned formaldehyde-removing composite functional fiber cotton is used in the manufacture of furniture, home textiles, clothing, filtration, automobiles, toys, textiles and other products.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The present invention adopts formaldehyde-removing composite inorganic functional particles and a fiber substrate to obtain a functional masterbatch by mixing and granulating, and then the functional masterbatch and the fiber substrate are blended and spun. The obtained fiber cotton has long-lasting formaldehyde removal, deodorization, antibacterial, antiviral, mildew-proof, anti-mite, far infrared, negative ion and other functions, and can be used for the manufacture of high-end fiber products.

[0035] (2) The present invention adopts a specific self-emulsifying amino silicone oil emulsion to post-finish the functional fiber cotton. The emulsion does not need to be emulsified and dispersed by a low-molecular emulsifier, thereby avoiding the adverse effect of the low-molecular emulsifier on the durability of the soft finishing.

[0036] (3) The amino silicone oil emulsion softening finishing agent of the present invention has a cyclopentasiloxane body cross-linking structure and has better antistatic and softening finishing effects. DETAILED DESCRIPTION

[0037] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0038] Example 1

[0039] The method for preparing a composite functional fiber cotton with formaldehyde removal, antibacterial, anti-mite and deodorizing properties in this embodiment comprises the following preparation steps:

[0040] (1) Titanium dioxide powder with an average particle size of 1.5 μm, activated carbon powder, silver oxide powder and polyester fiber substrate are melt-blended in an extruder at a mass ratio of 12:12:12:64 and then granulated to obtain a functional masterbatch; the functional masterbatch and the polyester fiber substrate are melt-blended and spun at a mass ratio of 10:90, and then a self-emulsifying amino silicone oil emulsion diluted to a solid content of 8% is sprayed on the surface of the obtained spun fiber, the spraying temperature is 30-40°C, and the emulsion spraying amount is 2.5% of the fiber mass, and then it is dried and shaped at a temperature of 160-170°C for 2 minutes to obtain a composite functional fiber with formaldehyde removal, antibacterial, anti-mite and deodorization.

[0041] (2) The obtained formaldehyde-removing, antibacterial, anti-mite and deodorizing composite functional fiber is opened, combed, laid, sprayed with glue, shaped, and wound to obtain the formaldehyde-removing, antibacterial, anti-mite and deodorizing composite functional fiber cotton.

[0042] The self-emulsifying amino silicone oil emulsion is prepared by the following method:

[0043] 2,4,6,8,10-cyclopentasiloxane (D5H) and allyl epoxy-terminated polyether (APE) were added to anhydrous ethanol solvent and stirred to dissolve uniformly. The temperature was raised to 80°C under nitrogen protection. Chloroplatinic acid catalyst was added and stirred to react until the olefinic reaction was complete. Then amino silicone oil (amino silicone oil with a viscosity of 1500mPa·s at 25°C and an ammonia value of 0.65) was added to carry out cross-linking reaction for 30 minutes. The total mass of D5H and APE added was 70% of the mass of amino silicone oil. After the reaction was completed, the solvent was removed by reduced pressure distillation. The obtained product was mixed with glacial acetic acid and water and homogenized and emulsified uniformly to obtain a self-emulsifying amino silicone oil emulsion with a pH value of 6 and a solid content of 40%.

[0044] In order to study the effect of the average molecular weight of APE on the performance of self-emulsifying amino silicone oil emulsion, APE-400 (the number represents the average molecular weight), APE-500, APE-800, and APE-1200 were used as reaction raw materials, and the reactions were carried out under different D5H:APE molar ratios. The appearance of the obtained self-emulsifying amino silicone oil emulsion was visually observed and its centrifugal stability was tested (centrifugation at 3000r / min for 30min to observe whether there was floating oil stratification and flocculent precipitation). The test results are shown in Table 1 below.

[0045] Table 1. Appearance and stability of finishing agent emulsion under different conditions

[0046] APE molecular weight D5H:APE Emulsion appearance Centrifugal stability APE-400 1:3 Milky white opaque liquid A large amount of flocculent precipitation APE-500 1:3 Translucent blue light microemulsion Uniform and stable APE-800 1:1 Milky white opaque liquid Floating oil stratification APE-800 1:2 Translucent blue light microemulsion Uniform and stable APE-800 1:3 Transparent blue light microemulsion Uniform and stable APE-800 1:4 Translucent blue light microemulsion Uniform and stable APE-800 1:5 Milky white opaque liquid A small amount of flocculent precipitation APE-1200 1:3 Transparent blue light microemulsion Uniform and stable

[0047] It can be seen from the results in Table 1 that too low molecular weight of allyl epoxy-terminated polyether will lead to shorter hydrophilic segments and increased crosslinking density, which will reduce the self-emulsification ability of the resulting amino silicone oil emulsion, and flocculent precipitation will occur easily, and the stability of the emulsion will decrease. Too low reaction ratio of allyl epoxy-terminated polyether will lead to insufficient hydrophilic modification, and the emulsion will easily have floating oil stratification, and the stability will be significantly reduced; too high reaction ratio of allyl epoxy-terminated polyether will lead to significantly increased crosslinking density, and flocculent precipitation will occur easily, and the stability of the emulsion will be reduced. Under the conditions of APE average molecular weight of 500-1200 and D5H:APE=1:2-4, the resulting amino silicone oil emulsion has good self-emulsification properties and stability.

[0048] The composite functional fiber cotton obtained in this embodiment (the sample obtained by post-finishing with the self-emulsifying amino silicone oil emulsion obtained under the conditions of APE-800 and D5H:APE=1:3 was used as the test sample) was tested for its formaldehyde removal effect (QB / T 2761-2006), antibacterial effect (GB / T20944.3-2008), anti-mite effect (GB / T 24253-2009) and deodorization effect (GB / T 33610.2-2017). The results are shown in Tables 2 to 5 below.

[0049] Table 2. Formaldehyde removal effect

[0050]

[0051] Note: Place 1 sample into 1.5m 3 Tests are carried out in the test chamber.

[0052] Table 3. Antibacterial effect

[0053]

[0054] Table 4. Anti-mite effect

[0055]

[0056] Table 5. Deodorization effect

[0057]

[0058] The above results show that the fiber cotton obtained by the present invention has good formaldehyde removal, antibacterial, anti-mite and deodorizing functions.

[0059] Example 2

[0060] The method for preparing a composite functional fiber cotton with formaldehyde removal, antibacterial, anti-mite and anti-mildew properties in this embodiment comprises the following preparation steps:

[0061] (1) Titanium dioxide powder, silver oxide powder, zinc oxide powder and polyester fiber substrate with an average particle size of 1.5 μm were melt-blended in an extruder at a mass ratio of 15:10:10:65 and then granulated to obtain a functional masterbatch; the functional masterbatch and the polyester fiber substrate were melt-blended and spun at a mass ratio of 10:90, and the obtained spun fiber was added to a self-emulsifying amino silicone oil emulsion diluted to a solid content of 8% (the self-emulsifying amino silicone oil emulsion obtained under the conditions of APE-800 and D5H:APE=1:3 in Example 1 was used as a finishing agent) and immersed for 30 minutes, and then dried and shaped at a temperature of 160-170°C for 2 minutes to obtain a formaldehyde-removing, antibacterial, anti-mite and anti-mildew composite functional fiber.

[0062] (2) The obtained formaldehyde-removing, antibacterial, anti-mite and anti-mildew composite functional fiber is opened, combed, laid, sprayed with glue, and shaped, and then wound to obtain the formaldehyde-removing, antibacterial, anti-mite and anti-mildew composite functional fiber cotton.

[0063] The test results show that the formaldehyde removal rate of the composite functional fiber cotton obtained in this embodiment is 85.6%; the antibacterial effect results show that the antibacterial rates of Staphylococcus aureus, Escherichia coli and Candida albicans are all greater than 99%; the anti-mite effect inhibition rate is 81.8%; anti-mildew test (petri dish method; circular sample with a diameter of 3.8 cm; high-pressure steam sterilization; test strains: Aspergillus niger ATCC16404 4th generation; Penicillium funiculum ATCC10509 4th generation; Chaetomium globosum ATCC6205 4th generation; Trichoderma viride ATCC28020 4th generation; bacterial solution concentration: 1.3×10 6 / mL; test temperature: 28°C; humidity: 90%; cycle: 28 days) The results showed that the mildew resistance level was level 0.

[0064] Example 3

[0065] The preparation method of a far-infrared composite functional fiber cotton with formaldehyde removal, antibacterial and anti-mite properties in this embodiment comprises the following preparation steps:

[0066] (1) Titanium dioxide powder with an average particle size of 1.5 μm, silver oxide powder, graphene, far-infrared ceramic powder and polyester fiber substrate are melt-blended in an extruder at a mass ratio of 12:10:10:12:56 and then granulated to obtain a functional masterbatch; the functional masterbatch and the polyester fiber substrate are melt-blended and spun at a mass ratio of 10:90, and the obtained spun fiber is added to a self-emulsifying amino silicone oil emulsion diluted to a solid content of 8% (the self-emulsifying amino silicone oil emulsion obtained under the conditions of APE-800 and D5H:APE=1:3 in Example 1 is used as a finishing agent) and immersed for 30 minutes, and then dried and shaped at a temperature of 160-170°C for 2 minutes to obtain a formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber.

[0067] (2) The obtained formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber is opened, combed, laid, sprayed with glue, and shaped to obtain formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber cotton.

[0068] After testing, the formaldehyde removal rate of the composite functional fiber cotton obtained in this embodiment is 87.5%; the antibacterial effect results show that the inhibition rates of Staphylococcus aureus, Escherichia coli and Candida albicans are all greater than 99%; the anti-mite effect inhibition rate is 86.1%; the far-infrared test results show that the far-infrared emissivity (Article 7.1 of GB / T30127-2013) is 0.89 (the standard requires ≥0.83), and the far-infrared radiation temperature rise (Article 7.2 of GB / T 30127-2013) is 4.9°C (the standard requires ≥1.7°C).

[0069] Example 4

[0070] The method for preparing a composite functional fiber cotton with formaldehyde removal, antibacterial, anti-mite and anti-viral properties in this embodiment comprises the following preparation steps:

[0071] (1) Titanium dioxide powder, diatomaceous earth powder, silver oxide powder, zinc oxide powder, negative ion powder, graphene and polyester fiber substrate with an average particle size of 1.5 μm are melt-blended in an extruder at a mass ratio of 7:7:7:7:7:5:60 and then granulated to obtain a functional masterbatch; the functional masterbatch and the polyester fiber substrate are melt-blended and spun at a mass ratio of 10:90, and the obtained spun fiber is added to a self-emulsifying amino silicone oil emulsion diluted to a solid content of 8% (the self-emulsifying amino silicone oil emulsion obtained under the conditions of APE-800 and D5H:APE=1:3 in Example 1 is used as a finishing agent) and immersed for 30 minutes, and then dried and shaped at a temperature of 160-170°C for 2 minutes to obtain a formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber.

[0072] (2) The obtained formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber is opened, combed, laid, sprayed with glue, shaped, and wound to obtain formaldehyde-removing, antibacterial and anti-mite far-infrared composite functional fiber cotton.

[0073] After testing, the formaldehyde removal rate of the composite functional fiber cotton obtained in this embodiment was 88.2%; the antibacterial effect results showed that the inhibition rates of Staphylococcus aureus, Escherichia coli and Candida albicans were all greater than 99%; the anti-mite effect inhibition rate was 84.3%; the antiviral test results showed that the antiviral activity rate was 85.11% (ISO 18184:2019 (E); influenza A virus H1N1: A / PR / 8 / 34 (ATCC VR-1469); host name: MDCK cells).

[0074] Comparative Example 1

[0075] Compared with Example 1, the preparation method of the formaldehyde-removing, antibacterial, anti-mite and deodorizing composite functional fiber cotton in this comparative example adopts the self-emulsifying grafted modified amino silicone oil emulsion obtained by the ring-opening grafting reaction of allyl epoxy-terminated polyether and amino silicone oil for post-finishing, and the other unlisted conditions are the same as those in Example 1.

[0076] The self-emulsifying graft-modified amino silicone oil emulsion is prepared by the following method:

[0077] Allyl epoxy-terminated polyether (APE-800) was added to anhydrous ethanol solvent and stirred to dissolve uniformly, and then heated to 80°C under nitrogen protection, and then amino silicone oil (amino silicone oil with a viscosity of 1500mPa·s at 25°C and an ammonia value of 0.65) was added to carry out ring-opening grafting reaction for 30 minutes. The addition ratio of APE-800 and amino silicone oil was the same as that in Example 1. After the reaction was completed, the solvent was removed by reduced pressure distillation, and the obtained product was mixed with glacial acetic acid and water and homogenized and emulsified uniformly to obtain a self-emulsifying graft-modified amino silicone oil emulsion with a pH value of 6 and a solid content of 40%. The obtained self-emulsifying graft-modified amino silicone oil emulsion was a transparent blue light microemulsion, and the centrifugal stability test results showed uniformity and stability.

[0078] Comparative Example 2

[0079] The method for preparing a composite functional fiber cotton with formaldehyde removal, antibacterial, anti-mite and deodorizing properties in this comparative example is, compared with Example 1, a method for preparing an amino silicone oil emulsion finishing agent by cross-linking reaction between an epoxy-terminated polyether (average molecular weight of 800) as described in CN 116239778A and amino silicone oil for post-finishing, and the other unlisted conditions are the same as those in Example 1.

[0080] The amino silicone oil emulsion finishing agent is prepared by the following method:

[0081] Epoxy-terminated polyether (average molecular weight of 800) was added to anhydrous ethanol solvent and stirred to dissolve uniformly. The temperature was raised to 80°C under nitrogen protection, and then amino silicone oil (amino silicone oil with a viscosity of 1500 mPa·s at 25°C and an ammonia value of 0.65) was added to carry out cross-linking reaction for 30 minutes. The ratio of epoxy-terminated polyether to amino silicone oil was the same as that in Example 1. After the reaction was completed, the solvent was removed by vacuum distillation. The obtained product was mixed with glacial acetic acid and water and homogenized and emulsified uniformly to obtain an amino silicone oil emulsion finishing agent with a pH value of 6 and a solid content of 40%. The obtained amino silicone oil emulsion finishing agent was a milky white opaque liquid, and the centrifugal stability test results showed that a large amount of flocculent precipitates.

[0082] From the above results, it can be seen that the self-emulsification performance of the amino silicone oil emulsion finishing agent obtained by directly crosslinking epoxy-terminated polyether without introducing the cyclic siloxane structure is significantly deteriorated, flocculent precipitation is easy to occur, and the stability is deteriorated. It shows that the introduction of the cyclic siloxane structure of the present invention is conducive to the extension of the hydrophilic polyether chain, reduces its entanglement and wrapping, reduces the crosslinking strength, and the self-emulsification performance and stability of the obtained amino silicone oil emulsion are significantly improved.

[0083] The soft finishing effect (softness and fluffiness (evaluated by hand touch method, the highest hand feeling evaluation score is 5 points, the lowest is 0 points, five people evaluate at the same time, and the average score is taken), stiffness (tested with reference to ZB W04003-87 "Fabric Stiffness Test Method Inclined Cantilever Method"; the smaller the stiffness, the better the softness of the fabric)) and long-lasting water washing resistance (tested according to GB / T 8629-2001 "Household Washing and Drying Procedure for Textile Testing" after washing 10 times) of the fiber cotton obtained in the above Example 1 and Comparative Examples 1-2 were tested. The results are shown in Table 6 below.

[0084] Table 6. Test results of soft finishing and durable water washing performance

[0085]

[0086] It can be seen from the results in Table 6 that the present invention can significantly enhance the softening finishing effect and water-washing resistance of the amino silicone oil emulsion finishing agent by introducing the cross-linked structure of cyclopentasiloxane. In addition, the raw material source of cyclopentasiloxane is wide and the cost is lower.

[0087] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing formaldehyde-removing composite functional fiber cotton, characterized in that: The method comprises the following preparation steps: (1) The formaldehyde-removing composite inorganic functional particles and the fiber substrate are mixed and granulated to obtain a functional masterbatch, and then the functional masterbatch and the fiber substrate are blended and spun, and then a self-emulsifying amino silicone oil emulsion is used for post-finishing to obtain a formaldehyde-removing composite functional fiber; (2) subjecting the obtained formaldehyde-removing composite functional fiber to an opening treatment or to a plurality of steps of opening, combing, web laying, glue spraying, shaping, and winding in sequence to obtain formaldehyde-removing composite functional fiber cotton; The self-emulsifying amino silicone oil emulsion is prepared by the following method: 2,4,6,8,10-cyclopentasiloxane and allyl epoxy-terminated polyether are added to an anhydrous solvent and stirred to be uniformly dissolved, the temperature is raised to 60-90°C under the protection of an inert gas, chloroplatinic acid catalyst is added and stirred to react until the alkenyl reaction is complete, and then amino silicone oil is added for cross-linking reaction, and after the reaction is completed, the solvent is removed by reduced pressure distillation, and the obtained product is mixed with glacial acetic acid and water and homogenized and emulsified uniformly to obtain a self-emulsifying amino silicone oil emulsion; The molecular formula of the allyl epoxy terminated polyether is as follows: , where a is an integer from 1 to 40, and b is an integer from 0 to 20; The average molecular weight of the allyl epoxy terminated polyether is 500-1200 g / mol; The molar ratio of the 2,4,6,8,10-cyclopentasiloxane to the allyl epoxy terminated polyether is 1:2-4; The amino silicone oil is an amino silicone oil with a viscosity of 1500 mPa·s at 25° C. and an amine value of 0.65; the mass ratio of the total mass of the 2,4,6,8,10-cyclopentasiloxane and the allyl epoxy-terminated polyether to the amino silicone oil is 0.7:1; The amount of glacial acetic acid added is used to adjust the pH value of the emulsion to 5.5-6.5; the amount of water added is used to adjust the solid content of the emulsion to 20%-60%.

2. The method for preparing the formaldehyde-removing composite functional fiber cotton according to claim 1, characterized in that: The formaldehyde-removing composite inorganic functional particles in step (1) are a mixture of an inorganic formaldehyde-removing powder with a particle size of 0.5 to 5 μm and at least one inorganic functional particle selected from inorganic deodorizing powder, inorganic antibacterial powder, inorganic antiviral powder, inorganic mildew-proof powder, inorganic anti-mite powder, inorganic far-infrared powder, inorganic negative ion powder, inorganic light-absorbing heating powder, inorganic aerogel, and inorganic flame retardant; the inorganic formaldehyde-removing powder and inorganic deodorizing powder are at least one selected from titanium dioxide powder, bamboo charcoal powder, activated carbon powder, diatomaceous earth powder, nano-mineral crystal powder, silicon dioxide powder, and negative ion powder; the inorganic antibacterial powder, inorganic antiviral powder, inorganic mildew-proof powder, and inorganic anti-mite powder are silver oxide powder, zinc oxide powder, copper oxide powder, graphene powder, aluminum oxide powder, sodium oxide powder, and magnesium oxide powder. , calcium oxide powder, manganese oxide powder, iron oxide powder, and ceramic powder containing silver, copper or zinc ions; the inorganic far-infrared powder is at least one of far-infrared ceramic powder, tourmaline powder, graphene powder, germanium powder, and medical stone powder; the inorganic negative ion powder is at least one of tourmaline negative ion powder, tourmaline powder, and graphene powder; the inorganic light-absorbing heat-generating powder is at least one of heat-storage heat-generating powder, graphene powder, and far-infrared ceramic powder; the inorganic aerogel is at least one of silica aerogel, alumina aerogel, titanium dioxide aerogel, graphene oxide aerogel, zirconium oxide aerogel, and carbon aerogel; the inorganic flame retardant is at least one of inorganic red phosphorus, sulfate, magnesium hydroxide, and aluminum hydroxide.

3. The method for preparing the formaldehyde-removing composite functional fiber cotton according to claim 1, characterized in that: The fiber substrate in step (1) includes at least one of polyester fiber, polypropylene fiber, polyethylene fiber, polylactic acid fiber, polyaramid fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber and cellulose fiber; the co-spinning includes solution co-spinning or melt co-spinning; the mass ratio of the formaldehyde-removing composite inorganic functional particles and the fiber substrate after mixed granulation is 6~45:55~94; the mass ratio of the functional masterbatch and the fiber substrate after co-spinning is 2~30:70~98.

4. The method for preparing the formaldehyde-removing composite functional fiber cotton according to claim 1, characterized in that: The post-finishing step in step (1) is: adding the spun fiber to the diluted self-emulsifying amino silicone oil emulsion for immersion treatment, and then drying and shaping at a temperature of 150-180°C; or spraying the diluted self-emulsifying amino silicone oil emulsion on the fiber surface, and then drying and shaping at a temperature of 150-180°C to obtain the formaldehyde-removing composite functional fiber.

5. The method for preparing the formaldehyde-removing composite functional fiber cotton according to claim 1, characterized in that: The anhydrous solvent is ethanol, propanol or isopropanol.

6. A formaldehyde-removing composite functional fiber cotton, characterized in that: It is prepared by the method according to any one of claims 1 to 5.

7. Application of the formaldehyde-removing composite functional fiber cotton described in claim 6 in the manufacture of furniture, home textiles, clothing, filtration, automobiles, and toys.

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