A composite deodorant, its preparation method and application

Abstract

The present invention belongs to the technical field of adsorbents, and particularly relates to a modified porous adsorbent protective powder, a composite deodorant and their applications. The modified porous adsorbent protective powder of the present invention is prepared according to the following steps: dispersing an inorganic porous material dispersion or a β-cyclodextrin organic porous material dispersion, and spray-drying to obtain a porous material powder; dissolving hemicellulose and / or polypeptide in an ionic liquid to obtain a mixed solution with a mass concentration of 2-5%; adding the porous material powder into the mixed solution in the previous step, stirring and mixing evenly, filtering, adding water, and performing spray-drying to obtain the modified porous adsorbent protective powder. The present invention provides a modified porous adsorbent protective powder, which plays a role in protecting the effective active ingredients against antibacterial and deodorizing. The composite deodorant prepared by the method of the present invention has greatly improved stability and functional persistence of antibacterial and deodorizing effects.

Description

Technical Field

[0001] The present invention belongs to the technical field of adsorbents, and particularly relates to a composite deodorant and its preparation method and application. Background Art

[0002] With the continuous development of society and the improvement of people's living standards, people are becoming more and more sensitive to unpleasant odors, which not only affect the sense of smell and mood, but also seriously affect physical health. Especially in hot and high-temperature environments or during strenuous exercise, people sweat more, and sweat, sebum, and other various human secretions become a breeding ground for bacteria and pathogenic microorganisms. The odors remaining on clothing and textiles affect people's quality of life. Therefore, deodorant products that can quickly and efficiently eliminate odors and have a pleasant smell are becoming more and more popular and have become people's first choice. However, traditional deodorants are inefficient, lack stability, and may cause varying degrees of harm to the human body and the environment.

[0003] As an adsorbent that can eliminate odors, absorb moisture, and sterilize, it not only consists of surfactants but also includes an adsorption carrier. In particular, it is difficult to obtain an adsorbent that can stably play a deodorizing role on fabric fibers. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects existing in the prior art and provide modified porous adsorbent protective powder to protect the effective active ingredients for antibacterial and deodorizing.

[0005] The present invention also provides a composite deodorant prepared from the modified porous adsorbent protective powder, and the stability and functional durability of its antibacterial and deodorizing effects are greatly improved.

[0006] The composite deodorant prepared by the present invention is directly applied to synthetic fibers for melt spinning, or a composite deodorant dispersion system is prepared using the composite deodorant and applied to chemical fibers for wet spinning.

[0007] A composite deodorant: specifically includes the following steps:

[0008] a. Prepare composite alkaline deodorant powder

[0009] a1. Add one or more of alginic acid, lactic acid, and chlorogenic acid to water at 25 - 30°C for dissolution to obtain a solution with a mass concentration of 4% - 6%; the alginic acid, lactic acid, and chlorogenic acid are biological.

[0010] a2. Add the prepared modified porous adsorption and protection powder to the solution in step a1, where the mass ratio of the modified porous adsorption and protection powder to the solution in a1 is 1:20 - 30, perform stirring adsorption for 30 - 50 min, and then spray dry to obtain the first composite alkaline odor eliminating powder;

[0011] a3. Add the first composite alkaline odor eliminating powder to an aqueous solution with a mass concentration of 3% - 5% of polycarboxylic acid, 1% - 3% of zinc salt, and a temperature of 25°C - 35°C, perform adsorption for 30 min - 40 min, filter, and subject the solid to electron beam irradiation treatment and then vacuum drying to obtain the composite alkaline odor eliminating powder; the irradiation dose is 20 - 50 kGy, and the irradiation time is 60 - 120 s, so as to react with polycarboxylic acid, biological acid, and the hydroxyl group when using hemicellulose. At the same time, use the zinc salt to form a complex reaction with part of the biological acid, which not only endows the powder with zinc antibacterial property, but also increases the stability and functional durability of the composite alkaline odor eliminating powder. Then perform vacuum drying to obtain the final composite alkaline odor eliminating powder. The use of polycarboxylic acid can further enhance the effect of eliminating alkaline odor; the polycarboxylic acid is one of butanetetracarboxylic acid, citric acid, and maleic acid, and the zinc salt is one of zinc sulfate or zinc acetate.

[0012] b. Prepare the composite acid odor eliminating and senile odor powder

[0013] b1. Mix one or more of amino acids, tannin substances, and polyphenol substances and add them to water for dissolution to obtain a solution with a mass concentration of 5% - 7%; the amino acid is one of glycine, tyrosine, serine, and cysteine; the polyphenol substances are flavonoid substances and tea polyphenols, etc., where the flavonoid substances are one of flavonol, flavanonol, flavanol, and isoflavanone, mainly from plant extracts; tannin substances include plant extracts such as persimmon tannin and green tea tannin; the reactive groups in the molecules of tannin substances and polyphenol substances can have various bonding effects with the functional groups in the molecules of amino acids and proteins, preventing the reproduction of bacteria, endowing them with antibacterial properties, and improving the stability and functional durability of antibacterial and odor eliminating substances;

[0014] b2. Add the prepared modified porous adsorption and protection powder to the solution in step b1, where the mass ratio of the modified porous adsorption and protection powder to the solution in a1 is 1:20 - 30, perform stirring adsorption for 30 - 50 min, and then spray dry to obtain the first composite acid odor eliminating and senile odor powder;

[0015] b3. Add the first composite deacidic and geriatric odor powder into an aqueous solution with a mass concentration of 1.5% - 3% of ethylene glycol diglycidyl ether or transglutaminase and a temperature of 25°C - 35°C, conduct adsorption for 20 min - 30 min, filter, conduct a cross-linking reaction on the solid, with a reaction temperature of 30°C - 40°C, a reaction time of 50 min - 70 min, and a pH of 7.0 - 8.5. After the reaction ends, conduct vacuum drying to obtain the composite deacidic and geriatric odor powder;

[0016] c. Mix the prepared composite dealkaline odor powder with the composite deacidic and geriatric odor powder to prepare a composite deodorant. In step c, mix the prepared composite dealkaline odor powder with the composite deacidic and geriatric odor powder, or a copolymer of 3-hydroxybutyrate and 3-hydroxypentanoate or an aromatic substance can be added to prepare a composite deodorant.

[0017] The modified porous adsorption protective powder described in the present invention is prepared according to the following steps:

[0018] (1) Disperse an inorganic porous material dispersion or a β-cyclodextrin organic porous material dispersion, and after spray drying, obtain a porous material powder;

[0019] (2) Dissolve hemicellulose and / or polypeptide in an ionic liquid to obtain a mixed solution with a mass concentration of 2% - 5%;

[0020] (3) Add the porous material powder in step (1) into the mixed solution in step (2), where the mass ratio of the porous material powder to the mixed solution in step (2) is 1:20 - 30, stir and mix evenly, then fully adsorb for 30 - 50 min, filter, add water, and conduct spray drying to obtain the modified porous adsorption protective powder.

[0021] The inorganic porous material dispersion in step (1) is prepared by grinding an inorganic porous material powder to a particle size D90 ≤ 3.350 μm, dispersing it, and then adding a silane coupling agent and dispersing it evenly; the inorganic porous material powder is one of activated carbon, binchotan, silica gel, zeolite, and silicate minerals; the addition amount of the silane coupling agent is 10% - 15% of the mass of the inorganic porous material powder. The silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane. By using the silane coupling agent to treat the porous material powder, necessary reactive groups are provided for subsequent modification of the inorganic porous material powder with organic substances, and the stability of the adsorbed substances is improved.

[0022] Preferably, the mass concentration of the inorganic porous material powder in the inorganic porous material dispersion is 30% - 50%; the mass concentration of β-cyclodextrin in the β-cyclodextrin organic porous material dispersion is 30% - 50%.

[0023] In step (2), the degree of polymerization of hemicellulose is 50 - 80; the number average molecular weight of the polypeptide is 5000 - 10000; the ionic liquid is an alkylimidazole ionic liquid, where the cation is one of ethyl and butyl; the anion is Cl - , SCN - One of them. Since hemicellulose and polypeptide have many hydrophilic groups, the porous material is modified to improve its hygroscopicity, facilitating subsequent full adsorption of functional substances. At the same time, a crosslinked matrix for adsorption in the subsequent pores is provided to increase its stability.

[0024] The parameters of spray drying in steps (1) and (3) are: inlet air temperature 150°C - 180°C, outlet air temperature 95°C - 105°C, feed rate 15 mL / min - 25 mL / min. The porous material powder obtained by spray drying has good dispersion and relatively uniform particles.

[0025] Application of the composite deodorant: The prepared composite deodorant is used in synthetic fibers for melt spinning, or a composite deodorant dispersion is made from the composite deodorant and used in chemical fibers for wet spinning, or the composite deodorant dispersion is directly applied to fabrics and the fabrics are treated by padding process.

[0026] The specific steps for making a composite deodorant dispersion from the composite deodorant are: adding the prepared composite deodorant to water with a mass fraction of 35% - 45%, adding a dispersant accounting for 15% - 20% of the mass of the composite deodorant, an antifoaming agent accounting for 2% - 5% of the mass of the composite deodorant, stirring and mixing evenly and then dispersing, and then adding a thickener accounting for 3% - 6% of the mass of the composite deodorant, stirring evenly to obtain the composite deodorant dispersion. The dispersion speed is 1500 r / min - 2000 r / min, the temperature is maintained at 18°C - 20°C during the dispersion process, and the dispersion time is 60 min - 90 min. The dispersant is one of sodium dodecylbenzenesulfonate and sodium hexametaphosphate; the antifoaming agent is one of polyoxypropylene polyoxyethylene glycerol ether and polyoxypropylene glycerol ether; the thickener is one of sodium alginate, polyvinylpyrrolidone, and sodium carboxymethylcellulose to increase the viscosity of the dispersion system and thus improve its dispersion stability.

[0027] Specifically, the steps are divided into the following processes:

[0028] 1. Preparation of modified porous adsorption protection powder

[0029] 1) Preparation of porous material powder

[0030] Inorganic porous substances such as activated carbon, binchotan, silica gel, zeolite, and silicate minerals are ground and dispersed in water by using a sand mill disperser, where the zirconia bead filling rate is 50% - 80%, the concentration of the inorganic porous substances is 30% - 50%, the grinding speed is 2000 - 3000 r / min. During the grinding process, the particle size of the inorganic porous substance powder is detected until the particle size reaches D90 ≤ 2.950 μm, obtaining a primary inorganic porous substance powder dispersion; and a silane coupling agent is added to the inorganic porous substance powder dispersion for surface modification treatment, and the addition amount is 10% - 15% of the inorganic porous substance powder. The reaction continues for 30 min - 50 min at a speed of 5000 r / min - 650 r / min, thereby obtaining the final inorganic porous substance dispersion.

[0031] Or an organic porous dispersing substance, β-cyclodextrin, is directly dispersed in water to obtain a β-cyclodextrin organic porous dispersing substance dispersion with a concentration of 30% - 50%.

[0032] The inorganic porous substance dispersion or the organic porous dispersing substance dispersion prepared above is dried by using a spray dryer by the method of spray drying, where the inlet air temperature is 150°C - 180°C, the outlet air temperature is 95°C - 105°C, and the feeding speed is 15 mL / min - 25 mL / min, obtaining a porous substance powder.

[0033] 2) Preparation of modified porous adsorption protective powder

[0034] Hemicellulose with a degree of polymerization of 50 - 80, or a high molecular polypeptide with a molecular weight of 5000 - 10000, or a mixture of the two in any proportion is dissolved in an ionic liquid to obtain a hemicellulose or polypeptide solution or a mixture solution of the two with a concentration of 2% - 5%.

[0035] The prepared porous substance powder is added to the solution prepared above. During the addition process, stirring is carried out while adding, and the stirring speed is 300 r / min - 350 r / min. After the addition is completed, stirring continues for 30 min - 50 min to enable the above-mentioned porous substance to fully adsorb the solution, and then filtration is carried out to obtain a wet modified porous substance. Then, deionized water is added to the wet modified porous substance to precipitate the adsorbed hemicellulose or polypeptide, which adheres to the surface of the pores of the porous substance. Then, spray drying is carried out again, where the inlet air temperature is 150°C - 180°C, the outlet air temperature is 95°C - 105°C, and the feeding speed is 15 mL / min - 25 mL / min, obtaining a modified porous adsorption protective powder.

[0036] 2. Preparation of composite alkaline odor elimination powder

[0037] One or more of biogenic alginic acid, lactic acid, and chlorogenic acid are added to deionized water at 25°C - 30°C in any proportion for dissolution to obtain a solution with a concentration of 4% - 6%. Then, the prepared modified porous adsorbent and protective powder is added to the above solution for adsorption. Stirring is started when adding the modified porous adsorbent and during adsorption, with a stirring speed of 200 r / min - 300 r / min. After adding, continue stirring for 30 min - 50 min to allow it to fully adsorb the biogenic acid, and then dry it using the spray drying process to obtain the first composite de-alkaline odor powder.

[0038] Then, the first composite de-alkaline odor powder is added to a solution containing 3% - 5% of polycarboxylic acid, 1% - 3% of zinc salt, and at a temperature of 25°C - 35°C, and adsorption continues for a treatment time of 30 min - 40 min. After adsorption, filter and perform electron beam irradiation treatment on the filtered solid, with an irradiation dose of 20 kGy - 50 kGy and an irradiation time of 60 s - 120 s, and then perform vacuum drying to obtain the composite de-alkaline odor powder.

[0039] 3. Preparation of composite de-acidic odor and senile odor powder

[0040] One or more of amino acids, tannin substances, and polyphenol substances are added to deionized water in any proportion for dissolution to obtain a solution with a concentration of 5% - 7%. Then, the prepared modified porous adsorbent and protective powder is added to the above solution for adsorption. Stirring is started when adding the modified porous adsorbent and during adsorption, with a stirring speed of 200 r / min - 300 r / min. After adding, continue stirring for 30 min - 50 min to allow it to fully adsorb, and then dry it using the spray drying process to obtain the first composite de-acidic odor and senile odor powder.

[0041] Then, the first composite de-acidic odor and senile odor powder is added to a solution containing 1.5% - 3% of crosslinking agent ethylene glycol diglycidyl ether or transglutaminase and at a temperature of 25 - 35°C, and adsorption continues for a treatment time of 20 min - 30 min. After adsorption and filtration, perform a crosslinking reaction on the filtered solid, with a reaction temperature of 30°C - 40°C, a reaction time of 50 min - 70 min, and a pH of 7.0 - 8.5, and then perform vacuum drying to obtain the composite de-acidic odor and senile odor powder.

[0042] 4. Preparation and application of composite deodorant

[0043] The prepared composite de-alkaline odor powder and composite de-acidic odor and senile odor powder are mixed in any proportion, preferably in a ratio of 1:1 - 1:2, and can also be blended with PHBV (copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate) or aromatic substances such as lavender to obtain the composite deodorant.

[0044] The prepared antibacterial composite absorbent powder contains natural or plant-based substances or is prepared therefrom, all of which have antibacterial effects, are harmless to the human body, and through cross-linking and metal complexation, the functions are further strengthened, and it has good effects on acidic odors (such as acetic acid, isovaleric acid, etc.), alkaline odors (such as ammonia, trimethylamine, etc.) and senile odor (such as 2-nonenal, etc.). The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is ≥97.5%, the antibacterial rate against Escherichia coli is ≥98.9%, and the antibacterial rate against Candida albicans is ≥98.1% (GB / T20944.3-2008 "Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method"); its ammonia reduction rate is ≥96.1%, acetic acid reduction rate is ≥97.5% (GB / T33610.2-2017 Determination of Deodorizing Properties of Textiles - Part 2: Detection Tube Method), isovaleric acid reduction rate is ≥99.6%, and 2-nonenal reduction rate is ≥98.3% (GB / T33610.3-2019 Determination of Deodorizing Properties of Textiles - Part 3: Gas Chromatography Method).

[0045] The prepared composite deodorant is used for synthetic fibers for melt spinning. First, it is used to prepare synthetic fiber masterbatch, and the addition amount of the composite deodorant powder in the final fiber is 6.0% - 8.0%.

[0046] 5. Preparation and Application of Composite Deodorant Dispersion

[0047] The prepared composite deodorant is added to deionized water, and its mass fraction is 35% - 45%. A dispersant accounting for 15% - 20% of the mass of the composite deodorant and an antifoaming agent accounting for 2% - 5% of the mass of the composite deodorant are added to the system. After stirring and mixing evenly, it is added to a high-speed disperser for dispersion. The dispersion speed is 1500 - 2000 r / min. During the dispersion process, the temperature is maintained at 18 - 20 °C, and the dispersion time is 60 - 90 min. Then a thickener accounting for 3% - 6% of the mass of the composite deodorant is added and mixed evenly to obtain the composite deodorant dispersion.

[0048] The composite deodorant dispersion prepared by the present invention is used for chemical fibers for wet spinning, and the addition amount calculated according to the active ingredient is 4.0% - 6.0%; at the same time, the composite deodorant dispersion can be used, and the fabric is treated by padding process to obtain a deodorized fabric. Different ratios can be used according to different application fields, and the final total addition amount is 7.0% - 10.0%.

[0049] The antibacterial rate of the fibers or fabrics prepared by the present invention against Staphylococcus aureus is ≥81.2%, the antibacterial rate against Escherichia coli is ≥82.5%, and the antibacterial rate against Candida albicans is ≥83.3% (GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method"); the reduction rate of ammonia is ≥79.5%, the reduction rate of acetic acid is ≥76.9% (GB / T 33610.2-2017 "Determination of deodorization performance of textiles - Part 2: Detection tube method"), the reduction rate of isovaleric acid is ≥88.5%, and the reduction rate of 2-nonenal is ≥77.5% (GB / T 33610.3-2019 "Determination of deodorization performance of textiles - Part 3: Gas chromatography method").

[0050] Aiming at the deficiencies of the prior art, the composite deodorant of the present invention adopts multiple mechanisms. Firstly, porous substances are selected, which not only play a protective role for antibacterial and deodorant substances, but also adsorb odors through the physical adsorption of their porous substances, reducing the concentration of odors, so as to achieve the effect of physical deodorization. Secondly, according to different odor mechanisms such as acid-base neutralization and oxidation, different antibacterial and deodorant substances are prepared and modified to improve stability and functional durability, and different odors such as ammonia, acetic acid, isovaleric acid and old-age odor can be treated. At the same time, it can also be modified by adding aromatic substances, thus meeting the needs of multiple uses and multiple application scenarios.

[0051] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0052] (1) The composite deodorant of the present invention adopts multiple mechanisms. Firstly, porous substances are selected, which not only play a protective role for antibacterial and deodorant substances, but also achieve the effect of physical deodorization through the physical adsorption of their porous substances. Secondly, different antibacterial and deodorant substances are prepared according to different odor mechanisms and modified to improve stability and functional durability, and different odors can be treated, meeting the needs of multiple uses and multiple application scenarios.

[0053] (2) The present invention first treats the porous substance powder with a silane coupling agent, providing necessary reactive groups for subsequent modification of the inorganic porous substance powder with hydrophilic substances, improving the stability of the adsorbed substances. At the same time, by using hemicellulose and polypeptides with more hydrophilic groups to modify the porous substances to improve their hygroscopicity, it is convenient to fully adsorb more functional substances subsequently. At the same time, a crosslinked matrix for adsorption in the subsequent pores is provided, which interacts with antibacterial and deodorant substances through chemical bonds and the like, increasing the stability and functional durability of the functional substances.

[0054] (3) The composite deodorant prepared by the present invention contains natural or plant-based substances or is prepared therefrom, all of which have antibacterial effects, are harmless to the human body, and are further strengthened in function through crosslinking and metal complexation.

[0055] (4) Different porous materials and different functional antibacterial and deodorizing agents are selected in the present invention, which can endow the fibers with different colors, such as black (activated carbon, binchotan, etc.), white, yellow, etc., to meet the requirements of multiple colors.

[0056] (5) The antibacterial and deodorizing agent prepared in the present invention can be used in the preparation of chemical fibers, including chemically fiberized fibers by wet spinning and synthetic fibers by melt spinning, etc. It can also be used to treat fabrics by padding process with this antibacterial and deodorizing agent to obtain antibacterial and deodorizing fabrics, and different ratios can be used according to different application fields. Detailed implementation mode

[0057] The present invention will be further described below in conjunction with specific embodiments.

[0058] The raw materials and auxiliaries used in the following examples and comparative examples are all normal commercially available products.

[0059] Example 1

[0060] 1. Preparation of modified porous adsorption and protection powder, including the following steps:

[0061] 1) Preparation of porous material powder

[0062] The binchotan inorganic porous material is ground and dispersed by using a sand mill disperser, with a zirconia bead filling rate of 50%, a concentration of inorganic porous material of 30%, a grinding speed of 2000 r / min. During the grinding process, the particle size of the inorganic porous material powder is detected until the particle size reaches D90 = 2.950 μm to obtain a primary inorganic porous material powder dispersion; and vinyltriethoxysilane, a silane coupling agent, is added to the inorganic porous material powder dispersion for surface modification treatment, with an addition amount of 10% of the inorganic porous material powder, and the reaction continues for 30 min at a speed of 500 r / min to obtain an inorganic porous material powder dispersion.

[0063] The above-prepared inorganic porous material dispersion is dried by a spray dryer, with an inlet air temperature of 150 °C, an outlet air temperature of 95 °C, and a feeding speed of 15 mL / min to obtain porous material powder.

[0064] 2) Preparation of modified porous adsorption and protection powder

[0065] The hemicellulose with a polymerization degree of 80 is dissolved in an ionic liquid to obtain a hemicellulose solution with a concentration of 2%. The ionic liquid is an alkylimidazole-based ionic liquid, where the cation is ethyl; the anion is Cl - .

[0066] Add the prepared porous material powder to the above-prepared solution. During the addition process, stir while adding, with a stirring speed of 300 r / min. After the addition is completed, continue stirring for 30 min to allow the above porous material to fully adsorb the solution. Then, filter to obtain the wet modified porous material. Add deionized water to the wet modified porous material to precipitate the adsorbed hemicellulose and attach it to the surface of the pores of the porous material. Then, perform spray drying, with an inlet air temperature of 150 °C, an outlet air temperature of 95 °C, and a feed rate of 15 mL / min to obtain the modified porous adsorption protection powder.

[0067] 2. A composite deodorant: It is prepared using the above-mentioned modified porous adsorption protection powder, and specifically includes the following steps:

[0068] a. Prepare the composite alkaline odor elimination powder

[0069] a1. Dissolve the biological alginic acid in deionized water at 25 °C to obtain a solution with a concentration of 4%.

[0070] a2. Add the prepared modified porous adsorption protection powder to the above solution for adsorption. Start stirring when adding the modified porous adsorption protection powder and during adsorption, with a stirring speed of 200 r / min. After the addition is completed, continue stirring for 30 min to allow it to fully adsorb the biological acid, and dry it using the spray drying process to obtain the first composite alkaline odor elimination powder.

[0071] a3. Add the first composite alkaline odor elimination powder to a solution containing 3% butanetetracarboxylic acid, 1% zinc sulfate, and at a temperature of 25 °C, and continue the adsorption for 30 min. After adsorption, filter and perform electron beam irradiation treatment on the filtered solid, with an irradiation dose of 20 kGy and an irradiation time of 120 s, and then perform vacuum drying to obtain the composite alkaline odor elimination powder.

[0072] b. Prepare the composite acid odor and old-age odor elimination powder

[0073] b1. Add glycine and persimmon tannin in a mass ratio of 1:1 to deionized water for dissolution to obtain a solution with a total concentration of 5%.

[0074] b2. Add the prepared modified porous adsorption protection powder to the above solution for adsorption. Start stirring when adding the modified porous adsorption protection powder and during adsorption, with a stirring speed of 200 r / min. After the addition is completed, continue stirring for 30 min to allow it to fully adsorb, and then dry it using the spray drying process to obtain the first composite acid odor and old-age odor elimination powder.

[0075] b3. Add the first composite deacidifying and anti-aging odor powder into a solution containing 1.5% cross-linking agent ethylene glycol diglycidyl ether at a temperature of 25°C, continue the adsorption for 20 minutes. After filtration, conduct a cross-linking reaction on the filtered solid at a reaction temperature of 30°C, a reaction time of 70 minutes, and a pH of 7.0. Then conduct vacuum drying to obtain the final composite deacidifying and anti-aging odor powder.

[0076] c. Mix the prepared composite dealkalizing odor powder and the composite deacidifying and anti-aging odor powder in a mass ratio of 1:1 to prepare a composite deodorant.

[0077] The prepared antibacterial composite absorbent powder has an antibacterial rate of 97.5% against Staphylococcus aureus, 98.9% against Escherichia coli, and 98.1% against Candida albicans; its ammonia reduction rate is 96.1%, acetic acid reduction rate is 97.5%, isovaleric acid reduction rate is 99.6%, and 2-nonenal reduction rate is 98.3%.

[0078] d. Add the prepared composite deodorant into deionized water with a mass fraction of 35%, add 15% of the dispersant sodium dodecylbenzenesulfonate and 2% of the defoamer polyoxypropylene polyoxyethylene glycerol ether based on the mass of the composite deodorant to the system. After stirring and mixing evenly, add it into a high-speed disperser for dispersion at a dispersion speed of 1500 r / min. Maintain the temperature at 18°C during the dispersion process for 90 minutes. Then add 3% of the thickener sodium alginate based on the mass of the composite deodorant and mix evenly to obtain a composite deodorant dispersion.

[0079] The prepared composite deodorant dispersion is added to viscose fibers for the wet spinning process through the in-spinning injection process, with an addition amount of 6.0% (based on methyl cellulose) calculated by the effective component. Then, through processes such as cutting, washing, desulfurization, bleaching, oiling, and drying, viscose staple fibers with multifunctions such as antibacterial and deodorizing and a specification of 1.67 dtex × 38 mm are obtained. The antibacterial rate of this fiber against Staphylococcus aureus is 81.2%, against Escherichia coli is 82.5%, and against Candida albicans is 83.3%; its ammonia reduction rate is 79.5%, acetic acid reduction rate is 76.9%, isovaleric acid reduction rate is 88.5%, and 2-nonenal reduction rate is 77.5%.

[0080] Example 2

[0081] 1. Preparation of the modified porous adsorbent powder, including the following steps:

[0082] 1) Preparation of the porous material powder

[0083] The zeolite porous material is ground and dispersed using a sand mill disperser, with a zirconia bead filling rate of 68%, an inorganic porous material concentration of 39.5%, a grinding speed of 2560 r / min. During the grinding process, the particle size of the inorganic porous material powder is measured until the particle size reaches D90 = 2.736 μm, obtaining a primary inorganic porous material powder dispersion; and vinyltrimethoxysilane, a silane coupling agent, is added to the inorganic porous material powder dispersion for surface modification treatment, with the addition amount being 12.6% of the inorganic porous material powder, and the reaction continues at a speed of 592 r / min for 41 min to obtain an inorganic porous material powder dispersion.

[0084] The inorganic porous material dispersion prepared above is dried using a spray dryer, with an inlet air temperature of 168 °C, an outlet air temperature of 99.5 °C, and a feed rate of 20.5 mL / min, obtaining a porous material powder.

[0085] 2) Preparation of modified porous adsorption protective powder

[0086] A high molecular polypeptide with a molecular weight of 7500 is dissolved in an ionic liquid to obtain a polypeptide solution with a concentration of 3.6%. The ionic liquid is an alkylimidazole-based ionic liquid, where the cation is butyl; the anion is SCN - 。

[0087] The prepared porous material powder is added to the above-prepared solution. During the addition process, stirring is carried out while adding, with a stirring speed of 326 r / min. After the addition is completed, stirring continues for 42 min to allow the above porous material to fully adsorb the solution, and then filtration is carried out to obtain a wet modified porous material. Then, deionized water is added to the wet modified porous material to precipitate the adsorbed polypeptide, which adheres to the pore surface of the porous material, and then spray drying is carried out, with an inlet air temperature of 168 °C, an outlet air temperature of 99 °C, and a feed rate of 21 mL / min to obtain a modified porous adsorption protective powder.

[0088] 2. A composite deodorant: It is prepared using the above-mentioned modified porous adsorption protective powder, and specifically includes the following steps:

[0089] a. Preparation of composite de-alkaline odor powder

[0090] a1. Alginate and chlorogenic acid of biological origin are added to deionized water at 28.6 °C in a mass ratio of 1:1 for dissolution to obtain a solution with a concentration of 5.1%.

[0091] a2. Add the prepared modified porous adsorption and protection powder into the above solution for adsorption. Start stirring when adding the modified porous adsorption and protection powder, with a stirring speed of 255 r / min. Continue stirring for 41 min after adding to allow it to fully adsorb the biological acid, and then dry it using the spray drying process to obtain the first composite alkaline odor eliminating powder.

[0092] a3. Add the first composite alkaline odor eliminating powder into a solution containing 3.9% citric acid, 2.1% zinc acetate, and at a temperature of 31°C, and continue the adsorption for 35 min. After adsorption, filter, and perform electron beam irradiation treatment on the filtered solid, with an irradiation dose of 38 kGy and an irradiation time of 91 s, and then perform vacuum drying to obtain the final composite alkaline odor eliminating powder.

[0093] b. Prepare the composite acidic odor and senile odor eliminating powder

[0094] b1. Dissolve green tea tannin and flavonol in deionized water according to a mass ratio of 1:2 to obtain a solution with a concentration of 6.2%. The flavonol is from plant extracts.

[0095] b2. Add the prepared modified porous adsorption and protection powder into the above solution for adsorption. Start stirring when adding the modified porous adsorption and protection powder, with a stirring speed of 265 r / min. Continue stirring for 41 min after adding to allow it to fully adsorb, and then dry it using the spray drying process to obtain the first composite acidic odor and senile odor eliminating powder.

[0096] b3. Add the first composite acidic odor and senile odor eliminating powder into a solution containing 2.6% cross-linking agent transglutaminase and at a temperature of 29°C, and continue the adsorption for 26 min. After adsorption and filtration, perform a cross-linking reaction on the filtered solid, with a reaction temperature of 35°C, a reaction time of 61 min, and a pH of 7.9, and then perform vacuum drying to obtain the final composite acidic odor and senile odor eliminating powder.

[0097] c. Mix the prepared composite alkaline odor eliminating powder and the composite acidic odor and senile odor eliminating powder according to a mass ratio of 1:2, and then add 10% of PHBV (copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate) based on the total mass of the powder for blending to prepare the composite odor eliminator.

[0098] The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is 98.6%, against Escherichia coli is 99.1%, and against Candida albicans is 98.9%; its reduction rate of ammonia is 98.1%, reduction rate of acetic acid is 99.0%, reduction rate of isovaleric acid is 99.7%, and reduction rate of 2-nonenal is 98.6%.

[0099] The prepared composite deodorant is added to polyester fibers for melt spinning by pre-spinning injection. First, it is used to prepare deodorant polyester masterbatch chips. The polyester chip melt and the composite deodorant powder are fully mixed, with the addition amount of the composite deodorant powder being 30% (based on the polyester chips). Then, the deodorant polyester masterbatch chips and conventional polyester chips are mixed and melt-spun in proportion, so that the addition amount of the composite deodorant powder in the final fiber is 8.0%. Then, the fiber undergoes processes such as cutting, oiling, and drying to obtain polyester staple fibers with a specification of 2.22 dtex × 38 mm and multifunctions such as antibacterial and deodorizing. The antibacterial rate of this fiber against Staphylococcus aureus is 83.6%, against Escherichia coli is 85.1%, and against Candida albicans is 85.3%; its reduction rate of ammonia is 81.6%, of acetic acid is 79.2%, of isovaleric acid is 90.1%, and of 2-nonenal is 79.1%.

[0100] Example 3

[0101] 1. Preparation of modified porous adsorption protective powder, including the following steps:

[0102] 1) Preparation of porous material powder

[0103] Using the organic porous dispersant β-cyclodextrin for direct dispersion to obtain a β-cyclodextrin organic porous dispersant dispersion with a concentration of 50%.

[0104] The above-prepared β-cyclodextrin organic porous dispersant dispersion is dried using a spray dryer, with an inlet air temperature of 180 °C, an outlet air temperature of 105 °C, and a feeding speed of 25 mL / min, to obtain porous material powder.

[0105] 2) Preparation of modified porous adsorption protective powder

[0106] Dissolve the mixture of hemicellulose with a degree of polymerization of 50 and a high molecular polypeptide with a molecular weight of 5000 in an ionic liquid to obtain a hemicellulose and polypeptide mixture solution with a concentration of 5%. The ionic liquid is an alkylimidazole-based ionic liquid, where the cation is butyl and the anion is Cl - .

[0107] Add the prepared porous material powder to the above-prepared solution. During the addition process, stir while adding, with a stirring speed of 350 r / min. After the addition is completed, continue stirring for 50 min to enable the above porous material to fully adsorb the solution. Then, filter to obtain the wet modified porous material. Then, add deionized water to the wet modified porous material to precipitate the adsorbed substances and attach them to the pore surfaces of the porous material. Then, perform spray drying again, with an inlet air temperature of 180 °C, an outlet air temperature of 105 °C, and a feeding speed of 25 mL / min, to obtain the modified porous adsorption protective powder.

[0108] 2. A composite deodorant: It is prepared by using the above-mentioned modified porous adsorption protective powder, and specifically includes the following steps:

[0109] a. Preparation of composite alkaline odor-eliminating powder

[0110] a1. Add biological chlorogenic acid to deionized water at 30 °C for dissolution to obtain a solution with a concentration of 6%.

[0111] a2. Add the prepared modified porous adsorption protective powder to the above solution for adsorption. Start stirring when adding the modified porous adsorption protective powder and during adsorption, with a stirring speed of 300 r / min. Continue stirring for 50 min after adding to allow it to fully adsorb the biological acid, and then dry it using the spray drying process to obtain the first composite alkaline odor-eliminating powder.

[0112] a3. Add the first composite alkaline odor-eliminating powder to a solution containing 5% maleic acid, 3% zinc sulfate, and at a temperature of 35 °C, and continue the adsorption for 40 min. After adsorption, filter and conduct electron beam irradiation treatment on the filtered solid, with an irradiation dose of 50 kGy and an irradiation time of 60 s, and then perform vacuum drying to obtain the composite alkaline odor-eliminating powder.

[0113] b. Preparation of composite acid odor-eliminating and senile odor-eliminating powder

[0114] b1. Add cysteine and tea polyphenols in a mass ratio of 1:1 to deionized water for dissolution to obtain a solution with a concentration of 7%. The tea polyphenols are from plant extracts.

[0115] b2. Add the prepared modified porous adsorption protective powder to the above solution for adsorption. Start stirring when adding the modified porous adsorption protective powder and during adsorption, with a stirring speed of 300 r / min. Continue stirring for 50 min after adding to allow it to fully adsorb, and then dry it using the spray drying process to obtain the first composite acid odor-eliminating and senile odor-eliminating powder.

[0116] b3. Add the first composite acid odor-eliminating and senile odor-eliminating powder to a solution containing 3% cross-linking agent ethylene glycol diglycidyl ether and at a temperature of 35 °C, and continue the adsorption for 30 min. After adsorption and filtration, conduct a cross-linking reaction on the filtered solid, with a reaction temperature of 40 °C, a reaction time of 50 min, and a pH of 8.5, and then perform vacuum drying to obtain the final composite acid odor-eliminating and senile odor-eliminating powder.

[0117] c. Mix the prepared composite alkaline odor-eliminating powder and composite acid odor-eliminating and senile odor-eliminating powder in a mass ratio of 1:1, and then add 15% of the total powder mass of lavender as an aromatic substance for blending to obtain the composite deodorant.

[0118] The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is 99.2%, against Escherichia coli is 99.5%, and against Candida albicans is 99.6%; its ammonia reduction rate is 98.9%, acetic acid reduction rate is 99.3%, isovaleric acid reduction rate is 99.9%, and 2-nonenal reduction rate is 99.4%.

[0119] d. Add the prepared composite deodorant to deionized water with a mass fraction of 45%, add sodium dodecylbenzenesulfonate as a dispersant accounting for 20% of the mass of the composite deodorant and polyoxypropylene polyoxyethylene glycerol ether as an antifoaming agent accounting for 5% of the mass of the composite deodorant to the system. After stirring and mixing evenly, add it to a high-speed disperser for dispersion. The dispersion speed is 2000 r / min. During the dispersion process, maintain the temperature at 20 °C and the dispersion time is 60 min. Then add sodium carboxymethylcellulose as a thickening agent accounting for 6% of the mass of the composite deodorant and mix well to obtain a composite deodorant dispersion.

[0120] Use the prepared composite deodorant dispersion to treat the fabric by a two-rolling and two-pressing treatment process with a bath ratio of 1:20 to obtain a deodorant fabric. The antibacterial rate of this fiber against Staphylococcus aureus is 87.5%, against Escherichia coli is 87.6%, and against Candida albicans is 88.9%; its ammonia reduction rate is 83.9%, acetic acid reduction rate is 82.5%, isovaleric acid reduction rate is 93.2%, and 2-nonenal reduction rate is 81.6%.

[0121] Comparative Example 1

[0122] In comparison with Example 1, in this comparative example, when preparing the porous material powder, it is not treated with a silane coupling agent, and other preparation steps are the same.

[0123] The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is 96.1%, against Escherichia coli is 96.8%, and against Candida albicans is 95.9%; its ammonia reduction rate is 93.2%, acetic acid reduction rate is 94.1%, isovaleric acid reduction rate is 96.8%, and 2-nonenal reduction rate is 95.6%.

[0124] Add the prepared composite deodorant to deionized water with a mass fraction of 35%, add sodium dodecylbenzenesulfonate as a dispersant accounting for 15% of the mass of the composite deodorant and polyoxypropylene polyoxyethylene glycerol ether as an antifoaming agent accounting for 2% of the mass of the composite deodorant to the system. After stirring and mixing evenly, add it to a high-speed disperser for dispersion. The dispersion speed is 1500 r / min. During the dispersion process, maintain the temperature at 18 °C and the dispersion time is 90 min. Then add sodium alginate as a thickening agent accounting for 3% of the mass of the composite deodorant and mix well to obtain a composite deodorant dispersion.

[0125] The prepared composite deodorant dispersion is added to viscose fibers for the wet spinning process through the in-line injection process, and the addition amount is 6.0% (based on the alpha cellulose) calculated by the active ingredient. Then, through processes such as cutting, washing, desulfurization, bleaching, oiling, and drying, viscose staple fibers with multifunctions such as antibacterial and deodorizing and a specification of 1.67 dtex × 38 mm are obtained. The antibacterial rate of this fiber against Staphylococcus aureus is 77.1%, against Escherichia coli is 79.2%, and against Candida albicans is 78.0%; its ammonia reduction rate is 71.2%, acetic acid reduction rate is 72.0%, isovaleric acid reduction rate is 83.2%, and 2-nonenal reduction rate is 73.8%.

[0126] Comparative Example 2

[0127] Compared with Example 1 in this comparative example, when preparing the modified porous adsorbent powder in step 2), hemicellulose is not used for treatment, and other preparation steps are the same.

[0128] The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is 95.5%, against Escherichia coli is 96.1%, and against Candida albicans is 95.1%; its ammonia reduction rate is 91.9%, acetic acid reduction rate is 93.2%, isovaleric acid reduction rate is 95.5%, and 2-nonenal reduction rate is 94.1%.

[0129] The prepared composite deodorant is added to deionized water, and its mass fraction is 35%. A dispersant sodium dodecylbenzenesulfonate accounting for 15% of the mass of the composite deodorant and an antifoaming agent polyoxypropylene polyoxyethylene glycerol ether accounting for 2% of the mass of the composite deodorant are added to the system. After stirring and mixing evenly, it is added to a high-speed disperser for dispersion. The dispersion speed is 1500 r / min, the temperature is maintained at 18 °C during the dispersion process, the dispersion time is 90 min, and then a thickener sodium alginate accounting for 3% of the mass of the composite deodorant is added and mixed evenly to obtain the composite deodorant dispersion.

[0130] The prepared composite deodorant dispersion is added to viscose fibers for the wet spinning process through the in-line injection process, and the addition amount is 6.0% (based on the alpha cellulose) calculated by the active ingredient. Then, through processes such as cutting, washing, desulfurization, bleaching, oiling, and drying, viscose staple fibers with multifunctions such as antibacterial and deodorizing and a specification of 1.67 dtex × 38 mm are obtained. The antibacterial rate of this fiber against Staphylococcus aureus is 75.9%, against Escherichia coli is 77.8%, and against Candida albicans is 76.7%; its ammonia reduction rate is 70.1%, acetic acid reduction rate is 69.2%, isovaleric acid reduction rate is 81.0%, and 2-nonenal reduction rate is 71.1%.

[0131] Comparative Example 3

[0132] This comparative example, compared with Example 1, only uses amino acids for the persimmon tannin of b and for preparing the composite deacidifying and anti-aging odor powder, and the other preparation steps are the same.

[0133] The antibacterial rate of the prepared antibacterial composite absorbent powder against Staphylococcus aureus is 98.2%, the antibacterial rate against Escherichia coli is 98.5%, and the antibacterial rate against Candida albicans is 97.6%; its ammonia reduction rate is 96.3%, the acetic acid reduction rate is 96.9%, the isovaleric acid reduction rate is 99.2%, and the 2-nonenal reduction rate is 93.5%.

[0134] The prepared composite deodorant is added to deionized water, and its mass fraction is 35%. A dispersant sodium dodecylbenzenesulfonate accounting for 15% of the mass of the composite deodorant and an antifoaming agent polyoxypropylene polyoxyethylene glycerol ether accounting for 2% of the mass of the composite deodorant are added to the system. After stirring and mixing evenly, it is added to a high-speed disperser for dispersion. The dispersion speed is 1500 r / min, the temperature is maintained at 18 °C during the dispersion process, and the dispersion time is 90 min. Then, a thickener sodium alginate accounting for 3% of the mass of the composite deodorant is added and mixed evenly to obtain a composite deodorant dispersion.

[0135] The prepared composite deodorant dispersion is added to viscose fibers for the wet spinning process through a melt spinning injection process. The addition amount is 6.0% (based on methyl cellulose) calculated by the effective component. Then, through processes such as cutting, washing, desulfurization, bleaching, oiling, and drying, viscose staple fibers with multifunctions such as antibacterial and deodorizing and a specification of 1.67 dtex × 38 mm are obtained. The antibacterial rate of this fiber against Staphylococcus aureus is 81.5%, the antibacterial rate against Escherichia coli is 82.3%, and the antibacterial rate against Candida albicans is 83.5%; its ammonia reduction rate is 79.3%, the acetic acid reduction rate is 76.7%, the isovaleric acid reduction rate is 88.6%, and the 2-nonenal reduction rate is 72.2%.

[0136] Of course, the above content is only the preferred embodiment of the present invention and cannot be considered as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples. Equivalent changes and improvements made by those of ordinary skill in the art within the essence of the present invention shall fall within the scope covered by the patent of the present invention.

Claims

1. A method for preparing a composite deodorant, characterized in that: The following steps are involved: a. Preparation of composite alkaline deodorizing powder a1. Add one or more of alginic acid, lactic acid and chlorogenic acid into water at 25-30°C to dissolve the solution to obtain a solution with a mass concentration of 4%-6%; a2. Add the modified porous adsorption protection powder to the solution of step a1, stir and adsorb, and spray dry to obtain a first composite deodorizing alkaline powder; a3. Add the first composite deodorizing alkaline powder to a solution containing 3%-5% polycarboxylic acid and 1%-3% zinc salt at a temperature of 25°C-35°C, adsorb for 30-40 minutes, filter, irradiate the solid with electron beam, and vacuum dry to obtain a composite deodorizing alkaline powder; b. Preparation of composite powder for eliminating acidic odor and senile odor b1. Mix one or more of amino acids, tannins, and polyphenols, add them into water and dissolve them to obtain a solution with a mass concentration of 5% to 7%; b2, adding the modified porous adsorption protection powder to the solution of step b1, stirring and adsorbing, and spray drying to obtain the first composite powder for eliminating acid odor and senile odor; b3. Add the first composite deodorizing and acid odor removing powder to a solution of 1.5%-3% ethylene glycol diglycidyl ether or glutamine aminotransferase at a temperature of 25°C-35°C, adsorb for 20min-30min, filter, and cross-link the solid at a reaction temperature of 30°C-40°C, a reaction time of 50min-70min, and a pH of 7.0-8.

5. After the reaction, vacuum dry to obtain a composite deodorizing and acid odor removing powder; c. Mixing the prepared composite deodorizing alkaline odor removing powder with the composite deodorizing acidic odor removing and old age odor removing powder to prepare a composite deodorizing agent; The modified porous adsorption protection powder is prepared according to the following steps: (1) spray-drying an inorganic porous material dispersion or a β-cyclodextrin organic porous material dispersion to obtain a porous material powder; (2) dissolving hemicellulose and / or polypeptide in ionic liquid to obtain a mixed solution with a mass concentration of 2-5%; (3) adding the porous material powder of step (1) to the mixed solution of step (2), stirring and mixing, filtering, adding water, and spray drying to obtain a modified porous adsorption protection powder; The inorganic porous material dispersion in step (1) is prepared by grinding the inorganic porous material powder to a particle size D90≤3.350 μm, adding a silane coupling agent after dispersion, and uniformly dispersing the powder; the inorganic porous material powder is one of activated carbon, binchotan, silica gel, zeolite, and silicate minerals; and the amount of the silane coupling agent added is 10%-15% of the mass of the inorganic porous material powder.

2. The method for preparing the composite deodorant according to claim 1, characterized in that: The mass concentration of the inorganic porous substance powder in the inorganic porous substance dispersion is 30%-50%; the mass concentration of β-cyclodextrin in the β-cyclodextrin organic porous substance dispersion is 30%-50%.

3. The method for preparing the composite deodorant according to claim 2, characterized in that: In step (2), the degree of polymerization of hemicellulose is 50-80; the molecular weight of the polypeptide is 5000-10000; the ionic liquid is an alkyl imidazole type ionic liquid, wherein the cation is one of ethyl imidazole and butyl imidazole; the anion is Cl - 、SCN - One of them.

4. The method for preparing the composite deodorant according to claim 3, characterized in that: The spray drying parameters in step (1) and step (3) are: inlet air temperature 150°C-180°C, outlet air temperature 95°C-105°C, and feed rate 15mL / min-25mL / min.

5. A composite deodorant, characterized in that: The deodorant is prepared by the preparation method of the composite deodorant according to any one of claims 1 to 4.

6. An application of the composite deodorant according to claim 5, characterized in that: The prepared composite deodorant is used in synthetic fibers for melt spinning, or the composite deodorant is used to make a composite deodorant dispersion for use in chemical fibers for wet spinning, or the composite deodorant dispersion is directly applied to fabrics and the fabrics are treated by a padding process.

7. The use of the composite deodorant according to claim 6, characterized in that: The specific steps of using the composite deodorant to prepare the composite deodorant dispersion are as follows: adding the prepared composite deodorant into water with a mass fraction of 35%-45%, adding a dispersant accounting for 15%-20% of the mass of the composite deodorant and a defoamer accounting for 2%-5% of the mass of the composite deodorant, stirring and mixing evenly, dispersing, and then adding a thickener accounting for 3%-6% of the mass of the composite deodorant, stirring evenly, and preparing the composite deodorant dispersion; the dispersion speed is 1500r / min-2000r / min, the temperature is maintained at 18°C-20°C during the dispersion process, and the dispersion time is 60min-90min.