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CN115074992B - Fabric deodorant finishing liquid, application thereof and manufacturing method of photocatalysis deodorant fabric - Google Patents

Fabric deodorant finishing liquid, application thereof and manufacturing method of photocatalysis deodorant fabric Download PDF

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Publication number
CN115074992B
CN115074992B CN202210933176.7A CN202210933176A CN115074992B CN 115074992 B CN115074992 B CN 115074992B CN 202210933176 A CN202210933176 A CN 202210933176A CN 115074992 B CN115074992 B CN 115074992B
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Prior art keywords
fabric
parts
finishing liquid
titanium dioxide
deodorant
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CN202210933176.7A
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CN115074992A (en
Inventor
董红霞
马正升
马逸凡
赵亮东
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Shanghai Jieyikang Chemical Technology Co ltd
Shanghai Guofan Chemical New Material Co ltd
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Shanghai Jieyikang Chemical Technology Co ltd
Shanghai Guofan Chemical New Material Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a fabric deodorant finishing liquid, application thereof and a method for manufacturing photocatalysis deodorizing fabric, which mainly solve the problem of poor photocatalysis deodorizing effect of the fabric photocatalysis deodorizing finishing liquid in the prior art, and the invention adopts the fabric deodorant finishing liquid and comprises the following components in parts by weight: 10 parts of titanium dioxide-based photocatalyst; 5-20 parts of a surfactant; 0.2-1 part of thickener; 1-10 parts of cross-linking agent; 100-1000 parts of water; the titanium dioxide-based photocatalyst comprises titanium dioxide and doped metal elements, wherein the doped metal elements comprise at least one of the elements selected from the group consisting of IIB elements and VIII elements, so that the technical problem is well solved, and the titanium dioxide-based photocatalyst can be used in the production of fabric deodorant finishing liquid.

Description

Fabric deodorant finishing liquid, application thereof and manufacturing method of photocatalysis deodorant fabric
Technical Field
The invention relates to a fabric deodorant finishing liquid, application thereof and a method for manufacturing photocatalysis deodorant fabric.
Background
Solar energy belongs to green energy, is inexhaustible. The photocatalyst has the functions of degrading pollutant, resisting bacteria, deodorizing, etc. under the condition of sunlight irradiation. In the 30 s of the 20 th century, researchers have studied to find that titanium dioxide can decompose dyes and degrade fibers under aerobic and ultraviolet light irradiation. In the 80 s of the 20 th century, research has found that the photocatalyst can catalyze and degrade organic matters in sewage. With advances in technology and the development of measurement means, researchers have gradually perfected semiconductor band theory and have more profound interpretation of the mechanism of photocatalysis.
The photocatalyst is also called as photocatalyst, and is a compound capable of accelerating the chemical reaction process under the irradiation of light. Titanium dioxide (TiO 2) is also called titanium dioxide, is safe and harmless, has good photoreaction activity, can be used as a photocatalyst, an ultraviolet absorber, a bactericide and the like, but has the defects that (1) electron-hole recombination is easy to occur; (2) The forbidden bandwidth is large (3.2 eV), and solar energy cannot be effectively utilized; (3) higher requirements for the loading material; and (4) difficult dispersion, recovery and reuse. Thus limiting its industrial large-scale application.
The transition metal ion doped TiO2 is an effective method for improving the photocatalytic activity thereof. The positions of the valence band and the conduction band of different semiconductors are different, the prepared composite semiconductor material can form a Fermi level difference at the interface of the composite semiconductor material, and the forbidden band widths of different semiconductors are different.
Ammonia gas has been shown to be an odor-causing chemical. The higher the concentration of the malodor-generating chemicals, the higher the discomfort of the person, and chemical deodorizing and biological deodorizing can be used to remove the malodor. For more than 10 years, the deodorization finishing of textiles is more and more paid attention to, and researches show that TiO 2 has good deodorization function under ultraviolet irradiation, and can degrade odor into non-toxic and odorless micromolecular products (Wang Xiaoyan, wang Luohao, sun Ying, shang Lei, dai Yue, zhang Ruiping. The photocatalysis antibacterial deodorization self-cleaning finishing [ J ]. Dyeing and finishing technology of terylene fabrics, 2021,43 (05): 17-21.). However, the deodorizing performance of the photocatalyst in the prior art is still insufficient.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of poor photocatalysis deodorization effect of the fabric photocatalysis deodorization finishing liquid in the prior art, and the novel fabric photocatalysis deodorization finishing liquid is provided, and has the characteristic of good photocatalysis deodorization effect of the fabric when being used for fabric deodorization finishing. The technical proposal is as follows:
The fabric deodorant finishing liquid comprises the following components in parts by weight:
10 parts of titanium dioxide-based photocatalyst;
5-20 parts of a surfactant;
0.2-1 part of thickener;
1-10 parts of cross-linking agent;
100-1000 parts of water;
The titanium dioxide-based photocatalyst comprises titanium dioxide and a doped metal element, wherein the doped metal element comprises at least one selected from the group consisting of IIB elements and VIII elements.
The technical key of the invention is that the titanium dioxide photocatalyst adopted in the fabric deodorant finishing liquid endows the fabric deodorant finishing liquid with the characteristic of good deodorizing effect when being used for fabric deodorizing finishing.
In the above technical solution, preferably, the element IIB is selected from zinc.
In the above technical solution, preferably, the group VIII element is selected from iron, cobalt or nickel.
In the above technical solution, preferably, the content of the doped metal element in the titanium dioxide-based photocatalyst is greater than 0% and 10% or less in terms of doped metal oxide by weight. For example, but not limited to, the doped metal element content in the titania-based photocatalyst is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% and the like, based on the doped metal oxide. In the titanium oxide-based photocatalyst of examples and comparative examples, the content of the doped metal element in the titanium oxide-based photocatalyst is generally 3% in terms of doped metal oxide, by comparison only.
In the technical scheme, when the doped metal elements simultaneously comprise zinc and iron, the zinc and the iron have an interaction enhancement effect in improving the photocatalytic deodorizing effect of the fabric. At this time, the ratio between zinc and iron is not particularly limited, for example, but not limited to, the weight ratio between ZnO and Fe 2O3 is 0.1 to 10, more specific non-limiting weight ratio examples between ZnO and Fe 2O3 are 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1, 2,3, 4,5, 6, 7, 8, 9, etc., and more preferably the weight ratio between ZnO and Fe2O3 is 1 to 6.
In the above technical solution, the titanium dioxide photocatalyst may be obtained by a method including the following steps:
(1) Obtaining titanate solution I;
(2) Obtaining a solution II doped with metal element ions, wherein a solvent adopted by the solution II comprises water and acetic acid;
(3) Adding the solution II into the solution I under stirring to obtain sol, and continuing stirring until the sol is converted into gel;
(4) And roasting the gel to obtain the titanium dioxide-based photocatalyst.
In the above technical solution, preferably, the titanate in the step (1) corresponds to the following formula 1:
Wherein R 1～R4 is independently C1-C5 alkyl. Such as, but not limited to, R 1～R4 is independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl. By way of non-limiting example of a specific titanate, the titanate may be (tetra) methyl titanate, (tetra) ethyl titanate, (tetra) n-propyl titanate, (tetra) isopropyl titanate, (tetra) n-butyl titanate, (tetra) isobutyl titanate, (tetra) t-butyl titanate, (tetra) n-pentyl titanate, (tetra) isopentyl titanate, and the like, or mixtures thereof. For comparison only, the titanate esters used in the examples and comparative examples are generally (tetra) n-butyl titanate.
In the above technical scheme, the solvent used in the solution I in the step (1) is not particularly limited, as long as the titanate can be dissolved and the solution I and the solvent in the step (2) can be mutually dissolved. For example, the solvent used in the solution I in the step (1) is a lower alcohol, preferably the lower alcohol is a C1-C3 alcohol. By way of non-limiting example, the lower alcohol may be a monohydric alcohol, a dihydric alcohol, or a trihydric alcohol. Such as, but not limited to, methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, and the like. However, from the standpoint of mass transfer, monohydric alcohols are generally selected because they have a lower viscosity than dihydric and trihydric alcohols. In the examples and comparative examples, only the same ratio is used, but ethanol is generally used as the lower alcohol.
In the above technical solution, preferably, in step (1), the titanate is 5 to 20% by weight of the titanium dioxide in the solution I, such as but not limited to 6.0%, 7.0%, 8.0%, 9.0%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% by weight of the titanium dioxide in the solution I, and so on. The concentration by weight of titanium dioxide in the solutions I in the examples and comparative examples is generally 12.0% by weight, only by comparison.
In the above technical solution, preferably, the weight ratio of water to acetic acid in the solvent in the step (2) is 0.5 to 1.5. Such as, but not limited to, the ratio being 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc. The weight ratio of water to acetic acid in the mixed solvent described in examples and comparative examples was generally 1.0, by way of comparison only.
In the above technical solution, preferably, the doped metal element ion in the step (2) is provided by a salt of the doped metal, and preferably, the salt of the doped metal is acetate, nitrate or chloride.
In the above technical solution, preferably, when the doping metal element in the step (2) includes iron, the iron ion is preferably a ferric ion, and further preferably the ferric ion is provided by a ferric salt, and preferably the ferric salt is acetate, nitrate or chloride.
In the above technical solution, preferably, when the doping metal element in the step (2) includes zinc, the zinc ion is preferably a divalent zinc ion, more preferably the divalent zinc ion is provided by a divalent zinc salt, and even more preferably the divalent zinc salt is acetate, nitrate or chloride.
In the above technical solution, the manner of obtaining the solution II is not particularly limited, and a person skilled in the art can reasonably choose to obtain comparable technical effects without having to do creative efforts. By way of example only, the means for obtaining solution II may be, for example, but not limited to: dissolving the metal-doped salt in water, and then adding acetic acid; or dissolving the metal-doped salt in the solvent; when the doping metal comprises both iron and zinc, the trivalent iron salt and divalent zinc salt may be dissolved in water in any order (e.g., sequentially or simultaneously) followed by the addition of acetic acid; or the trivalent iron salt and the divalent zinc salt are dissolved in the solvent in any order (such as sequentially or simultaneously); or respectively dissolving trivalent ferric salt and divalent zinc salt in water, respectively adding acetic acid, and then mixing; or respectively dissolving trivalent ferric salt and divalent zinc salt in the solvent, and then mixing; etc. We have not found how these ways are significantly different for achieving the technical effect of the invention.
In the above technical scheme, the weight ratio of the solution I to the solution II in the step (3) is not particularly limited, but we recommend that the weight ratio of the solution I to the solution II is 2-20. For example, but not limited to, the weight ratio of the solution I to the solution II is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, etc., it is further recommended that the ratio be 5 to 10. The weight ratio of the solution I to the solution II in the step (3) in the examples and the comparative examples was 8.1 by comparison only.
In the above technical solution, the temperatures required for obtaining the sol and converting the sol into the gel in the step (3) are not particularly limited, and especially the effect on obtaining the sol is very small, and a person skilled in the art can reasonably select to achieve the comparable technical effects of the present invention. However, the time required for the conversion from sol to gel is longer as the temperature is lower, and the gelation time is shorter as the temperature is higher. We recommend that the temperature of step (3) is 10 to 50℃such as, but not limited to, the temperature controlled by step (3) is 15℃20℃25℃30℃35℃40℃45℃and the like. The temperatures used in step (3) in the examples and comparative examples are generally 35℃for the same comparison only.
In the above technical solution, the gel in step (4) may be subjected to an unnecessary drying stage before roasting, and the dried gel may reduce the release amount of the gas during the roasting process due to the removal of a large amount of solvent, so that the roasting process in mass production is easier to control. However, the deodorizing effect of the present invention is not significantly affected by the drying process.
In the above-mentioned technical scheme, the drying temperature and the drying temperature in the step (4) are not particularly limited, and the drying temperature may be, for example, 50 to 90℃such as, but not limited to, 55℃60℃65℃70℃75℃80℃85℃and the like. The drying temperature in step (4) in examples and comparative examples is generally 70℃by comparison only.
In the above-mentioned technical scheme, the drying time in the step (4) is not particularly limited, and may be, for example, 5 to 48 hours, such as but not limited to 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, etc. The drying time of step (4) in examples and comparative examples is generally 24 hours, only by comparison.
In the above technical scheme, the roasting temperature in the step (4) is preferably 350-650 ℃, such as, but not limited to, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, and the like, and preferably 400-600 ℃. The temperature of the calcination in step (4) in examples and comparative examples is generally 500℃by comparison only.
In the above technical solution, the baking time in the step (4) is preferably 3 to 12 hours, for example, but not limited to, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, etc. The calcination time in step (4) in examples and comparative examples is generally 5 hours, which is merely comparable.
In the above technical scheme, the baking atmosphere in the step (4) is not particularly limited. But from the economical point of view, air roasting is sufficient. However, the roasting in the step (4) is preferably carried out in an air-ammonia gas mixed atmosphere, and the photocatalyst obtained by roasting in the air-ammonia gas mixed atmosphere has better photocatalytic deodorization effect; more preferably, the volume percentage of ammonia in the air-ammonia mixed atmosphere is 0.1-5%. Such as, but not limited to ,0.2％、0.4％、0.6％、0.8％、1.0％、1.1％、1.2％、1.4％、1.6％、1.8％、2.0％、2.2％、2.4％、2.6％、2.8％、3.0％、3.2％、3.6％、3.8％、4.0％、4.2％、4.4％、4.6％、4.8％, etc., more preferably 0.5 to 2.5%. The ammonia volume content is 2.0% when the air-ammonia gas mixture atmosphere is adopted for roasting in the step (4) in the examples and the comparative examples.
In the above technical scheme, the finer the particles of the titanium dioxide-based photocatalyst are, the more favorable for the photocatalyst to play a role in photocatalysis deodorization, and also the more favorable for stable dispersion in the fabric deodorant finishing liquid, but the finer the particles are, the higher the processing cost of the titanium dioxide-based photocatalyst is, so that the technical effect can be obtained by reasonably selecting the technical effect factors by comprehensively considering economic factors and technical effect factors, and the technical effect can be obtained without creative labor. For example, the photocatalyst may be 200 to 3000 mesh, such as, but not limited to, specifically 250 mesh, 270 mesh, 325 mesh, 400 mesh, 500 mesh, 600 mesh, 800 mesh, 1000 mesh, 1500 mesh, and the like. The photocatalysts in the examples and comparative examples are generally particles crushed and passed through a 600 mesh sieve, only in the same ratio.
In the above-mentioned technical scheme, the kind of the surfactant is not particularly limited, and those well known in the art can be used, but water-soluble surfactants are preferable. For example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like may be used.
As non-limiting examples of useful nonionic surfactants, fatty alcohol-polyoxyethylene ethers, tween, as fatty alcohol-polyoxyethylene ethers of composition RO (EO) nH, R is C8-C18 alkyl (e.g., C10, C11, C12, C13, C14, C15, C16, C17, etc.), n is the number of ethylene oxide addition in the structure, preferably n is 7-11 (e.g., but not limited to n is 7, 8, 9, 10, etc.); as non-limiting examples of Tween, there may be mentioned, for example, tween 20-80 (such as Tween 20, tween 40, tween 60, tween 80, or mixtures thereof).
As non-limiting examples of useful anionic surfactants, dodecylbenzene sulfonate, dodecylsulfate, or fatty alcohol polyoxyethylene ether sulfate, commercially available sodium salts and triethanolamine salts are possible.
In the same way, the surfactant in the examples and the comparative examples generally adopts dodecanol polyoxyethylene (9) ether, namely AEO9.
In the above technical solutions, the thickener functions to increase the viscosity of the aqueous system and to increase the suspension stability of the photocatalyst, as known to the person skilled in the art. The thickener is not particularly limited, and those known to those skilled in the art to be capable of thickening aqueous systems, such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, polyacrylamide, sodium polyacrylate, maleic anhydride acrylic acid copolymer, polyurethane associative thickener, and the like, may be employed.
When sodium carboxymethyl cellulose is used as the thickener, the viscosity thereof is 400 to 1200mpa.s (aqueous solution with a concentration of 2% by weight, 25 ℃), for example, but not limited to, sodium carboxymethyl cellulose which can be used in the present invention may have a viscosity of ：450mPa.s、500mPa.s、550mPa.s、600mPa.s、650mPa.s、700mPa.s、750mPa.s、800mPa.s、850mPa.s、900mPa.s、950mPa.s、1000mPa.s、1050mPa.s、1100mPa.s、1150mPa.s and the like. It is known to the person skilled in the art that, as a general rule, the higher the viscosity of the carboxymethylcellulose the smaller the amount, so that the person skilled in the art can reasonably choose the viscosity and the amount of sodium carboxymethylcellulose on the basis of this principle. Sodium carboxymethylcellulose having a viscosity of 740 Pa.s (2% strength by weight aqueous solution, 25 ℃) is generally used as the thickener in examples and comparative examples, only in the same ratio.
In the technical scheme, the cross-linking agent can increase the binding fastness between the photocatalyst particles and the fabric in the process of using the fabric deodorant finishing liquid. The crosslinking agent may be a thermally crosslinkable crosslinking agent or a photocrosslinking crosslinking agent. As the name suggests, the crosslinking agent of the thermally crosslinkable type is a crosslinking agent which forms a three-dimensional network structure by a heat treatment process and then plays a crosslinking role, and the crosslinking agent of the photocrosslinking type is a crosslinking agent which forms a three-dimensional network structure by a light treatment process and then plays a crosslinking role. Examples of the thermally crosslinkable crosslinking agent that can be used in the present invention include, but are not limited to, polyacrylic crosslinking agents (i.e., crosslinking agents having a polyacrylic acid skeleton in the molecular structure of the crosslinking agent), polyurethane crosslinking agents (i.e., crosslinking agents having a polyurethane skeleton in the molecular structure of the crosslinking agent), amide-formaldehyde crosslinking agents (i.e., crosslinking agents having an amide-formaldehyde resin skeleton in the molecular structure of the crosslinking agent), urea-formaldehyde crosslinking agents (i.e., crosslinking agents having a urea-formaldehyde resin skeleton in the molecular structure of the crosslinking agent), and polycarboxylic acid crosslinking agents.
The thermally crosslinkable crosslinking agents used in examples and comparative examples are the same, and further, the thermally crosslinkable crosslinking agents used in examples and comparative examples are JYK FIX-DI crosslinking agents of Shanghai Jieykang chemical Co., ltd. JYK FIX-DI is the polyurethane cross-linking agent (namely, the cross-linking agent taking polyurethane as a framework in the molecular structure of the cross-linking agent). Suitable for preparing textile coating and foam coating sizing; the combination can improve wet rubbing fastness in pigment printing paste. Can also be used in functional auxiliary agents for improving the washing resistance of functional finishing. The JYK FIX-DI has good compatibility with various functional assistants, can be mixed with deionized water in any proportion, and can be treated for 2-5 minutes at 130-150 ℃. As a general rule, the higher the temperature, the shorter the heat treatment time required, based on which a person skilled in the art can reasonably adjust the heat treatment temperature and the heat treatment time, both of which can achieve the technical effects without having to make creative efforts.
In the above technical scheme, as non-limiting examples, the parts of the surfactant are 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts and the like. The parts commonly used for surfactants in examples and comparative examples are, by way of comparison only, 10 parts.
In the above technical solution, by way of non-limiting example, the parts of the thickener are 0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9 and so on. The parts commonly used for thickeners in the examples and comparative examples are, by way of example only, 0.5 parts.
In the above technical scheme, as non-limiting examples, the parts of the cross-linking agent are 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, etc. The parts generally used for the crosslinking agents in examples and comparative examples are 5 parts by comparison only.
In the above technical scheme, as a non-limiting example, the water in the fabric deodorant finishing liquid is used in an amount of 150 parts, 200 parts, 250 parts, 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, 750 parts, 800 parts, 850 parts, 900 parts, 950 parts, and the like. The parts of water in the examples and comparative examples are 250 parts by comparison only.
The technical key of the invention is the selection of the photocatalyst, and a person skilled in the art can reasonably select how to blend the photocatalyst into the fabric deodorant finishing liquid according to the knowledge of the prior art, and can reasonably select other components in the fabric deodorant finishing liquid except the photocatalyst, such as mildew preventive, flavoring agent, antioxidant and the like.
The particular method of preparing the fabric deodorant finish is not particularly limited, but it is known to those skilled in the art that the manner of addition is particularly important when the thickener is in powder form, and if added to water immediately upon agitation tends to agglomerate, upon agglomeration, it dissolves particularly slowly. Preferably, part or all of the water required in the formulation (typically at least the water required for the formulation) is placed in a large cross-section container, the thickener powder is sprinkled on a stationary water surface to allow the thickener powder to fully swell, and then heated and stirred, so that dissolution is quickly achieved, and the remaining water and other required components of the water required for the formulation are uniformly stirred during subsequent formulation. When the thickener is in powder form, the thickener is dissolved more quickly by adjusting the thickener powder to paste with a small amount of water-miscible organic solvent, then slowly adding the paste material to water under stirring, and heating to dissolve quickly. Such a water-miscible organic solvent is not particularly limited, and may be methanol, ethanol, acetone, glycerin, or the like.
The second technical problem to be solved by the invention is to provide the application of the fabric deodorant finishing liquid, which has the technical scheme that:
The application of the fabric deodorant finishing liquid in the photocatalysis deodorization finishing of fabrics.
The technical key of the invention is that the selection of the titanium dioxide photocatalyst in the fabric deodorant finishing liquid can reasonably select the method for finishing the fabric by adopting the deodorant finishing liquid, and those methods known to the person skilled in the art can reasonably select the method for loading the photocatalyst in the invention on the surface of the fabric through the fabric finishing process, so that the effect of comparable photocatalysis deodorization can be achieved, and the creative labor is not required.
As a non-limiting example of a fabric finishing process, for example, padding may be employed. If padding is adopted in the present invention, for example, the fabric may be padded with the fabric deodorant finishing liquid according to any one of the technical solutions of the above technical problems, and the deodorant fabric containing the photocatalyst of the present invention may be obtained when baking or after evaporation and heat treatment by other methods.
As a non-limiting example of a fabric finishing process, for example, an impregnation process may be employed. The present invention may be, for example, a deodorizing fabric containing the photocatalyst of the present invention obtained by immersing a fabric in the deodorizing agent finishing liquid for fabric according to any one of the above technical problems, dehydrating, drying, and baking.
As a non-limiting example of a fabric finishing process, a spray coating process may also be employed, for example. If the spraying method is adopted, for example, the fabric can be uniformly sprayed on the surface of the fabric by the fabric deodorant finishing liquid according to any one of the technical schemes of the technical problems, and then the fabric is dehydrated, dried and baked to obtain the deodorant fabric containing the photocatalyst.
And the like, and the loading methods known in the prior art can be flexibly combined for use.
By way of non-limiting example, the fabric deodorizing agent finishing liquid of the present invention may be applicable to the fabric materials, and may be cotton, acrylic, dacron, polypropylene, spandex, and other various materials. The fabric may be a textile, a knitwear, a nonwoven fabric, or the like.
Therefore, the third technical problem to be solved by the invention is to provide a manufacturing method of deodorizing fabric, which comprises the following steps:
a method of making a deodorizing fabric comprising:
(i) Contacting a raw material fabric with the fabric deodorant finishing liquid according to any one of the technical schemes of the technical problems to obtain a liquid-holding fabric a;
(ii) Drying to obtain a fabric b;
(iii) Baking to obtain deodorizing fabric.
In the above-mentioned technical scheme, the contact mode of the preferred step (i) is not particularly limited, and can be immersion contact, spray contact and roll contact.
In the above technical solution, the contact mode in the step (i) is impregnation contact, the contact time is not particularly limited, as long as the contact between the fabric deodorant finishing liquid and the fabric reaches or basically reaches balance, the contact time is prolonged without particularly affecting the technical effect, but the contact time is too long to cause the increase of the production time cost, and the contact time is too short to affect the load of the photocatalyst in a comparable way, based on the principle of the contact time, the person skilled in the art can comprehensively consider the factors to reasonably select the impregnation time, and can obtain the comparable technical effect without creative labor.
For example, but not limited to, a time of no less than 1 minute, further non-limiting examples of the time of impregnation may be 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 15 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, and the like. The impregnation times were 5 minutes in both the examples and comparative examples, which are merely comparable.
In the above technical solution, the liquid holdup in the liquid holdup fabric a of the step (i) is not particularly limited, and a person skilled in the art can reasonably control the liquid holdup according to the concentration of the fabric deodorant finishing liquid and the ability of the fabric to adsorb the finishing liquid, and whether to squeeze or not and the degree of squeezing after impregnation. For example, but not limited to, the liquid holdup in the liquid holdup fabric a is 70 to 100% by weight and relative to the raw fabric, more specific non-limiting examples of liquid holdups are 75%, 80%, 85%, 90%, 95% and the like. The liquid holdup of the liquid-holding fabric a in each of the examples and comparative examples was 90% by comparison only.
In the above technical solution, the temperature and time of drying in the step (ii) are not particularly limited, as long as a comparable technical effect can be obtained by removing part or all of the water in the liquid-holding fabric a. However, the person skilled in the art knows that the lower the temperature of drying, the more thoroughly the water needs to be removed, and that the longer the time needed for drying tends to be, and that the person skilled in the art is able to reasonably select the time and temperature for drying according to this principle without having to carry out the inventive task.
In the above-described embodiments, for example, but not limited to, the temperature of the drying in the step (ii) is 80 to 110 ℃, and more specific, non-limiting examples of the temperature of the drying in the step (ii) are 85 ℃, 90 ℃, 95 ℃,100 ℃, 105 ℃, and the like. The drying temperature in step (ii) in examples and comparative examples was 100℃for the same comparison only.
In the above technical solution, the drying time in the step (ii) is, for example, but not limited to, 4min or more, for example, but not limited to, 5min, 6min, 7min, 8min, 9min, 10min, 15min, 20min, 25min, 30min, 40min, 50min, 60min, etc. The drying time in step (ii) in examples and comparative examples was 5min, only in the same ratio.
In the above technical solution, the purpose of baking in step (iii) is to further remove the residual water introduced from the fabric deodorant finishing liquid in the fabric, and at the same time, the crosslinking agent added in the finishing liquid is crosslinked to fix the photocatalyst particles in the fabric, so that the baking temperature and baking time can be reasonably selected by a person skilled in the art.
In the above-mentioned embodiments, the baking temperature in the step (iii) is, for example, but not limited to, 120 to 160 ℃, and as a more specific non-limiting example, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃, 147 ℃, 148 ℃, 150 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃ and the like. The baking temperature in step (iii) in examples and comparative examples was 150℃by comparison only.
In the above technical scheme, for example, but not limited to, the baking time in the step (iii) is more than 1 min. As a more specific non-limiting example, the time for baking in step (iii) is 1.5min、2min、2.5min、3min、3.5min、4min、4.5min、5min、5.5min、6min、6.5min、7min、7.5min、8min、8.5min、9min、9.5min, and so on. The baking time of step (iii) in the examples and comparative examples was 3min, only by the same ratio.
The same materials and the same specifications are used in the examples and comparative examples.
In a specific embodiment of the present invention, the composition of the titanium oxide-based photocatalyst is measured by the ICP method.
The measurement of the photocatalytic deodorizing effect of the deodorizing fabric obtained after finishing with the textile deodorizing agent finishing liquid of the present invention was carried out according to the detection tube method in the standard JEC301-2013 formulated by the Japanese function textile evaluation Association (JAFET), the specification of the fabric sample specimen was 100cm 2, and the odor component used was ammonia gas in the laboratory atmosphere prescribed by the specimen. In the standard method, the photocatalytic deodorizing effect is represented by a V (%) value, and the calculation method is as follows:
V＝RL-RB
Where R L is a bright condition decrease rate (%), and R B is a dark condition decrease rate (%).
The present invention will be described in detail with reference to the following embodiments.
Detailed Description
[ Example 1]
1. Titanium dioxide-based photocatalyst preparation
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate solution II, wherein the solution contains Fe 2O3 3.0.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70℃for 24 hours and calcined at 500℃for 5 hours in an air atmosphere to give a titania-based photocatalyst in which the Fe 2O3 weight content was 3.0%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=41% as determined.
[ Example 2]
1. Titanium dioxide-based photocatalyst preparation
The procedure of example 1 was repeated except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to give the following:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate solution II, wherein the solution contains Fe 2O3 3.0.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70℃for 24 hours and calcined at 500℃for 5 hours in an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to obtain a titania-based photocatalyst in which Fe 2O3 weight content was 3.0%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=52% as determined.
[ Example 3]
1. Titanium dioxide-based photocatalyst preparation
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a zinc acetate solution II, wherein the solution contains ZnO 3.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air atmosphere to obtain a titania-based photocatalyst, wherein the ZnO content was 3.0% by weight.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=45% as determined.
[ Example 4]
1. Titanium dioxide-based photocatalyst preparation
The procedure of example 3 was repeated except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to give the following concrete:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a zinc acetate solution II, wherein the solution contains ZnO 3.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air ammonia gas mixture (ammonia gas volume content of 2.0%) to obtain a titania-based photocatalyst, wherein the ZnO weight content was 3.0%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=57% as determined.
[ Example 5]
1. Titanium dioxide-based photocatalyst preparation
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 1.5.5% and ZnO 1.5% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air atmosphere to obtain a titanium dioxide-based photocatalyst, wherein the content of Fe 2O3% by weight and the content of ZnO by weight were 1.5%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=74% as determined.
[ Example 6]
1. Titanium dioxide-based photocatalyst preparation
The procedure of example 5 was repeated except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to give the following concrete:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 1.5.5% and ZnO 1.5% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried at 70 ℃ for 24 hours, and is roasted at 500 ℃ for 5 hours in an air-ammonia gas mixture (ammonia gas volume content is 2.0%) to obtain the titanium dioxide-based photocatalyst, wherein the weight content of Fe 2O3 is 1.5% and the weight content of ZnO is 1.5%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=79% as determined.
[ Example 7]
1. Titanium dioxide-based photocatalyst preparation
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 1.0.0% and ZnO 2.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air atmosphere to obtain a titania-based photocatalyst, wherein the content of Fe 2O3 wt% was 1.0% and the content of ZnO was 2.0 wt%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=83% as determined.
[ Example 8]
1. Titanium dioxide-based photocatalyst preparation
The procedure of example 7 was repeated except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to give the following concrete:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 1.0.0% and ZnO 2.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried at 70 ℃ for 24 hours, and is roasted at 500 ℃ for 5 hours in an air-ammonia gas mixture (ammonia gas volume content is 2.0%) atmosphere, so that the titanium dioxide-based photocatalyst is obtained, wherein the Fe 2O3 weight content is 1.0% and the ZnO weight content is 2.0%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=89% as determined.
[ Example 9]
1. Titanium dioxide-based photocatalyst preparation
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 0.5.5% and ZnO 2.5% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air atmosphere to obtain a titania-based photocatalyst, wherein the content of Fe 2O3 wt% was 0.5% and the content of ZnO wt% was 2.5%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=81% as determined.
[ Example 10]
1. Titanium dioxide-based photocatalyst preparation
The procedure of example 9 was repeated except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%) to give the following:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate and zinc acetate mixed solution II, wherein the solution contains Fe 2O3 0.5.5% and ZnO 2.5% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried at 70 ℃ for 24 hours, and is roasted at 500 ℃ for 5 hours in an air-ammonia gas mixture (ammonia gas volume content is 2.0%) to obtain the titanium dioxide-based photocatalyst, wherein the weight content of Fe 2O3 is 0.5%, and the weight content of ZnO is 2.5%.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=85% as determined.
[ Comparative example 1]
1. Titanium dioxide-based photocatalyst preparation
The procedure was as in example 1, except that the solution II was not doped with metal ions, and specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Taking an acetic acid aqueous solution with the weight ratio of water to acetic acid being 1 as a solution II;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel was dried at 70 ℃ for 24 hours and calcined at 500 ℃ for 5 hours in an air atmosphere to obtain a titania-based photocatalyst.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=24% as determined.
[ Comparative example 2]
1. Titanium dioxide-based photocatalyst preparation
The procedure was as in comparative example 1, except that the firing atmosphere in step (4) was replaced with an air-ammonia gas mixture (ammonia gas volume content: 2.0%), and specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I which is equivalent to the n-butyl titanate with the weight concentration of 12.0 percent of titanium dioxide;
(2) Taking an acetic acid aqueous solution with the weight ratio of water to acetic acid being 1 as a solution II;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried at 70 ℃ for 24 hours, and is baked at 500 ℃ for 5 hours in the atmosphere of air ammonia gas mixture (ammonia gas volume content is 2.0%), so as to obtain the titanium dioxide-based photocatalyst.
Crushing and sieving with 600 mesh sieve to obtain 600 mesh titania base photocatalyst powder.
2. Fabric deodorant finishing liquid
The fabric deodorant finishing liquid comprises the following components in parts by weight:
Titanium dioxide-based photocatalyst (600 mesh), 10 parts;
10 parts of AEO 9;
sodium carboxymethylcellulose (740 Pa.s, 2% strength by weight aqueous solution, 25 ℃), 0.5 parts;
JYK FIX-DI,5 parts;
250 parts of water.
The preparation method comprises the following steps:
Placing 250 parts of water into a blending kettle, scattering powdery sodium carboxymethylcellulose on the water surface at the ambient temperature without stirring, standing overnight to enable the sodium carboxymethylcellulose to fully absorb water and swell, starting stirring, heating and dissolving at 60 ℃, and then cooling to room temperature; then adding titanium dioxide-based photocatalyst, AEO9 and JYK FIX-DI, and stirring uniformly.
3. Manufacturing of deodorizing fabrics
Soaking the raw material fabric in the fabric deodorant finishing liquid for 5min, extruding redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min.
The raw material fabric is pure cotton woven fabric, warp density: 133 roots/10 cm, weft density: 100 roots/10 cm, width 58cm, gram weight: 125g/m 2.
4. Determination of photocatalytic deodorizing Effect
The sample of the fabric was 100cm 2 in size according to the tube test method in JEC301-2013, a standard established by the Japanese society for evaluating textiles (JAFET), and the odor component used was ammonia gas in a laboratory atmosphere defined by the sample. V=31% as determined.

Claims (16)

1. The fabric deodorant finishing liquid comprises the following components in parts by weight:
10 parts of titanium dioxide-based photocatalyst;
5-20 parts of a surfactant;
0.2-1 parts of a thickener;
1-10 parts of a cross-linking agent;
100-1000 parts of water;
The titanium dioxide-based photocatalyst comprises titanium dioxide and doped metal elements, wherein the doped metal elements comprise zinc and iron at the same time, the zinc is calculated by ZnO, the iron is calculated by Fe2O3, and the weight ratio of the ZnO to the Fe2O3 is 2-5.
2. The fabric deodorant finishing liquid according to claim 1, wherein the photocatalyst is 200-3000 mesh.
3. The fabric deodorant finish of claim 1 wherein the surfactant is a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant.
4. The fabric deodorant finish of claim 3 wherein the nonionic surfactant is a fatty alcohol polyoxyethylene ether or tween.
5. The fabric deodorant finish of claim 1 wherein the thickener is sodium carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, polyacrylamide, sodium polyacrylate, maleic anhydride acrylic acid copolymer or polyurethane associative thickener.
6. The fabric deodorant finish of claim 1 wherein the cross-linking agent is a thermally cross-linking agent.
7. The fabric deodorant finishing liquid of claim 6, wherein the crosslinking agent is a polyurethane crosslinking agent, an amide-formaldehyde crosslinking agent, a urea-formaldehyde crosslinking agent or a polycarboxylic acid crosslinking agent.
8. The fabric deodorant finish of claim 7 wherein the polycarboxylic acid cross-linking agent is a polyacrylic acid cross-linking agent.
9. The use of the fabric deodorant finishing liquid according to any one of claims 1 to 8 in the photocatalytic deodorizing finishing of fabrics.
10. A method of making a photocatalytic deodorizing fabric comprising:
(i) Contacting the raw fabric with the fabric deodorant finishing liquid according to any one of claims 1-8 to obtain a liquid-holding fabric a;
(ii) Drying to obtain a fabric b;
(iii) Baking to obtain deodorizing fabric.
11. The method of claim 10, wherein the material of the raw fabric in step (i) is cotton, acrylic, dacron, polypropylene or spandex, and the raw fabric is in the form of a textile or nonwoven fabric.
12. The method of manufacturing according to claim 11, characterized in that the textile is a knitwear.
13. The method according to claim 10, wherein the liquid holding capacity of the liquid holding fabric a in the step (i) is 70 to 100% by weight and based on the raw fabric.
14. The method according to claim 10, wherein the drying temperature in step (ii) is 80 to 110 ℃ and/or the drying time in step (ii) is 4min or longer.
15. The method according to claim 10, wherein the baking temperature in step (iii) is 120-160 ℃.
16. The method according to claim 10, wherein the baking time in the step (iii) is 1min or longer.
CN202210933176.7A 2022-08-04 2022-08-04 Fabric deodorant finishing liquid, application thereof and manufacturing method of photocatalysis deodorant fabric Active CN115074992B (en)

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