KR102297882B1 - Antimicrobial deodorant fiber with excellent washing fastness, and manufacturing method thereof - Google Patents

Abstract

The present invention comprises the steps of a) preparing a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite including porous inorganic nanoparticles, and an antibacterial and deodorizing composition for dyeing comprising a water-dispersed polyurethane prepolymer; And b) dyeing by immersing the fabric material in the antibacterial and deodorizing composition for dyeing; it relates to a method for producing an antibacterial and deodorizing fiber comprising a, and an antibacterial and deodorizing fiber prepared therefrom.

Description

Antimicrobial deodorant fiber with excellent washing fastness, and manufacturing method thereof

The present invention relates to an antibacterial and deodorizing fiber having excellent washing fastness and a method for manufacturing the same.

Since the fiber is in direct contact with the sweat of the human body, it may cause an unpleasant odor problem due to the generation of a large amount of ammonia, and microorganisms harmful to the human body may attach to the textile product and cause various diseases.

In order to prevent discoloration and embrittlement of textile products from harmful microorganisms or contamination from various odors, antibacterial and antifungal deodorizing processing is performed to suppress the inhabitation or propagation of microorganisms such as bacteria or mold in textile products. .

As an antibacterial and deodorizing method, a method of applying an inorganic compound such as silver, copper, zinc, silver oxide and zinc oxide or applying an organic compound such as benzyl chloride is commonly known. However, sanitary processing agents made of such antibacterial compounds have a problem in that they cannot be organically adhered to the fibers and durability due to washing.

As a similar prior document for this, Korean Patent Registration No. 10-1577403 has been proposed.

Republic of Korea Patent Publication No. 10-1577403 (2015.12.08)

In order to solve the above problems, an object of the present invention is to provide an antibacterial and deodorizing fiber that can maintain antibacterial and deodorizing properties for a long time by having excellent washing fastness while having excellent antibacterial and deodorizing properties, and a method for manufacturing the same.

One aspect of the present invention for achieving the above object is a) a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and an antibacterial deodorant for dyeing containing a water-dispersed polyurethane prepolymer preparing a sex composition; And b) dyeing by immersing the fabric material in the antibacterial and deodorizing composition for dyeing;

In one aspect, the polyethyleneimine may have a weight average molecular weight of 600 to 1,500 g/mol.

In one aspect, the antibacterial and deodorizing composition for dyeing is 1 to 5 parts by weight of zinc pyrithione, 3 to 15 parts by weight of polyethyleneimine, 10 to 50 parts by weight of urea, 5 inorganic nanocomposites based on 100 parts by weight of the dye composition to 15 parts by weight, and 10 to 30 parts by weight of the water-dispersed polyurethane prepolymer. In this case, the weight ratio of the zinc pyrithione: polyethyleneimine: urea may be 1: 1.5 to 3: 5 to 10.

In one aspect, the average particle size of the inorganic nanocomposite may be an average particle size of 100 to 300 nm.

In one aspect, the inorganic nanocomposite may be one in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles.

In one aspect, the manufacturing method is, c) spraying a composition containing zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles and a water-dispersed polyurethane prepolymer on the dyed fiber step; may further include.

In addition, another aspect of the present invention is a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and an antibacterial and deodorizing composition for dyeing containing a water-dispersed polyurethane prepolymer. It relates to antibacterial and deodorizing fibers.

In another aspect, the antibacterial and deodorant composition for dyeing is 1 to 5 parts by weight of zinc pyrithione, 3 to 15 parts by weight of polyethyleneimine, 10 to 50 parts by weight of urea, inorganic nanocomposite based on 100 parts by weight of the dye composition. 5 to 15 parts by weight, and 10 to 30 parts by weight of the water-dispersed polyurethane prepolymer may be included.

The method for producing an antibacterial and deodorizing fiber according to the present invention is a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and an antibacterial and deodorizing composition for dyeing comprising a water-dispersed polyurethane prepolymer By using it, it is possible to manufacture antibacterial and deodorizing fibers with excellent antibacterial properties, deodorization properties and washing fastness.

In addition, as the textile fabric is dyed with the antibacterial and deodorant composition for dyeing, antibacterial and deodorizing treatment can be performed during dyeing without performing other additional processes, thereby simplifying the process.

1 is an antimicrobial test result for strain 1 of the antibacterial and deodorizing fiber prepared in Example 1.
2 is an antimicrobial test result for strain 2 of the antibacterial and deodorizing fiber prepared in Example 1.
3 is an antimicrobial test result for strain 1 after washing the antibacterial and deodorant fiber prepared in Example 1 50 times.

Hereinafter, an antibacterial and deodorizing fiber excellent in washing fastness and a manufacturing method thereof according to the present invention will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

One aspect of the present invention is a) dye composition, zinc pyrithione, polyethyleneimine, urea, preparing an antibacterial and deodorizing composition for dyeing comprising an inorganic nanocomposite and water-dispersed polyurethane prepolymer comprising porous inorganic nanoparticles ; And b) dyeing by immersing the fabric material in the antibacterial and deodorizing composition for dyeing;

As such, the method for manufacturing the antibacterial deodorant fiber according to the present invention is an antibacterial deodorant for dyeing containing a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and a water-dispersed polyurethane prepolymer By using the sex composition, it is possible to manufacture an antibacterial and deodorizing fiber having excellent antibacterial properties, deodorization properties and washing fastness.

In addition, as the textile fabric is dyed with the antibacterial and deodorant composition for dyeing, antibacterial and deodorizing treatment can be performed during dyeing without performing other additional processes, thereby simplifying the process.

Hereinafter, each step of the method for manufacturing an antibacterial and deodorizing fiber according to an example of the present invention will be described in more detail.

First, a) a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles and a water-dispersed polyurethane prepolymer for preparing an antibacterial and deodorizing composition for dyeing can be performed have.

In one embodiment of the present invention, the dye composition may be selected differently depending on the type of fabric to be dyed and a dyeing method, and may be a dye composition generally used in the art. For example, when the fabric material is cotton, the dye composition may be a reactive dye composition, a reducing dye composition, a sulfur dye composition, a direct dye composition, or an azo dye composition, and the dyeing method using the same may follow a conventional method. have.

In one embodiment of the present invention, the zinc pyrithione is a component for imparting antibacterial and antibacterial performance, and the zinc pyrithione may be added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the dye composition. In this range, excellent antibacterial properties can be imparted without affecting color development and dye adhesion. On the other hand, when zinc pyrithione is added in an amount of less than 1 part by weight, antibacterial properties may be reduced, and when zinc pyrithione is added in an amount of more than 5 parts by weight, dyeing properties may be deteriorated.

In one embodiment of the present invention, the polyethyleneimine is to help solubilize zinc pyrithione so that it can be absorbed well into the fiber dough, and the polyethyleneimine is added in an amount of 3 to 15 parts by weight based on 100 parts by weight of the dye composition. can be In this range, zinc pyrithione can be effectively dissolved. On the other hand, if the content of polyethylenimine is too small compared to zinc pyrithione, zinc pyrithione may not be completely dissolved and zinc pyrithione may not adhere well to the fiber. In this case, zinc pyrithione may be lost after washing. can Conversely, when polyethyleneimine is added in an amount of more than 15 parts by weight, the dyeing properties may be deteriorated.

Preferably, the polyethyleneimine may have a weight average molecular weight of 600 to 1,500 g/mol. It is possible to dissolve zinc pyrithione well by using such a low molecular weight polyethyleneimine. On the other hand, when the weight average molecular weight exceeds 1,500 g/mol, solubility gradually decreases, and when the weight average molecular weight exceeds 2,500 g/mol, zinc pyrithione may hardly be dissolved.

In one embodiment of the present invention, the urea is for zinc pyrithione dissolved by polyethyleneimine and permeated into the fiber to be well deposited on the fiber during the drying process, and the urea is based on 100 parts by weight of the dye composition. 10 to 50 parts by weight may be added. In this range, zinc pyrithione is effectively deposited, so that zinc pyrithione can remain solid even after 50 or more washings. On the other hand, if the content of urea compared to zinc pyrithione is too small, zinc pyrithione may not be well deposited on the fiber, and in this case, zinc pyrithione may be lost even after washing less than 50 times. Conversely, when urea is added in more than 50 parts by weight, the dyeing properties may be deteriorated.

Particularly preferably, it is good to control the content of zinc pyrithione, polyethyleneimine and urea in an appropriate ratio to improve solubility and depositability of zinc pyrithione. Specifically, the weight ratio of zinc pyrithione:polyethyleneimine:urea may be 1:1.5 to 3:5-10. In this range, zinc pyrithione is well dissolved by polyethyleneimine and can be absorbed into the fiber well, and it is well deposited on the fiber by urea during the subsequent drying process, so that it is hardly lost even after washing more than 50 times, so it can maintain excellent antibacterial properties. have.

In one embodiment of the present invention, the inorganic nanocomposite including the porous inorganic nanoparticles is for imparting deodorizing and deodorizing properties to the fibers, and inorganic nanoparticles having porosity can be used without particular limitation, and as a specific example, It may be any one or two or more selected from the group consisting of diatomaceous earth, zeolite and activated carbon. Such porous inorganic nanoparticles may be prepared by wet grinding the porous inorganic particles to have an average particle size of 100 to 300 nm. As such, by having an average particle size of 100 to 300 nm, it is possible to prevent deterioration of the dyeing properties of the dyed antibacterial and deodorizing fibers.

To this end, the step of wet grinding the porous inorganic particles to an average particle size of 100 to 300 nm may be additionally performed, and the wet grinding method is not particularly limited, but a method such as wet bead milling may be used. As a specific example, speed mill equipment using beads having a particle size of 0.5 to 3 mm, nanoset mill equipment using beads having a particle size of 0.1 to 0.5 mm, or twin nanoset mill equipment using beads having a particle size of 0.03 to 0.5 mm may be used. have.

The inorganic nanocomposite including the porous inorganic nanoparticles may be added in an amount of 5 to 15 parts by weight based on 100 parts by weight of the dye composition. While effective in improving the deodorizing properties in this range, it may not reduce the dyeing properties. On the other hand, when the porous inorganic nanoparticles are added in an amount of less than 5 parts by weight, the deodorizing properties may be greatly reduced, and when the porous inorganic nanoparticles are added in an amount of more than 50 parts by weight, the adhesive properties of the water-dispersed polyurethane prepolymer are lowered, so that the washing fastness is reduced. may be lowered.

More preferably, the inorganic nanocomposite including the porous inorganic nanoparticles may be one in which zinc oxide nanoparticles are supported on the porous inorganic nanoparticles. As such, by using the inorganic nanocomposite in which zinc oxide nanoparticles are supported together with the porous inorganic nanoparticles, deodorizing properties can be imparted, and the antibacterial properties of the fibers can be further improved.

The inorganic nanocomposite in which the zinc oxide nanoparticles are supported on the porous inorganic nanoparticles is prepared from a manufacturing method comprising a; can be

In this case, the porous inorganic nanoparticles can be used without particular limitation as long as they have porosity and excellent deodorization performance and can support zinc oxide nanoparticles, but may preferably be diatomaceous earth, and an average particle size of 100 through wet grinding to 300 nm in size.

When the porous inorganic nanoparticles are prepared, the inorganic nanocomposite can be prepared by supporting the zinc oxide nanoparticles on the porous inorganic nanoparticles through a solvothermal synthesis reaction.

Usually, zinc oxide particles exist in the form of micron-sized secondary particles in which primary particles are aggregated. In this case, antibacterial activity is reduced due to aggregation, whereas the inorganic nanocomposite according to the present invention uses porous inorganic nanoparticles, and solvate heat By synthesizing zinc oxide through a synthesis reaction, aggregation of primary particles can be suppressed, thereby greatly improving antibacterial and antibacterial properties.

As a more specific example, in step a), i) a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent, and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent. preparing each; ii) preparing a reaction mixture by putting the first reaction solution and the second reaction solution in an ultrasonic stirrer and mixing them under an ice bath; iii) preparing an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles by applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor; and iv) calcining the inorganic nanocomposite.

First, the steps of i) preparing a first reaction solution obtained by adding porous inorganic nanoparticles and sodium hydroxide to a first alcohol solvent and a second reaction solution obtained by dissolving zinc chloride in a second alcohol solvent may be performed, respectively.

The concentration and ratio of each component can be important to perform well in a solvothermal synthesis reaction. As a specific example, the concentration of sodium hydroxide in the first reaction solution may be 0.1 to 2 M, more preferably 0.3 to 1 M, and the concentration of zinc chloride in the second reaction solution may be 0.01 to 0.5 M. and, more preferably, it may be 0.05 to 0.2 M, and the molar ratio of zinc chloride to sodium hydroxide may be 1: 7 to 13, and more preferably 1: 9 to 11. In such a concentration and molar ratio range, zinc oxide nanoparticles can be effectively prepared in the future.

In addition, the content of the porous inorganic nanoparticles added to the first reaction solution is also important. As a specific example, in the first reaction solution, 300 to 700 mg of the porous inorganic nanoparticles can be added to 1 mmol of zinc chloride, More preferably, 400 to 600 mg may be added. In this range, zinc oxide nanoparticles are not easily agglomerated and can be well dispersed and supported on porous inorganic nanoparticles, and since the surface of porous inorganic nanoparticles is not completely coated with zinc oxide nanoparticles, it has an adsorption effect on gases, etc. Deodorization performance can be secured. On the other hand, if the porous inorganic nanoparticles are added in too small a quantity, the surface may be completely coated with zinc oxide nanoparticles, and the open pores may be changed into completely closed pores, which may result in deterioration of the deodorization performance. can Conversely, if the porous inorganic nanoparticles are added in too much, an excessive amount of the inorganic nanocomposite should be mixed with the base resin in order to secure a similar level of antibacterial activity. Poor physical properties may deteriorate the washing fastness.

In this case, the first alcohol solvent and the second alcohol solvent may be independently of each other, such as methanol, ethanol or ethylene glycol, but preferably methanol. By using methanol, zinc oxide nanoparticles having a spherical shape with a size of 20 to 30 nm can be effectively prepared.

Next, the step of ii) putting the first reaction solution and the second reaction solution into an ultrasonic stirrer and mixing them under an ice bath to prepare a reaction mixture may be performed. Since heat may be generated when the first reaction solution and the second reaction solution are mixed, it is recommended to mix for 30 minutes or more, specifically for 1 to 3 hours under an ice bath, through which zinc hydroxide (Zn hydroxide (Zn (OH) ₂ ) It is possible to prepare an inorganic nanocomposite precursor on which nanoparticles are supported.

_{In this way, zinc hydroxide (Zn(OH) 2} ) nanoparticles synthesized by vigorously mixing the first and second reaction solutions through ultrasonic treatment are effectively prevented from agglomeration with each other while being well dispersed in the primary particle level. Zinc particles can be effectively supported and adsorbed on the porous inorganic nanoparticles. In this case, the ultrasonic treatment may be performed at a frequency of 1 kHz to 200 MHz to apply energy of 1 W to 200 kW.

Next, iii) applying a temperature of 80 to 150° C. to the reaction mixture and reacting it in a high-pressure reactor to prepare an inorganic nanocomposite in which zinc oxide nanoparticles are supported on porous inorganic nanoparticles may be performed.

In this step, the zinc hydroxide (Zn(OH) ₂ ) nanoparticles prepared in the previous step are oxidized to zinc oxide (ZnO) nanoparticles of the inorganic nanocomposite precursor loaded with zinc oxide (Zn(OH) _{2 ) nanoparticles.} As a step, zinc oxide (ZnO) nanoparticles can be effectively prepared by applying a temperature of 80 to 150° C. and performing a solvothermal synthesis reaction in a high-pressure reactor.

The reaction time is not particularly limited, but it is preferable to carry out for 6 hours or more, specifically, 12 to 24 hours, since most of the zinc oxide (Zn(OH) ₂ ) nanoparticles can be converted into zinc oxide (ZnO) nanoparticles.

Thereafter, of course, the process of removing excess sodium hydroxide and product sodium chloride and drying may be further performed.

Next, the step of iv) calcining the inorganic nanocomposite may be performed.

Through this step, zinc oxide (ZnO) can be firmly bound to the porous inorganic nanoparticles, and zinc oxide can be prevented from desorbing from the porous inorganic nanoparticles well even during washing.

As a preferred example, the sintering temperature may be 400 to 600 °C. In this range, the zinc oxide nanoparticles can be well bound to the porous inorganic nanoparticles. In this case, the calcination time is preferably 1 hour or more, and may be specifically carried out for 2 to 6 hours.

On the other hand, in an example of the present invention, the water-dispersed polyurethane prepolymer is for the inorganic nanocomposite containing the porous inorganic nanoparticles to be well bound to the fiber, and the water-dispersed polyurethane prepolymer is included in 100 parts by weight of the dye composition. It may be added in an amount of 10 to 30 parts by weight. In this range, the inorganic nanocomposite can be well bound to the fiber so that it is not easily detached from the fiber even after washing.

As a more specific example, the water-dispersed polyurethane prepolymer is polymerized from a reaction composition including a polyether polyol having a weight average molecular weight of 1,000 to 3,000 g/mol, a diol compound, and a diisocyanate compound, and the reaction composition is NCO/OH The equivalent ratio of may be 1.2 to 1.8.

The polyether polyol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers or block copolymers of ethylene oxide and propylene oxide, random copolymers or block copolymers of ethylene oxide and butylene oxide, etc. It may be any one or two or more selected from the group consisting of, the diol compound is 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol And it may be any one or two or more selected from the group consisting of dipropylene glycol and the like. In this case, the molar ratio of the polyether polyol: the diol compound may be 1:1 to 2.5, more preferably 1:1.3 to 2. In this range, the adhesive property may be excellent.

The diisocyanate compound may be used without particular limitation as long as it is commonly used in the art, and preferably 2,4-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), It may be any one or two or more selected from the group consisting of hexamethylene diisocyanate (HDI) and methylene bis(p-cyclohexyl isocyanate) (H12MDI)).

In addition, the reaction composition may further include 2,2-bis(hydroxymethyl)propionic acid (DMPA) as an emulsifier, and may further include dibutyltin dilaurate (DBTDL) as a catalyst, can be added at a conventional level.

On the other hand, the antibacterial deodorant composition for dyeing may further include a polyether polyol having a weight average molecular weight of 1,000 to 3,000 g/mol as a chain extender, and the polyether polyol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol , may be any one or two or more selected from the group consisting of random copolymers or block copolymers of ethylene oxide and propylene oxide and random copolymers or block copolymers of ethylene oxide and butylene oxide, and the water dispersion It may be added in an amount of 80 to 120 parts by weight based on 100 parts by weight of the polyurethane prepolymer.

In addition, the antibacterial and deodorizing composition for dyeing may further include a curing agent for accelerating the reaction of the water-dispersible polyurethane prepolymer and the chain extender. At this time, the curing agent may be used without particular limitation as long as it is commonly used in the art, and as a specific example, a group consisting of triethylamine, dimethylcyclohexylamine, bis(dimethyl aminoether) and tris(dimethyl aminopropylamine), etc. It may be any one or two or more amine-based curing agents selected from. The amount of the curing agent to be added is not particularly limited, but may be added, for example, in an amount of 1 to 5 parts by weight based on 100 parts by weight of the water-dispersed polyurethane prepolymer. In such a range, the polymerization reaction may occur effectively and the curing rate may be adequate, so that workability may be excellent.

When the antibacterial and deodorant composition for dyeing is prepared as described above, the step of dyeing by immersing the fabric dough in the antibacterial and deodorizing composition for dyeing may be performed.

In this case, the dye method may be selected differently depending on the type of fabric material and the type of the dye composition, and detailed description will be omitted as it may be performed by a method commonly used in the art. Preferably, the fiber material may be cotton, polyester, nylon or rayon. It is good that the use of such a fiber material can better deposit zinc pyrithione on the fiber.

In addition, the manufacturing method of the antibacterial deodorant fiber according to the present invention can perform heat treatment such as hot air drying, ultraviolet drying, steam heat, dry heat, etc. in order to fix the dye after padding the fiber dough in the antibacterial and deodorizing composition for dyeing, at this time At the same time as the dye is fixed, zinc pyrithione permeated into the fabric can be deposited on the fabric. For this purpose, the heat treatment is preferably performed at 60° C. or higher, and preferably at 80 to 100° C. In this range, dye fixing and zinc pyrithione deposition can occur effectively without damaging the fibers.

In addition, the method for producing an antibacterial and deodorizing fiber according to an embodiment of the present invention, c) an inorganic nanocomposite containing zinc pyrithione, polyethyleneimine, urea, and porous inorganic nanoparticles in the dyed fiber and water-dispersed polyurethane prepolymer It may further include; spraying a composition comprising a. At this time, since each component is the same as described above, a redundant description is omitted, and a solvent such as water may be further added for easy spraying, and the content of the solvent is sufficient enough to facilitate spraying.

On the other hand, another aspect of the present invention is a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and an antibacterial and deodorizing composition for dyeing containing a water-dispersed polyurethane prepolymer. It relates to an antibacterial and deodorizing fiber, and as the antibacterial and deodorizing composition for dyeing is the same as described above, a duplicate description will be omitted.

Hereinafter, an antibacterial and deodorizing fiber excellent in washing fastness and a manufacturing method thereof according to the present invention will be described in more detail through examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

[Production Example 1]

35 mol% of polytetramethylene glycol having a weight average molecular weight of 1,800 g/mol, 30 mol% of 1,3-propanediol, 25 mol% of 1,4-butanediol and 2,2-bis(hydroxymethyl)propionic acid ( DMPA) 10 mol% was prepared.

0.03 parts by weight of dibutyltin dilaurate (DBTDL) was added based on 100 parts by weight of the mixture, and stirred for 30 minutes at 80° C. and under a nitrogen atmosphere, and then hexamethylene diisocyanate (HDI) so that the equivalent ratio of NCO/OH was 1.6 was added and synthesized at 80° C. for 300 minutes to prepare an aqueous dispersion polyurethane prepolymer.

[Production Example 2]

Diatomaceous earth nanoparticles having an average particle size of 100 nm were obtained by wet grinding diatomaceous earth using a nanoset mill (model name TNS010) equipment.

[Production Example 3]

Diatomaceous earth nanoparticles having an average particle size of 100 nm were obtained by wet grinding diatomaceous earth using a nanoset mill (model name TNS010) equipment.

Next, an inorganic nanocomposite in which zinc oxide (ZnO) nanoparticles were supported on diatomaceous earth nanoparticles was prepared through the following solvothermal synthesis reaction.

First, sodium hydroxide was dissolved in 20 ml of methanol to prepare a 0.5 M sodium hydroxide solution, and 500 mg of diatomaceous earth nanoparticles were added to prepare a first reaction solution. At the same time, zinc chloride (ZnCl ₂ ) was dissolved in 10 ml of methanol to prepare a 0.1 M zinc chloride solution, which was prepared as a second reaction solution.

Under an ice bath, the first reaction solution and the second reaction solution were put into an ultrasonic reactor, and then ultrasonically stirred vigorously for 1 hour. Thereafter, the reaction mixture was put into a high-pressure reactor, and the temperature was raised to 120° C. and reacted for 12 hours. Thereafter, the resulting precipitate was filtered and washed with methanol to obtain an inorganic nanocomposite in which zinc oxide nanoparticles were supported on diatomaceous earth nanoparticles.

The inorganic nanocomposite was placed in a rotary kiln and calcined at 500° C. for 6 hours.

[Example 1]

C.I. After dissolving 10 g of reactive blue 19 dye and 10 g of urea in 100 ml of water to prepare a dye solution, and dissolving 70 mg of sodium silicate and 20 mg of sodium hydroxide in 390 ml of water to make an alkali solution, the dye solution: A dye composition was prepared by mixing an alkali solution in a volume ratio of 80:20.

Next, with respect to 100 parts by weight of the dye composition, 3 parts by weight of zinc pyrithione (ZPT), 6 parts by weight of polyethyleneimine (PEI, weight average molecular weight 800 g/mol), 20 parts by weight of urea, prepared in Preparation Example 2 8 parts by weight of the prepared diatomaceous earth nanoparticles, 20 parts by weight of the water-dispersed polyurethane prepolymer prepared in Preparation Example 1, 20 parts by weight of polytetramethylene glycol having a weight average molecular weight of 1,800 g/mol, and 0.5 parts by weight of triethylamine for dyeing An antibacterial deodorant composition was prepared, and the cotton dough was dyed through a conventional cold pad batch method, and dried with hot air at 80° C. for 2 hours to prepare an antibacterial deodorant fiber.

[Examples 2 to 19, Comparative Examples 1 to 9]

All processes were carried out in the same manner as in Example 1 except that the content (parts by weight) of each component of the antibacterial deodorant composition for dyeing was mixed as described in Table 1 above.

[Examples 20 to 22]

All processes were performed in the same manner as in Example 1 except that the weight average molecular weight (Mw, g/mol) of polyethyleneimine was changed as described in Table 1 above.

[Example 23]

All processes were performed in the same manner as in Example 1 except that 8 parts by weight of the inorganic nanocomposite prepared in Preparation Example 3 was used instead of the diatomaceous earth nanoparticles prepared in Preparation Example 2.

Antibacterial and deodorizing composition for dyeing (parts by weight) dye composition ZPT PEI
(Mw) Element diatomaceous earth PU prepolymer Example 1 100 3 6 20 8 20 Example 2 100 0.1 6 20 8 20 Example 3 One Example 4 5 Example 5 10 Example 6 100 3 3 20 8 20 Example 7 9 Example 8 30 Example 9 100 3 6 5 8 20 Example 10 15 Example 11 50 Example 12 100 3 6 20 One 20 Example 13 5 Example 14 15 Example 15 30 Example 16 100 3 6 20 8 3 Example 17 10 Example 18 30 Example 19 100 Example 20 100 3 6
(600) 20 8 20 Example 21 6
(1,500) Example 22 6
(2,500) Example 23 100 3 6 20 Inorganic Nanocomposite 8 20 Comparative Example 1 100 - - - - - Comparative Example 2 - - - 8 20 Comparative Example 3 3 6 20 - - Comparative Example 4 3 - - 8 20 Comparative Example 5 100 - 6 20 8 20 Comparative Example 6 3 - 20 8 20 Comparative Example 7 3 6 - 8 20 Comparative Example 8 3 6 20 - 20 Comparative Example 9 3 6 20 8 -

[Characteristic evaluation method]

1) Antibacterial performance test: The antibacterial property was tested by the method of KS K 0693:2016.

Specifically, Staphylococos aureus ATCC 6538, strain 1) 2.1×10 ⁴ CFU/ml and Klebsiella pneumoniae AATCC 4352, Strain 2) 2.2×10 ⁴ CFU/ml was inoculated at the initial concentration (A _{0 , CFU/ml), and the concentration (A 1} , CFU/ml) was checked after leaving it at 37.0 ± 0.2 ° C for 18 hours, The bacteriostatic reduction rate (%) was calculated therefrom, and the results are shown in Table 2 below. As a control, an unstained fibrous material was prepared. In addition, the bacteriostatic reduction rate was _{calculated as (A 0} -A ₁ )/A ₀ ×100.

2) Deodorization performance test: The deodorization performance was tested according to the FITI test guideline FTM-5-2:2004.

In detail, each of the antibacterial and deodorizing fibers prepared in Examples 1 to 22 and Comparative Examples 1 to 9 was cut into 10 cm × 10 cm to prepare a test piece, and after inserting it into an ammonia gas test gas pack having an initial concentration of 100 ppm, gas The deodorization rate (%) was measured using a detector tube method (KICM-FIR-1004), and the results are shown in Table 2 below. At this time _{, the deodorization rate was calculated as (C b} -C _s )/C _b × 100, where C _b is the concentration of ammonia gas remaining in the test gas pack after 2 hours without the antibacterial and deodorizing fiber test piece (blank) (ppm) and C _s is the concentration (ppm) of ammonia gas remaining in the test gas pack after 2 hours of putting the antibacterial and deodorizing fiber test piece.

3) Washing fastness: After washing 50 times according to KS K ISO 6330: 2011, 8B method and drying it once on a clothesline, antibacterial and deodorizing performance were tested.

bacteriostatic reduction rate (%) deodorization rate
(%) strain 1 strain 2 before washing After 50 washes before washing After 50 washes before washing After 50 washes initial concentration 2.1×10 ⁴ 2.2×10 ⁴ 2.2×10 ⁴ 2.2×10 ⁴ - control 1.2×10 ⁷ 1.1×10 ⁷ 4.2×10 ⁷ 3.8×10 ⁷ Example 1 99.9 99.9 99.9 99.9 85.6 84.4 Example 2 82.7 79.6 85.4 84.1 84.9 82.6 Example 3 99.9 99.9 99.9 99.9 84.6 83.1 Example 4 99.9 99.9 99.9 99.9 84.4 82.9 Example 5 99.9 99.9 99.9 99.9 85.1 84.2 Example 6 85.1 83.4 90.1 87.2 84.9 82.9 Example 7 99.9 99.9 99.9 99.9 85.0 84.1 Example 8 99.9 99.9 99.9 99.9 84.2 82.8 Example 9 77.5 75.9 82.4 79.8 83.7 82.8 Example 10 99.9 99.9 99.9 99.9 84.9 83.8 Example 11 99.9 99.9 99.9 99.9 85.2 84.2 Example 12 99.9 99.9 99.9 99.9 72.8 70.9 Example 13 99.9 99.9 99.9 99.9 81.6 80.9 Example 14 99.9 99.9 99.9 99.9 89.3 83.4 Example 15 99.9 99.9 99.9 99.9 75.4 52.6 Example 16 99.9 99.9 99.9 99.9 67.1 46.3 Example 17 99.9 99.9 99.9 99.9 84.5 80.1 Example 18 99.9 99.9 99.9 99.9 85.3 84.9 Example 19 99.9 99.9 99.9 99.9 82.6 80.9 Example 20 99.9 99.9 99.9 99.9 83.6 83.0 Example 21 99.9 99.9 99.9 99.9 84.0 83.2 Example 22 82.2 80.4 80.9 79.6 84.2 83.4 Example 23 99.9 99.9 99.9 99.9 88.1 85.4 Comparative Example 1 (Increase in the number of bacteria) (Increase in the number of bacteria) (Increase in the number of bacteria) (Increase in the number of bacteria) 31.2 33.4 Comparative Example 2 62.1 57.2 64.3 55.9 85.7 80.8 Comparative Example 3 99.9 99.9 99.9 99.9 43.9 41.3 Comparative Example 4 81.6 72.5 81.3 70.7 84.4 84.5 Comparative Example 5 65.3 64.6 68.9 66.8 86.6 85.2 Comparative Example 6 89.6 73.6 93.2 68.3 85.1 82.9 Comparative Example 7 93.6 69.2 97.9 75.1 82.9 83.1 Comparative Example 8 99.9 99.9 99.9 99.9 35.4 32.6 Comparative Example 9 99.9 99.9 99.9 99.9 52.9 30.4

As shown in Table 2 above, when the fabric fabric is dyed using the antibacterial and deodorizing composition for dyeing prepared according to the present invention, not only excellent antibacterial and deodorizing properties but also excellent antibacterial and deodorizing properties are maintained even after washing 50 times. It was confirmed that the wash fastness was very good.

However, in the case of Example 2, the content of zinc pyrithione was small, so the antibacterial property was somewhat inferior, and in Example 6, the content of polyethylenimine was small, so zinc pyrithione was not completely dissolved, and in Example 9, the content of urea was small. As the content of zinc pyrithione bound to each fiber is decreased, it is judged that the antibacterial properties are also somewhat lowered.

In the case of Example 12, the content of porous inorganic nanoparticles was low, and the deodorization rate was not good. In Example 15, the content of porous inorganic nanoparticles compared to the water-dispersed polyurethane prepolymer was high, and Example 16 was water-dispersed polyurethane compared to the inorganic nanocomposite. Since the content of the prepolymer was too small, the washing fastness was rather poor as the adhesive properties were deteriorated.

In the case of Example 22, zinc pyrithione did not dissolve well due to the use of polyethyleneimine having a high molecular weight, and the content of zinc pyrithione binding to the fiber was decreased, so that the antibacterial property was also somewhat lowered.

In addition, in the case of Examples 5, 8, 11 and 19, antibacterial properties, deodorization properties, and washing fastness were all excellent, but the color development characteristics were not good during dyeing.

On the other hand, in the case of Comparative Example 1, only a simple dyeing process was performed, and there was no antibacterial property, and the deodorization property was greatly deteriorated. In Comparative Examples 3 and 8 in which no particles were added, the deodorization properties were greatly reduced.

In Comparative Examples 4, 6 and 7, polyethyleneimine and/or urea were not added, and a lot of zinc pyrithione was lost in the washing process, so the antibacterial durability was not good, and in Comparative Example 9, water-dispersed polyurethane prepolymer was Since it was not added, the porous inorganic nanoparticles did not adhere well, and the deodorization properties were greatly reduced.

Although the present invention has been described through the specific matters and limited examples as described above, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention pertains to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (9)

a) preparing an antibacterial and deodorizing composition for dyeing comprising a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite including porous inorganic nanoparticles, and a water-dispersed polyurethane prepolymer; and
b) dyeing the fabric by immersing it in the antibacterial and deodorizing composition for dyeing;
includes,
The inorganic nanocomposite is prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on diatomaceous earth having an average particle size of 100 to 300 nm. The method of claim 1,
The polyethyleneimine has a weight average molecular weight of 600 to 1,500 g/mol, a method for producing an antibacterial and deodorizing fiber. The method of claim 1,
The antibacterial deodorant composition for dyeing is 1 to 5 parts by weight of zinc pyrithione, 3 to 15 parts by weight of polyethyleneimine, 10 to 50 parts by weight of urea, 5 to 15 parts by weight of inorganic nanocomposite, and A method of producing an antibacterial and deodorizing fiber comprising 10 to 30 parts by weight of a water-dispersed polyurethane prepolymer. 4. The method of claim 3,
The weight ratio of the zinc pyrithione: polyethylene imine: urea is 1: 1.5 to 3: 5 to 10, the method for producing an antibacterial and deodorizing fiber. delete delete The method of claim 1,
The manufacturing method comprises: c) spraying a composition comprising an inorganic nanocomposite containing zinc pyrithione, polyethyleneimine, urea, and porous inorganic nanoparticles and a water-dispersed polyurethane prepolymer on the dyed fiber; further comprising The method for producing an antibacterial and deodorizing fiber. An antibacterial and deodorizing fiber dyed with an antibacterial and deodorizing composition for dyeing containing a dye composition, zinc pyrithione, polyethyleneimine, urea, an inorganic nanocomposite containing porous inorganic nanoparticles, and a water-dispersed polyurethane prepolymer,
The inorganic nanocomposite is an antibacterial and deodorizing fiber prepared by supporting zinc oxide nanoparticles through a solvothermal synthesis reaction on diatomaceous earth having an average particle size of 100 to 300 nm. 9. The method of claim 8,
The antibacterial deodorant composition for dyeing is 1 to 5 parts by weight of zinc pyrithione, 3 to 15 parts by weight of polyethyleneimine, 10 to 50 parts by weight of urea, 5 to 15 parts by weight of inorganic nanocomposite, and An antibacterial and deodorizing fiber comprising 10 to 30 parts by weight of a water-dispersed polyurethane prepolymer.

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