KR20230146187A - Ecofriendly functional bio material and method for manufacturing same - Google Patents

Abstract

The present invention relates to an eco-friendly functional biomaterial and a preparation method thereof, and more specifically, to an eco-friendly functional biomaterial that is obtained by dyeing cellulose fibers with pigments extracted from Dryopteris crassirhizoma, thereby having excellent antibacterial, deodorizing, color fastness and UV protection properties and a preparation method thereof. The present invention comprises: an extract extraction step (S10) of extracting a flavonoid-based pigment extract from Dryopteris crassirhizoma; a pigment obtaining step (S20) of obtaining a flavonoid-based pigment by concentrating the flavonoid-based pigment extract extracted in the extract extraction step (S10) under reduced pressure; a fiber pretreatment step (S30) of preparing cellulose fibers by pretreating the same with alginic acid; and a fiber dyeing step (S40) of dyeing the cellulose fibers pretreated in the fiber pretreatment step (S30) with the flavonoid-based dye.

Description

Eco-friendly functional bio material and method for manufacturing same {Ecofriendly functional bio material and method for manufacturing same}

The present invention relates to an eco-friendly functional biomaterial and a method of manufacturing the same. More specifically, the present invention relates to an eco-friendly functional biomaterial with excellent antibacterial properties, deodorization, fastness and UV protection rate by dyeing cellulose fibers with pigment extracted from the fiber, and a method of manufacturing the same. It's about.

Recently, environmental problems such as the increase in the average temperature of the Earth's atmosphere and the occurrence of abnormal climates due to the greenhouse effect caused by global warming have become issues around the world. As the standard of living has improved along with recent rapid social development, hygiene, etc. As the demand for well-being materials is increasing socially, the same desire is reflected for various textile materials that directly contact the body, and the demand for so-called 'functional fibers' with various functions is increasing.

In response to these consumer desires, the development of fibers that are eco-friendly and have antibacterial, deodorizing, and UV-blocking properties is in full swing.

Accordingly, Korean Patent No. 10-2199081 goes through an enzyme treatment process and a microbial treatment process during the manufacturing process, thereby solving the problems of destruction of the functionality of natural fibers and environmental pollution caused by methods using chemicals. Technology regarding eco-friendly fibers and their manufacturing methods, including processing processes, has been announced.

In addition, Korean Patent No. 10-1427226 is an eco-friendly biodegradable composite fiber containing excellent thermoplastic cellulose whose physical properties are improved by using an eco-friendly plasticizer in the plasticization process of thermoplastic cellulose and polylactic acid with biodegradability, and its production. The technology regarding the method has been announced.

Research and development on functional fibers that are eco-friendly and have antibacterial, deodorizing, and UV-blocking properties are actively underway.

Republic of Korea Patent No. 10-2199081 (2020.12.30.) Republic of Korea Patent No. 10-1427226 (July 31, 2014)

The present invention was devised to solve the above-mentioned problems. The purpose of the present invention is to dye cellulose fibers with pigments extracted from fiber, thereby providing excellent antibacterial properties, deodorizing properties, fastness, and UV protection, so that they can be used in the field of sportswear such as mountaineering clothing, as well as functionality. The goal is to provide eco-friendly functional biomaterials and manufacturing methods that can be used in various fields such as cosmetics such as patches.

The objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the description below.

In order to achieve the above object, in the eco-friendly functional biomaterial and its manufacturing method according to the present invention, an extract extraction step (S10) of extracting a flavonoid-based pigment extract from Dryopteris crassirhiaoma; A pigment acquisition step (S20) of obtaining a flavonoid pigment by concentrating the flavonoid pigment extract extracted in the extract extraction step (S10) under reduced pressure; A fiber pretreatment step (S30) of preparing cellulose fibers by pretreating them with alginic acid; and a fiber dyeing step (S40) of dyeing the flavonoid-based pigment to the cellulose fiber pretreated in the fiber pretreatment step (S30).

Here, the extract extraction step (S10) involves extracting the flavonoid-based pigment extract by simultaneously ultrasonic extraction and hot water extraction of Dryopteris crassirhiaoma for 20 to 40 minutes at a temperature of 40 to 70 ° C. It is characterized by

Meanwhile, the fiber pretreatment step (S30) is characterized in that the cellulose fiber is pretreated with the alginic acid extracted by hydrothermal export of kelp for 2 to 4 hours at a temperature of 80 to 120 ° C.

In addition, in the fiber dyeing step (S40), the flavonoid dye is dyed on the pretreated cellulose fiber at a temperature of 60 to 120° C., and calcium chloride (CaCl ₂ ) is added to increase the dyeing amount of the flavonoid dye. It is characterized by addition.

In addition, in order to achieve the above object, the present invention can provide an eco-friendly functional biomaterial manufactured by the above-described manufacturing method.

The present invention has the advantage of being able to produce biomaterials in an environmentally friendly manner using natural cellulose fibers and pigments extracted from bamboo shoots.

In addition, the present invention has the advantage of being applicable to various fields due to its excellent antibacterial properties, deodorizing properties, fastness, and ultraviolet ray blocking rate.

Figure 1 is a flowchart showing a method for manufacturing an eco-friendly functional biomaterial according to a preferred embodiment of the present invention.
Figure 2 is a reaction diagram showing a method for manufacturing an eco-friendly functional biomaterial according to a preferred embodiment of the present invention.

The advantages and features of the present invention and methods for achieving them will become clear by referring to the embodiments described in detail below along with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various different forms. The present embodiments only serve to ensure that the disclosure of the present invention is complete and that common knowledge in the technical field to which the present invention pertains is not limited. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

Specific details for implementing the present invention will be described in detail with reference to the drawings attached below. Regardless of the drawings, the same reference numerals refer to the same elements, and “and/or” includes each and all combinations of one or more of the mentioned items.

The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used in the specification, “comprises” and/or “comprising” does not exclude the presence or addition of one or more other elements in addition to the mentioned elements.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used with meanings that can be commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless clearly specifically defined.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings.

Figure 1 is a flowchart showing a manufacturing method of an eco-friendly functional biomaterial according to a preferred embodiment of the present invention, and Figure 2 is a reaction diagram showing a manufacturing method of an eco-friendly functional biomaterial according to a preferred embodiment of the present invention.

As shown in Figure 1, the manufacturing method of eco-friendly functional biomaterial includes an extract extraction step (S10), a pigment acquisition step (S20), a fiber pretreatment step (S30), and a fiber dyeing step (S40).

First, in the extract extraction step (S10), a flavonoid pigment extract is extracted from Dryopteris crassirhiaoma.

Dryopteris crassirhiaoma is a perennial root-growing fern belonging to the Aespidiaceae family, and grows in mountains or shady, moist soil in various regions such as Korea, Japan, Sakhalin, Kuril Islands, and northeastern China.

Meanwhile, the main pigment component contained in Dryopteris crassirhiaoma is flavonoid, a group of substances having a structure in which two benzene rings are connected by carbon. The flavonoid, which has a maximum absorption wavelength of 280 nm, is antibacterial, It has anti-cancer, anti-viral, anti-allergic and anti-inflammatory activities and is known to inhibit oxidation in vivo.

According to a preferred embodiment, in the extract extraction step (S10), the dryopteris crassirhiaoma is subjected to ultrasonic extraction and hot water extraction in parallel at a temperature of 40 to 70° C. for 20 to 40 minutes to obtain the flavonoid pigment extract. Extract.

According to a more preferred embodiment, in the extract extraction step (S10), the flavonoid-based pigment extract is extracted from Dryopteris crassirhiaoma at a temperature of 60° C. for 30 minutes in parallel with ultrasonic extraction and hot water extraction.

Traditional methods such as hot water extraction, Soxhlet method, high-temperature solvent extraction, and mechanical compression are mainly used to extract useful components such as pigments from plants. Traditional extraction methods have low yields and high consumption of extraction solvents, resulting in high costs. It has disadvantages such as:

However, the ultrasonic extraction method generates a very large amount of energy due to cavitation caused by ultrasonic vibration, and the local temperature increases the kinetic energy of the surrounding reactant particles, so sufficient energy required for the reaction is obtained, and ultrasonic extraction generates a large amount of energy due to cavitation. The impact effect of energy induces high pressure and increases the mixing effect.

Therefore, by combining the ultrasonic extraction and the hot water extraction in the extract extraction step (S10), it is possible to shorten the extraction time, improve the flavonoid content in the flavonoid pigment extract, and safely elute useful components.

Next, in the pigment acquisition step (S20), the flavonoid pigment extract extracted in the extract extraction step (S10) is concentrated under reduced pressure to obtain a flavonoid pigment.

Next, the fiber pretreatment step (S30) is prepared by pretreating cellulose fibers with alginic acid, as shown in FIG. 2.

The cellulose fiber has a high degree of polymerization and excellent quantity and arrangement of crystal regions, so its dyeability is lower than that of protein fiber.

On the other hand, alginic acid is a polysaccharide that constitutes the cell membrane of brown algae, and exhibits acidic properties due to the carboxyl group of uronic acid, and has viscosity, hydration, water retention, reactivity with metal ions such as Ca ² , binding properties, film formation, etc. It has various characteristics and is used not only in the food industry but also in the pharmaceutical industry and textile industry.

Therefore, by pretreating the cellulose fiber with the alginic acid, it is possible to increase the dyeing amount of the flavonoid pigment in the next step, the fiber dyeing step (S40).

According to a preferred embodiment, in the fiber pretreatment step (S30), the cellulose fiber is pretreated with the alginic acid extracted by hydrothermal export of kelp for 2 to 4 hours at a temperature of 80 to 120 ° C.

According to a more preferred embodiment, in the fiber pretreatment step (S30), the cellulose fiber is pretreated with the alginic acid extracted by hydrothermal export of kelp at a temperature of 100° C. for 3 hours.

Next, in the fiber dyeing step (S40), the flavonoid pigment is dyed on the cellulose fiber pretreated in the fiber pretreatment step (S30).

According to a preferred embodiment, in the fiber dyeing step (S40), the flavonoid-based dye is dyed on the pretreated cellulose fiber at a temperature of 60 to 120°C.

According to a more preferred embodiment, in the fiber dyeing step (S40), the flavonoid-based dye is dyed on the pretreated cellulose fiber at a temperature of 100°C.

At this time, as shown in FIG. 2, calcium chloride (CaCl ₂ ) may be further added to increase the dyeing amount of the flavonoid pigment in the fiber dyeing step (S40).

As the alginic acid, which has good reactivity with metal ions such as Ca ² , reacts with calcium chloride (CaCl ₂ ), the amount of dyeing of the flavonoid-based pigment increases on the cellulose fiber pretreated with alginic acid.

Therefore, by adding more calcium chloride (CaCl ₂ ) in the fiber dyeing step (S40), the dyeing properties and fastness of the eco-friendly functional biomaterial thus manufactured can be increased.

Hereinafter, the configuration and operation of the present invention will be described in more detail through examples, comparative examples, and experimental examples of the present invention. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. Any information not described here can be technically inferred by anyone skilled in the art, so description thereof will be omitted.

Example 1

A flavonoid pigment extract was extracted from Dryopteris crassirhiaoma at a temperature of 60°C for 30 minutes in parallel, followed by concentration of the flavonoid pigment extract under reduced pressure to obtain a flavonoid pigment.

Cellulose fibers were prepared by pretreatment with the alginic acid extracted by exporting kelp in hot water for 3 hours at a temperature of 100℃, and then calcium chloride (CaCl ₂ ) was added at a temperature of 100℃ to add flavonoid pigment to the cellulose fibers pretreated with alginic acid. was dyed.

Comparative Example 1

Proceeding in the same manner as Example 1, except for the ultrasonic extraction method, cellulose fibers were dyed using only the hot water extraction method.

Comparative Example 2

It was prepared in the same manner as in Example 1, except for the steps of pretreating cellulose fibers with alginic acid and adding calcium chloride (CaCl ₂ ).

Experimental Example 1 - UV blocking effect experiment

The above Experimental Example 1 is a test of the UV-blocking effect of the eco-friendly functional biomaterial manufactured according to the present invention, using an ultraviolet/visible spectrophotometer with an integrating sphere (UV-vis 2101 Scanning spectophotometer, Shimadzu, Japan) in accordance with KS K 0850. The ultraviolet ray blocking rates of standard white fabric and each cellulose fiber were measured using the Auto method in a wavelength range of 280 to 400 nm, at a wavelength interval of 5 nm, and the results are shown in Table 1 below.

UV protection rate (%) = 100 - UV transmission rate (%)

Ultraviolet A transmittance = (T ₃₁₅ + T ₃₂₀ + ... + T ₃₉₅ + T ₄₀₀ )/18

Ultraviolet B transmittance = (T ₂₈₀ + T ₂₈₅ + ... + T ₃₁₀ + T ₃₁₅ )/18

T _λ : Spectral transmittance at wavelength λ

wavelength Example 1 Comparative Example 1 Comparative Example 2 standard back four 315~400nm 91.47 80.20 74.19 58.60 280~315nm 94.50 85.84 81.35 82.91

As shown in Table 1, Example 1 increased the ultraviolet ray blocking rate at a wavelength of 315 to 400 nm and 280 to 315 nm compared to the standard white cloth and Comparative Examples 1 to 2.

That is, it can be confirmed that Example 1 has an excellent UV blocking effect compared to Comparative Examples 1 to 2 and the standard white cloth.

In addition, the UV protection rate according to the dyeing amount of cellulose fibers (Example 1) dyed at different concentrations was measured under the conditions of standard white fabric and dyeing solution PH 3, which had the best apparent dyeing amount, and the results are shown in Table 2 below.

wavelength Example 1 standard back four K/S: 1.96 K/S: 2.85 K/S: 3.24 K/S: 4.41 K/S: 5.86 315~400nm 85.31 93.40 94.78 96.62 97.97 45.60 280~315nm 92.43 94.12 95.73 97.70 98.40 83.91

As shown in Table 2, Example 1 had an increased UV protection rate compared to the standard white fabric, and the UV protection rate increased depending on the amount of flavonoid dye dyed on the cellulose fiber.

That is, Example 1 confirms that the ultraviolet ray blocking effect is improved as the concentration of cellulose fiber dyeing of the flavonoid pigment increases.

Experimental Example 2 - Fastness experiment

Experimental Example 2 was a fastness test for the eco-friendly functional biomaterial manufactured according to the present invention, and the fastness of Example 1 and Comparative Examples 1 to 2 were measured, and the results are shown in Table 3 below.

test item Example 1 Comparative Example 1 Comparative Example 2 note washing fading color 4-5 4 4 KS K ISO 105-C06:2007 stain acetate 4-5 4-5 4-5 cotton 4-5 3-4 3-4 nylon 4-5 4-5 4-5 polyester 4-5 4-5 4-5 acrylic 4-5 4-5 4-5 wool 4-5 4-5 4-5 rubbing stain dryness 4-5 4-5 4-5 KS K 0650 moisture 4-5 4-5 4-5 perspiration acid/alkaline acid/alkaline acid/alkaline KS K ISO 105-E04:2010 fading color 4-5/4-5 4-5/4-5 4-5/4-5


stain acetate 4-5/4-5 4-5/4-5 4-5/4-5 cotton 4/3-4 4 4 nylon 4/3-4 4/3-4 4/3-4 polyester 4-5/4-5 4-5/4-5 4-5/4-5 acrylic 4-5/4-5 4-5/4-5 4-5/4-5 wool 4/4 4/4 4/4 dry cleaning fading color 4-5 4-5 4-5 KS K ISO 105-D01:2010 stain 4-5 4-5 4-5 light fading color 4-5 3-4 3-4 KS K ISO 105-B02:2010

As shown in Table 3, it can be seen that Example 1 has improved sunlight fastness by one level compared to Comparative Examples 1 and 2.

Experimental Example 3 - Antibacterial Experiment

The above Experimental Example 3 is an antibacterial test on the eco-friendly functional biomaterial manufactured according to the present invention. Bacteria and fungi were used as test bacteria, and the bacteriostatic reduction rate was measured according to the equation below in accordance with KS K 0693. The results were It is shown in Table 4 below.

Bacteriostatic reduction rate (%) = (((B or C or (B+C)/2)-A)/(B or C or (B+C)/2))×100

A: Number of bacteria reproduced from the cultured test piece over a certain contact time after inoculation

B: Number of bacteria reproduced from the test piece at contact time [0] (immediately after contact) after inoculation

C: Number of bacteria regenerated from the control piece at contact time [0] (immediately after contact) after inoculation

Example 1 Comparative Example 1 Comparative Example 2 Day 10 Bacteria (Pseudomonas aerugonosa) 99.9% death 99.9% death 99.9% death Fungus (Aspergillus brasiliensis) 99.9% death 97% dead 95% death Day 20 Bacteria (Pseudomonas aerugonosa) 100% death 100% death 100% death Fungus (Aspergillus brasiliensis) 100% death 100% death 100% death

As shown in Table 4, the reduction rate of bacteria and fungi in Example 1 increased on the 10th and 20th days compared to Comparative Examples 1 and 2.

That is, it can be confirmed that Example 1 shows an excellent antibacterial effect of close to 100% as a result of the antibacterial test.

Experimental Example 4 - Deodorizing test

Experimental Example 4 is a deodorization test for the eco-friendly functional biomaterial manufactured according to the present invention, in which 28% of ammonoa water ((NH4)OH=35.05), Yakuri pure chemical, Ltd, Japan) was directly added to a 2L triangular plast. After adjusting to inhale 100 ml using a self-contained gas detector (Chromogenic gas detector tubes gastec, Japan) and a gas detection tube, the ammonia gas concentration value (ppm) and deodorization rate were measured four times at 30-minute intervals from 30 to 120 minutes. The results are shown in Table 5 below.

Deodorization rate (%)=[(A-B)/A]×100

A: gas concentration of blank

B: gas concentration under specimen existence

Time(min) 30 60 90 120 Example 1 ammonia gas
Concentration value (ppm) 13 8 7 4 Deodorization rate 57 73 77 87 Comparative Example 1 ammonia gas
Concentration value (ppm) 23 20 20 16 Deodorization rate 35 48 57 55 Comparative Example 2 ammonia gas
Concentration value (ppm) 20 17 17 14 Deodorization rate 33 43 53 53 standard back four ammonia gas
Concentration value (ppm) 24 22 19 17 Deodorization rate 20 27 37 43 Blank ammonia gas
Concentration value (ppm) 30 30 30
30 Deodorization rate - - - -

As shown in Table 5, Example 1 showed the lowest ammonia gas concentration value (ppm) and the highest deodorization rate compared to the standard white cloth and Comparative Examples 1 to 2.

That is, it can be confirmed that Example 1 has the best deodorizing properties compared to Comparative Examples 1 to 2 and the standard white cloth.

Therefore, it can be confirmed that the eco-friendly functional biomaterial manufactured according to the present invention has excellent antibacterial properties, deodorizing properties, fastness, and ultraviolet ray blocking rate by dyeing cellulose fibers with pigments extracted from fiber.

Although embodiments of the present invention have been described with reference to the above and the attached drawings, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical idea or essential features. You will understand that it exists. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

S10: Extract extraction step
S20: Pigment acquisition stage
S30: Fiber pretreatment step
S40: Fiber dyeing step

Claims (5)

An extract extraction step (S10) of extracting a flavonoid pigment extract from Dryopteris crassirhiaoma;
A pigment acquisition step (S20) of obtaining a flavonoid pigment by concentrating the flavonoid pigment extract extracted in the extract extraction step (S10) under reduced pressure;
A fiber pretreatment step (S30) of preparing cellulose fibers by pretreating them with alginic acid; and
A fiber dyeing step (S40) of dyeing the flavonoid pigment to the cellulose fiber pretreated in the fiber pretreatment step (S30). According to paragraph 1,
The extract extraction step (S10),
A method for producing an eco-friendly functional biomaterial, characterized in that the flavonoid pigment extract is extracted from the Dryopteris crassirhiaoma by simultaneously ultrasonic extraction and hot water extraction for 20 to 40 minutes at a temperature of 40 to 70 ° C. According to paragraph 1,
The fiber pretreatment step (S30) is,
A method for producing an eco-friendly functional biomaterial, characterized in that the cellulose fiber is pretreated with the alginic acid extracted by exporting kelp in hot water for 2 to 4 hours at a temperature of 80 to 120 ° C. According to paragraph 1,
In the fiber dyeing step (S40),
The flavonoid pigment is dyed on the pretreated cellulose fiber at a temperature of 60 to 120°C, and calcium chloride (CaCl ₂ ) is further added to increase the dyeing amount of the flavonoid pigment. Manufacturing method. An eco-friendly functional biomaterial manufactured by the manufacturing method of any one of claims 1 to 4.