WO2023214798A1 - Method for manufacturing mycelium into leather using plant-derived polyphenol group - Google Patents

Method for manufacturing mycelium into leather using plant-derived polyphenol group Download PDF

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WO2023214798A1
WO2023214798A1 PCT/KR2023/006047 KR2023006047W WO2023214798A1 WO 2023214798 A1 WO2023214798 A1 WO 2023214798A1 KR 2023006047 W KR2023006047 W KR 2023006047W WO 2023214798 A1 WO2023214798 A1 WO 2023214798A1
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leather
tannin
mycelium mat
mycelium
mat
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PCT/KR2023/006047
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French (fr)
Korean (ko)
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김성원
양시중
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주식회사 마이셀
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Priority claimed from KR1020230057635A external-priority patent/KR20230156655A/en
Publication of WO2023214798A1 publication Critical patent/WO2023214798A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/14—Fungi; Culture media therefor
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/02—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with cellulose derivatives

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  • the present invention relates to a method for effective cross-linking reaction in the production of leather materials using mushroom mycelium, an eco-friendly material that can replace animal leather and artificial leather using petrochemical-based synthetic polymers, specifically. is a technology for producing leather by effectively crosslinking mycelium mat using pH-controlled vegetable tannin.
  • the purpose of the present invention is to provide a leather material with improved physical strength, flexibility, and durability while using mushroom mycelium, an eco-friendly material that can replace animal skin and artificial leather using petrochemical-based synthetic polymers.
  • the present invention provides a composition for crosslinking artificial leather based on a mycelium mat containing tannin derived from an extract of Caesalpinia spinosa , wherein the pH of the tannin is It may be characterized as being 7.5 to 11.5.
  • the pH of the tannin may be 8 to 11.
  • the pH of the tannin may be 9 to 10.
  • the present invention includes a first step of inactivating the mycelium mat; A second step of allowing the polysaccharide solution to penetrate the mycelium mat; And a third step of allowing a solution containing tannin derived from a tara ( Caesalpinia spinosa ) extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated.
  • the polysaccharide solution includes chitosan, kappa- carrageenan , iota-carrageenan, l -carrageenan, l -carrageenan, guar gum, and xanthan. , Gum Arabic, pectin, peptone, konjac, dextran, heparin, and fucoidan. You can.
  • the buffering agents used to adjust the pH of the tannin include potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium hydrogen carbonate (NaHCO 3 ), bis-tris propane buffer, and BES buffer (N, N-bis). (2-hydroxyethyl)-2-aminoethanesulfonic acid), MOPS buffer (3-(N-morpholino)propanesulfonic acid), HEPES buffer (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES Buffer (N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid), MOBS buffer (4-(N-Morpholino)butanesulfonic acid), TRIS buffer (Tris(hydroxymethyl)aminomethane), DIPSO buffer (3-(N,N- It may include one or more selected from the group consisting of Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid), P
  • the present invention may further include a fourth step of plasticizing the mycelium mat with a plasticizer solution after the third step.
  • the plasticizer solution includes ethylene glycol, ethylene glycerol, glycerol, polyethylene glycerol (PEG), polypropylene glycol (PPG), and polysorbate. , cyclodextrin, lavender oil, castor oil, and cinnamaldehyde.
  • mycelium mat-based leather that is environmentally friendly and has improved physical properties such as tensile strength, flexibility, and durability.
  • Figure 1 is a graph showing the results of tensile strength measurement of leather samples using mycelium mat prepared according to an embodiment of the present invention.
  • Figure 2 is a graph showing the results of tensile elongation measurement of leather samples using mycelium mat prepared according to an embodiment of the present invention.
  • Figure 3 is a diagram schematically showing the process of manufacturing leather using mycelium mat according to an embodiment of the present invention.
  • Figure 4 is a photograph of a mycelium mat cross-linked with tara tannin and pH-adjusted tara tannin according to an embodiment of the present invention.
  • the present invention provides a composition for crosslinking artificial leather based on a mycelium mat containing tannin derived from a Caesalpinia spinosa extract, wherein the tannin has a pH of 7.5 to 11.5. can do.
  • Vegetable tannin is a type of plant polyphenol molecule that is abundant in nature, and more than 800 types exist in nature. It is known that tannin is rich in hydroxyl groups (-OH) and can aggregate proteins, and tannin with a molecular weight of 3,000 Da or less is known to be able to penetrate into the fiber structure of animal skin.
  • -OH hydroxyl groups
  • Plant-derived tannins can be divided into condensed tannins and hydrolysable tannins. Tannins commonly used in leathering animal skins include oak, spruce bark, and chestnut ( Tannin extracted from chestnuts, willow bark, valonea, mimosa, tara, quebracho, etc. can be used.
  • tara extract may contain some condensable tannin, gallotannin, and epigallocatechin, and these substances can be used to modify the surface of various materials through oxidation at a pH near the pKa. It is known that it can be done.
  • the pKa of epigallocatechin is around 8
  • the pKa of gallotannin is around 6.
  • the present inventors adjusted the pH of the tannin derived from the commonly used tara extract to improve the tensile strength and the tensile strength of mycelium mat-based alternative leather.
  • the present invention for a mycelium mat-based leather material with improved physical properties such as tensile elongation was completed.
  • the pH of the tannin derived from the tara extract may be 7.5 to 11.5, preferably 8 to 11, and more preferably 9 to 10.
  • the pH of the tannin derived from the tara extract may be 8 to 9, 8 to 10, 8 to 11, 9 to 10, 9 to 11, or 10 to 11.
  • the pH of the tannin derived from the tara extract is 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0. , 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11 .2, 11.3, 11.4 or 11.5 It can be.
  • the present invention includes a first step of inactivating the mycelium mat; A second step of allowing the polysaccharide solution to penetrate the mycelium mat; And a third step of allowing a solution containing tannin derived from a tara ( Caesalpinia spinosa ) extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated. It provides a method of manufacturing a mycelium mat into leather, including a.
  • a first step process of inactivating the mycelium mat may be included, and methods such as sterilization, ultrasonic treatment, and chemical treatment may be used here.
  • the sterilization method uses an autoclave, and may be a method of sterilizing living mycelium under temperature and pressure conditions higher than the maximum temperature at which organisms can live medically, 119°C and 1.2 atm, specifically 121°C. , the mycelial mat can be inactivated by sterilizing at 1.5 atm for 30 minutes.
  • Inactivation of the mycelium mat using ultrasound can be performed for 2 hours by adding live mycelium to distilled water in the frequency range of 35 to 50 Hz.
  • the chemical treatment method may be a method of inactivating the mycelium mat using hydrogen peroxide (H 2 O 2 ), sodium hypochlorite (NaClO), sodium hydroxide (NaOH), etc.
  • the hydrogen peroxide solution is a substance that can dissolve cell walls or cell membranes by reacting with enzymes to generate active oxygen or oxygen radicals, and a 3% hydrogen peroxide solution is commonly used for medical purposes.
  • the concentration of hydrogen peroxide may be 5 to 30% of the total volume of the hydrogen peroxide solution, and the mycelium mat is immersed in the solution at a temperature of 25 to 60 ° C. for 1 minute to 2 hours. It can be done. At this time, if the concentration of hydrogen peroxide is 10 to 30% of the total solution volume, ultrasonic treatment must be performed for more than 1 hour before treating the hydrogen peroxide solution.
  • Sodium hypochlorite is known as the main ingredient of bleach, and can be diluted depending on the intended use and used for sterilization.
  • the concentration of sodium hypochlorite may be 0 to 30% of the total solution volume, and the mycelium mat is treated with the solution at a temperature of 25 to 60 ° C for 1 minute to 2 hours. It can be performed by immersion in . At this time, in order to inactivate the mycelium, it is preferable to immerse in a solution containing more than 5% sodium hypochlorite by ultrasonic treatment for more than 1 hour, or to immerse in a solution containing more than 5% sodium hypochlorite for more than 2 hours without ultrasonic treatment. .
  • the present invention may include a second step of allowing the polysaccharide solution to penetrate the mycelium mat, where the chitin of the mycelium is relatively anionic and the polysaccharide is relatively cationic, so the polysaccharide is absorbed through electrostatic attraction. It can play a role in cross-linking the mycelium mat.
  • the polysaccharide solution includes chitosan, kappa- carrageenan , iota-carrageenan, l -carrageenan, l -carrageenan, guar gum, and xanthan. , Gum Arabic, pectin, peptone, konjac, dextran, heparin, and fucoidan. You can.
  • chitosan and adipic acid can be infiltrated into the inactivated mycelium mat. Heat pressing after simply infiltrating chitosan and adipic acid and drying is performed to remove the amine group of chitosan. It may be unsuitable for cross-linking through an amide bond, which is a bond that can occur between adipic acid and the carboxyl group of adipic acid.
  • the present invention may include a third step of allowing a solution containing tannin derived from tara extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated.
  • the gallol group of the tannin derived from the tara extract can be oxidized under weakly basic conditions to form quinone, and the quinone of the oxidized gallol group is a nucleophilic functional group (amine group, A nucleophilic addition reaction can occur by reacting with a thiol group, or a covalent bond such as an imine bond can be formed through a dehydration condensation reaction.
  • the solution containing tannin derived from the tara extract used in the third step may be characterized in that its pH is adjusted to 7.5 to 11.5 using a buffer or the like.
  • the pH of the tannin derived from the tara extract may be 7.5 to 11.5, preferably 8 to 11, and more preferably 9 to 10.
  • the pH of the tannin derived from the tara extract can be characterized as being 7.5 to 11.5, and when the adjusted pH is less than 7.5, the formation of quinone through oxidation of the gallol group of tannin is reduced, resulting in cross-linking treatment of the mycelium. may not be sufficient, and if the adjusted pH exceeds 11.5, a problem may occur in which tannin derived from tara extract may lose cross-linking as the ester group (-COO-) is broken under strong basic conditions. You can.
  • the buffering agents include potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium hydrogen carbonate (NaHCO 3 ), bis-tris propane buffer, BES buffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), and MOPS.
  • Buffer (3-(N-morpholino)propanesulfonic acid), HEPES buffer (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES buffer (N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid) acid), MOBS buffer (4-(N-Morpholino)butanesulfonic acid), TRIS buffer (Tris(hydroxymethyl)aminomethane), DIPSO buffer (3-(N,N-Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid ), PBS buffer (Phosphate-buffered saline), and glycine (glycine).
  • NaOH sodium hydroxide
  • All commonly used buffering agents can be used.
  • the present invention may further include a fourth step of plasticizing the mycelium mat with a plasticizer solution after the third step.
  • plasticizer used in the present invention refers to an additive that reduces the viscosity or plasticity of a material and is added to change physical properties such as softening point, glass transition point, thermal and mechanical properties of a polymer. It may be a material commonly used in the manufacture of plastic.
  • the plasticizer solution includes ethylene glycol, ethylene glycerol, glycerol, polyethylene glycerol (PEG), polypropylene glycol (PPG), and polysorbate. , cyclodextrin, lavender oil, castor oil, and cinnamaldehyde.
  • a mycelium mat-based leather sample was prepared using a composition for cross-linking artificial leather containing tannin derived from a pH-adjusted tara extract, and the tensile strength and tensile strength of the produced leather were measured. Tensile elongation was measured (Experimental Example 1, Experimental Example 2).
  • PDA potato dextrose agar
  • Fragments of lignocellulosic mushroom ( Ganoderma sp., Fomitella Sp. Inonotus sp., etc.) mycelium were cut from the sterile zone, transplanted into PDA medium, and cultured in an incubator at 28°C for 7 days.
  • a nutritional composition was prepared by mixing 40 g of dextrose, 20 g of yeast extract, and 20 g of guar gum with 920 mL of distilled water at 25°C. Additionally, 0.5 g of magnesium sulfate (MgSO 4 ), 0.5 g of calcium carbonate (CaCO 3 ), and 0.5 g of potassium phosphate (KH 2 PO 4 ). And 0.5 g of calcium chloride (CaCl 2 ) was dissolved in 998 mL of distilled water at 25°C to prepare an inorganic salt composition.
  • MgSO 4 magnesium sulfate
  • CaCO 3 calcium carbonate
  • KH 2 PO 4 potassium phosphate
  • the nutrient composition and the inorganic salt composition were mixed and stirred for 10 minutes at a speed of 200 rpm at 25° C. using a stirring device (DAIHAN scientific, HT-120DX) to prepare a 2 L medium composition.
  • a stirring device DAIHAN scientific, HT-120DX
  • the medium composition was sterilized through an autoclave at 132°C and a vapor pressure of 5kgf/cm 2 for 25 minutes, and the sterilized medium composition was cooled to 25°C to prepare a semi-liquid medium, adding up to 1000 mL in a 1/2 bag. Filled it in.
  • the seed culture step 200 mL of the composition containing the seed cultured for 7 days at 25 °C was inoculated into 1000 mL of the semi-liquid medium, then covered with a lid with a filter and a vent and darkened for 4 weeks at 28 °C and 90% humidity. was cultured, and 300 g of live mycelium mat was extracted.
  • Example 1 Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 8 conditions
  • the mycelium mat extracted in the preparation example was immersed in 400 mL of 30% hydrogen peroxide at 60°C and sonicated at 35 kHz for 2 hours at a temperature of 60°C.
  • Tara tannin solution concentration: 10 g/L
  • Tara tannin Ormotan T, SILVATEAM
  • NaOH sodium hydroxide
  • the mycelium mat immersed in the chitosan solution was immersed in the Tara tannin solution whose pH was adjusted to 8 at 25°C for 2 hours.
  • the mycelium mat soaked in the poly-ethylene glycol (PEG) solution was dried at 40°C for more than 24 hours to remove moisture, and then heat-pressed at 90°C at a pressure of 98 MPa for 20 seconds (custom village, CDH). -4050) was used to produce mycelial leather measuring 25 cm wide, 20 cm long, and 0.3 cm thick.
  • PEG poly-ethylene glycol
  • Example 2 Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 9 conditions
  • Example 2 The experiment was performed in the same manner as in Example 1, except that the mycelium mat was immersed in a Tara tannin solution mixed with 0.8 g of sodium hydroxide (NaOH) to adjust the pH to 9.
  • NaOH sodium hydroxide
  • Example 3 Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 11 conditions
  • Example 2 The experiment was performed in the same manner as in Example 1, except that the mycelium mat was immersed in a Tara tannin solution mixed with 2 g of sodium hydroxide (NaOH) to adjust the pH to 9.
  • NaOH sodium hydroxide
  • the mycelium mat extracted in the preparation example was immersed in 400 mL of 30% hydrogen peroxide at 60°C and sonicated at 35 kHz for 2 hours at a temperature of 60°C.
  • a 2% chitosan solution 400 mL of a 2% chitosan solution was prepared by mixing 8 g of chitosan, 8 g of adipic acid, and distilled water at 25°C, and then the sonicated mycelium mat was immersed in the chitosan solution for 1 day at 25°C.
  • the mycelium mat soaked in the poly-ethylene glycol (PEG) solution was dried at 40°C for more than 24 hours to remove moisture, and then heat-pressed at 90°C at a pressure of 98 MPa for 20 seconds (custom village, CDH). -4050) was used to produce mycelial leather measuring 25 cm wide, 20 cm long, and 0.3 cm thick.
  • PEG poly-ethylene glycol
  • Comparative Example 2 Manufacturing of mycelium mat-based alternative leather using plant-derived tannin - pH 7 conditions
  • Example 2 The experiment was performed in the same manner as in Example 1, except that the pH was adjusted to 7 by mixing with 10 mg of sodium hydroxide (NaOH).
  • NaOH sodium hydroxide
  • Example 2 The experiment was performed in the same manner as in Example 1, except that the pH was adjusted to 12 by mixing with 4 g of sodium hydroxide (NaOH).
  • the tensile strength is the maximum tensile strength when the leather sample breaks by placing the mycelial leather samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 using a tensile tester (QMESYS) and pulling at 100 mm/min. After calculating (N), the average tensile strength value of each of the five samples in Examples 1 to 3 and Comparative Examples 1 to 3 was obtained, and when the average tensile strength value of Comparative Example 1 was set to 1, the relative tensile strength was It is shown in Table 1 below.
  • Example 1 Adjust the pH of tara tannin to 8 1.56 218.21
  • Example 2 Adjust the pH of tara tannin to 9 1.64 235.19
  • Example 3 Adjust the pH of tara tannin to 11 1.60 229.15 Comparative Example 1 Immerse only in chitosan solution One 143.22 Comparative Example 2 Adjust the pH of tara tannin to 7 0.91 130.54 Comparative Example 3 Adjust the pH of tara tannin to 12 0.63 89.93
  • Tensile elongation was measured by taking five mycelial leather samples from each taxonomic group (examples or comparative examples shown in Table 2 below), marking the center with a mark, and testing them in a tensile tester (QMESYS) (clamp spacing 40 mm) at a tensile speed of 100 mm. The maximum weight was measured until the test specimen broke by tensioning at /min. The tensile elongation was calculated and expressed according to Equation 1 below, and the average elongation of each sample of five was obtained.
  • QMESYS tensile tester
  • Example 1 Adjust the pH of tara tannin to 8 1.48 44.38
  • Example 2 Adjust the pH of tara tannin to 9 1.50 45.31
  • Example 3 Adjust the pH of tara tannin to 11 1.38 42.81 Comparative Example 1 Immerse only in chitosan solution One 31.05 Comparative Example 2 Adjust the pH of tara tannin to 7 0.87 26.82 Comparative Example 3 Adjust the pH of tara tannin to 12 0.49 15.34
  • the present invention is a technology for manufacturing an eco-friendly leather material that can replace animal leather and artificial leather, and is very useful in the eco-friendly alternative material industry.

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Abstract

The present invention relates to a method for effectively carrying out a crosslinking reaction when manufacturing a leather material using mushroom mycelium which is an eco-friendly material capable of substituting for animal leather and artificial leather using a petrochemistry-based synthetic polymer. Specifically, the present invention relates to a method for manufacturing a mycelial mat into leather by effectively carrying out a crosslinking reaction of the mycelial mat by using pH-adjusted tannin derived from a tara (Caesalpinia spinosa) extract.

Description

식물유래 폴리페놀기를 이용한 균사체의 가죽화 방법Method for leathering mycelium using plant-derived polyphenol groups
본 발명은 동물가죽 및 석유화학 기반 합성 고분자를 이용한 인조가죽을 대체할 수 있는 친환경 소재인 버섯의 균사체(mycelium)을 이용한 가죽 소재의 제조에서 효과적인 가교반응을 하기 위한 방법에 관한 기술로서, 구체적으로는 pH가 조절된 식물성 탄닌을 이용하여 균사체 매트를 효과적으로 가교반응 시켜 가죽으로 제조하는 방법에 관한 기술이다.The present invention relates to a method for effective cross-linking reaction in the production of leather materials using mushroom mycelium, an eco-friendly material that can replace animal leather and artificial leather using petrochemical-based synthetic polymers, specifically. is a technology for producing leather by effectively crosslinking mycelium mat using pH-controlled vegetable tannin.
세계적으로 가죽에 대한 선호도와 소요량이 늘어나고 있지만 소비자들의 도덕적인 소비에 대한 눈높이가 함께 높아짐에 따라 가죽을 얻기 위한 과정에서 광범위한 살육과 환경파괴가 없는 대체가죽(인조가죽)에 대한 요구도가 높아지고 있다.Globally, the preference for and demand for leather is increasing, but as consumers' awareness of ethical consumption is also increasing, the demand for alternative leather (artificial leather) that does not involve extensive slaughter and environmental destruction in the process of obtaining leather is increasing.
하지만 인공가죽의 질감이 천연가죽과 차이가 많아 소비자 눈높이를 맞추기 위한 성형공정 과정이 까다로워지면서 염색 및 접착을 통한 가공성형 공정이 늘어나 제조공정 비용이 급격히 증가하고 석유기반 폴리머를 사용하는 제조부터 분해가 잘 되지 않아 재활용이 불가능하여 산업 쓰레기로 폐기될 때까지 전 공정 내에서 심각한 환경오염이 발생하는 등 여러가지 문제에 직면하고 있다.However, as the texture of artificial leather is very different from that of natural leather, the molding process to meet the consumer's expectations has become more difficult, and the processing molding process through dyeing and adhesion has increased, resulting in a rapid increase in manufacturing cost and the need for disassembly from manufacturing using petroleum-based polymers. It is facing a variety of problems, including serious environmental pollution occurring throughout the entire process until it is discarded as industrial waste as it is not recyclable.
이에 동물가죽 및 기존 인조가죽을 대체할 수 있는 새로운 소재를 가지고 환경적이며, 윤리적인 가죽 제조에 대한 제조방법 개발이 시급한 실정이다.Accordingly, there is an urgent need to develop environmentally friendly and ethical leather manufacturing methods using new materials that can replace animal leather and existing artificial leather.
상기와 같은 실정에서 동물가죽과 같은 천연 가죽을 대체할 수 있는 식물의 섬유질, 버섯, 실리콘 등과 같은 소재를 통한 가죽의 제조에 대한 연구가 활발히 진행되고 있다.In the above-mentioned situation, research is being actively conducted on the production of leather using materials such as plant fiber, mushrooms, silicon, etc., which can replace natural leather such as animal leather.
하지만 상기와 같은 대체 소재를 산업적으로 이용하기 위해서는 가죽의 추가적인 가교제(cross-linker)나 가소제(plasticizer) 등을 이용하여 물리적 강도, 유연성, 내구성을 강화시키기 위한 연구가 필요하다.However, in order to use the above alternative materials industrially, research is needed to enhance the physical strength, flexibility, and durability of leather by using additional cross-linkers or plasticizers.
본 발명의 목적은 동물가죽 및 석유화학 기반 합성 고분자를 이용한 인조가죽을 대체할 수 있는 친환경 소재인 버섯의 균사체(mycelium)을 이용하면서, 물리적 강도, 유연성, 내구성이 향상된 가죽 소재를 제공하는 것이다.The purpose of the present invention is to provide a leather material with improved physical strength, flexibility, and durability while using mushroom mycelium, an eco-friendly material that can replace animal skin and artificial leather using petrochemical-based synthetic polymers.
상기 목적을 달성하기 위하여, 본 발명은 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌(tannin)을 포함하는 균사체 매트(mat) 기반의 인조가죽 가교용 조성물을 제공하며, 상기 탄닌(tannin)의 pH는 7.5 내지 11.5인 것을 특징으로 할 수 있다.In order to achieve the above object, the present invention provides a composition for crosslinking artificial leather based on a mycelium mat containing tannin derived from an extract of Caesalpinia spinosa , wherein the pH of the tannin is It may be characterized as being 7.5 to 11.5.
또한, 상기 탄닌(tannin)의 pH는 8 내지 11인 것을 특징으로 할 수 있다.Additionally, the pH of the tannin may be 8 to 11.
또한, 상기 탄닌(tannin)의 pH는 9 내지 10인 것을 특징으로 할 수 있다.Additionally, the pH of the tannin may be 9 to 10.
또한, 본 발명은 균사체 매트를 불활성화 시키는 제1 단계; 상기 균사체 매트에 다당류 용액이 침투하도록 하는 제2 단계; 및 상기 다당류 용액이 침투된 균사체 매트에 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌을 포함하는 용액이 침투하도록 하는 제3 단계;를 포함하는, 균사체 매트를 이용하여 가죽을 제조하는 방법을 제공한다.In addition, the present invention includes a first step of inactivating the mycelium mat; A second step of allowing the polysaccharide solution to penetrate the mycelium mat; And a third step of allowing a solution containing tannin derived from a tara ( Caesalpinia spinosa ) extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated.
또한, 상기 다당류 용액은 키토산(chitosan), 카파-카라기난(k-carrageenan), 아이오타-카라기난(I-carrageenan), 람다-카라기난(L-carrageenan), 구아검(Guar gum), 잔탄(xanthan), 아라비아 검(Gum Arabic), 펙틴(pectin), 펩톤(peptone), 곤약(konjac), 덱스트란(dextran), 헤파린(heparin) 및 후코이단(fucoidan)으로 이루어진 군에서 선택되는 어느 하나 이상을 포함할 수 있다.In addition, the polysaccharide solution includes chitosan, kappa- carrageenan , iota-carrageenan, l -carrageenan, l -carrageenan, guar gum, and xanthan. , Gum Arabic, pectin, peptone, konjac, dextran, heparin, and fucoidan. You can.
또한, 상기 탄닌(tannin)의 pH 조절에 사용하기 위한 완충제는 수산화칼륨(KOH), 수산화소듐(NaOH), 탄산수소소듐(NaHCO3), bis-tris propane 완충제, BES 완충제(N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), MOPS 완충제(3-(N-morpholino)propanesulfonic acid), HEPES 완충제(2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES 완충제(N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonicd acid), MOBS 완충제(4-(N-Morpholino)butanesulfonic acid), TRIS 완충제(Tris(hydroxymethyl)aminomethane), DIPSO 완충제(3-(N,N-Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid), PBS 완충제(Phosphate-buffered saline) 및 글라이신(glycine)로 이루어진 군에서 선택되는 어느 하나 이상을 포함할 수 있다.In addition, the buffering agents used to adjust the pH of the tannin include potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium hydrogen carbonate (NaHCO 3 ), bis-tris propane buffer, and BES buffer (N, N-bis). (2-hydroxyethyl)-2-aminoethanesulfonic acid), MOPS buffer (3-(N-morpholino)propanesulfonic acid), HEPES buffer (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES Buffer (N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid), MOBS buffer (4-(N-Morpholino)butanesulfonic acid), TRIS buffer (Tris(hydroxymethyl)aminomethane), DIPSO buffer (3-(N,N- It may include one or more selected from the group consisting of Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid), PBS buffer (Phosphate-buffered saline), and glycine.
또한, 본 발명은 상기 제3 단계 이후, 균사체 매트를 가소제 용액으로 가소 처리하는 제4 단계를 더 포함할 수 있다.In addition, the present invention may further include a fourth step of plasticizing the mycelium mat with a plasticizer solution after the third step.
또한, 상기 가소제 용액은 에틸렌 글리콜(ehylene glycol), 에틸렌 글리세롤(ehylene glycerol), 글리세롤(glycerol), 폴리에틸렌글리콜(polyehylene glycerol, PEG), 폴리프로필렌글리콜(polypropylene glycol, PPG), 폴리소르베이트(Polysorbate), 사이클로덱스트린(cyclodextrin) 라벤더 오일 (lavender oil), 피마자 오일 (castor oil), 및 시남알데하이드(cinnamaldeyde)로 이루어진 군에서 선택되는 어느 하나 이상을 포함할 수 있다.In addition, the plasticizer solution includes ethylene glycol, ethylene glycerol, glycerol, polyethylene glycerol (PEG), polypropylene glycol (PPG), and polysorbate. , cyclodextrin, lavender oil, castor oil, and cinnamaldehyde.
본 발명에서는 식물성 탄닌을 이용하여 균사체 매트를 효과적으로 가교반응시킴으로써, 친환경적이면서도, 인장강도, 유연성, 내구성 등 물리적 특성이 향상된 균사체 매트 기반의 가죽을 제공할 수 있다.In the present invention, by effectively crosslinking the mycelium mat using vegetable tannin, it is possible to provide mycelium mat-based leather that is environmentally friendly and has improved physical properties such as tensile strength, flexibility, and durability.
도 1은 본 발명의 일실시예에 따라 제조된 균사체 매트를 이용한 가죽 샘플의 인장강도 측정 결과를 나타낸 그래프이다.Figure 1 is a graph showing the results of tensile strength measurement of leather samples using mycelium mat prepared according to an embodiment of the present invention.
도 2는 본 발명의 일실시예에 따라 제조된 균사체 매트를 이용한 가죽 샘플의 인장신율 측정 결과를 나타낸 그래프이다.Figure 2 is a graph showing the results of tensile elongation measurement of leather samples using mycelium mat prepared according to an embodiment of the present invention.
도 3은 본 발명의 일실시예에 따른 균사체 매트를 이용한 가죽을 제조하는 과정을 개략적으로 나타낸 도면이다.Figure 3 is a diagram schematically showing the process of manufacturing leather using mycelium mat according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 tara tannin과 pH 를 조절한 tara tannin으로 가교한 균사체 매트에 관한 사진이다.Figure 4 is a photograph of a mycelium mat cross-linked with tara tannin and pH-adjusted tara tannin according to an embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌(tannin)을 포함하는 균사체 매트(mat) 기반의 인조가죽 가교용 조성물을 제공하며, 상기 탄닌(tannin)의 pH는 7.5 내지 11.5인 것을 특징으로 할 수 있다.The present invention provides a composition for crosslinking artificial leather based on a mycelium mat containing tannin derived from a Caesalpinia spinosa extract, wherein the tannin has a pH of 7.5 to 11.5. can do.
소비자들의 도덕적인 소비에 대한 눈높이가 함께 높아짐에 따라 가죽을 얻기 위한 과정에서 광범위한 살육과 환경파괴가 없는 대체가죽(인조가죽)에 대한 요구도가 높아지고 있다.As consumers' awareness of ethical consumption increases, the demand for alternative leather (artificial leather) that does not involve extensive slaughter and environmental destruction in the process of obtaining leather is increasing.
하지만 인공가죽의 질감이 천연가죽과 차이가 많아 성형공정 과정이 까다로워지고, 염색 및 접착을 통한 가공성형 공정이 늘어나 제조공정 비용이 급격히 증가하고 있다.However, the texture of artificial leather is very different from that of natural leather, making the molding process more difficult, and the manufacturing cost is rapidly increasing as the number of molding processes through dyeing and adhesion increases.
아울러, 석유기반 폴리머를 사용하는 제조부터 분해가 잘 되지 않아 재활용이 불가능하여 산업 쓰레기로 폐기될 때까지 전 공정 내에서 심각한 환경오염이 발생하는 등 여러가지 문제에 직면하고 있다.In addition, it faces various problems, such as serious environmental pollution occurring throughout the entire process, from manufacturing using petroleum-based polymers to disposal as industrial waste as it is difficult to decompose and cannot be recycled.
식물성 탄닌은 자연계에 풍부한 식물성 폴리페놀 분자의 일종으로 자연계에 800 가지 이상의 종류가 존재한다. 탄닌은 수산화기(-OH)가 풍부하여 단백질을 응집시킬수 있다고 알려져 있으며, 분자량 3,000 Da 이하의 크기의 탄닌은 동물 피부의 섬유사 구조 내부로 침투할 수 있는 것으로 알려져 있다.Vegetable tannin is a type of plant polyphenol molecule that is abundant in nature, and more than 800 types exist in nature. It is known that tannin is rich in hydroxyl groups (-OH) and can aggregate proteins, and tannin with a molecular weight of 3,000 Da or less is known to be able to penetrate into the fiber structure of animal skin.
식물 유래 탄닌은 축합성 탄닌(condensed tannin), 가수분해성 탄닌(hydrolysable tannin)으로 나눌 수 있으며, 동물피혁의 가죽화에 흔히 이용되는 탄닌은 참나무(oak), 가문비나무피(spruce bark), 밤나무(chestnuts), 윌로우바크(willow bark), 발로네아(valonea), 미모사(mimosa), 타라(tara), 케브라초(quebracho) 등으로부터 추출된 탄닌을 이용할 수 있다.Plant-derived tannins can be divided into condensed tannins and hydrolysable tannins. Tannins commonly used in leathering animal skins include oak, spruce bark, and chestnut ( Tannin extracted from chestnuts, willow bark, valonea, mimosa, tara, quebracho, etc. can be used.
이중 타라(tara) 추출물에는 약간의 축합성 탄닌, 갈로탄닌(gallotannin) 및 에피갈로카테킨(epigallocatechin)을 포함할 수 있으며, 이들 물질들을 통해 pKa 인근의 pH 에서의 산화를 통해 다양한 소재의 표면 개질을 할 수 있는 것으로 알려져 있다. 에피갈로카테킨(epigallocatechin)의 pKa는 8 인근이고, 갈로탄닌(gallotannin)의 pKa는 6 인근이다.Among them, tara extract may contain some condensable tannin, gallotannin, and epigallocatechin, and these substances can be used to modify the surface of various materials through oxidation at a pH near the pKa. It is known that it can be done. The pKa of epigallocatechin is around 8, and the pKa of gallotannin is around 6.
본 발명자들은 상기와 같은 타라(tara) 추출물의 특성에 착안하여, 일반적으로 이용되는 타라(tara) 추출물로부터 유래한 탄닌의 pH를 조절함으로써, 균사체 매트 기반의 대체 가죽의 인장강도(tensile strength) 및 인장신율(tensile elongation)과 같은 물리적 특성을 향상시킨 균사체 매트(mat) 기반의 가죽 소재에 대한 본 발명을 완성하였다.Focusing on the characteristics of the tara extract as described above, the present inventors adjusted the pH of the tannin derived from the commonly used tara extract to improve the tensile strength and the tensile strength of mycelium mat-based alternative leather. The present invention for a mycelium mat-based leather material with improved physical properties such as tensile elongation was completed.
상기 타라(tara) 추출물로부터 유래한 탄닌의 pH는 7.5 내지 11.5, 바람직하게는 8~11, 더욱 바람직하게는 9~10 일 수 있다.The pH of the tannin derived from the tara extract may be 7.5 to 11.5, preferably 8 to 11, and more preferably 9 to 10.
바람직한 구체예로서, 상기 타라(tara) 추출물로부터 유래한 탄닌의 pH는 8~9, 8~10, 8~11, 9~10, 9~11 또는 10~11 일 수 있다. As a preferred embodiment, the pH of the tannin derived from the tara extract may be 8 to 9, 8 to 10, 8 to 11, 9 to 10, 9 to 11, or 10 to 11.
다른 바람직한 구체예로서, 상기 타라(tara) 추출물로부터 유래한 탄닌의 pH는 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4 또는 11.5 일 수 있다.In another preferred embodiment, the pH of the tannin derived from the tara extract is 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0. , 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11 .2, 11.3, 11.4 or 11.5 It can be.
본 발명에서는 타라(tara) 추출물로부터 유래한 탄닌의 pH가 7.5~11.5가 되었을 때 가교반응이 최적화함을 확인하였고, 상기 최적화된 타라(tara) 추출물로부터 유래한 탄닌을 활용하여 균사체 매트를 활용하여 가죽을 제조하였을 때 인장강도 및 인장신율이 현저히 향상되었음을 확인하였다(실시예 1~3, 실험예 1 및 실험예 2).In the present invention, it was confirmed that the cross-linking reaction was optimized when the pH of the tannin derived from the tara extract was 7.5 to 11.5, and the tannin derived from the optimized tara extract was utilized to utilize a mycelium mat. It was confirmed that the tensile strength and tensile elongation were significantly improved when leather was manufactured (Examples 1 to 3, Experimental Examples 1 and 2).
본 발명은 균사체 매트를 불활성화 시키는 제1 단계; 상기 균사체 매트에 다당류 용액이 침투하도록 하는 제2 단계; 및 상기 다당류 용액이 침투된 균사체 매트에 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌을 포함하는 용액이 침투하도록 하는 제3 단계;를 포함하는, 균사체 매트를 가죽으로 제조하는 방법을 제공한다.The present invention includes a first step of inactivating the mycelium mat; A second step of allowing the polysaccharide solution to penetrate the mycelium mat; And a third step of allowing a solution containing tannin derived from a tara ( Caesalpinia spinosa ) extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated. It provides a method of manufacturing a mycelium mat into leather, including a.
본 발명에서는 균사체 매트를 불활성화 하는 제1 단계 과정이 포함될 수 있고, 여기에는 멸균, 초음파 처리, 화학적 처리 등의 방법이 사용될 수 있다.In the present invention, a first step process of inactivating the mycelium mat may be included, and methods such as sterilization, ultrasonic treatment, and chemical treatment may be used here.
상기 멸균 방식은 멸균기(autoclave)를 이용하는 방식으로, 살아있는 균사체를 의학적으로 생물이 살 수 있는 최대 극한의 온도 119 ℃, 1.2 기압보다 높은 온도와 압력조건에서 멸균하는 방식일 수 있으며, 구체적으로 121 ℃, 1.5 기압에서 30 분간 멸균하여 균사체 매트를 불활성화 할 수 있다.The sterilization method uses an autoclave, and may be a method of sterilizing living mycelium under temperature and pressure conditions higher than the maximum temperature at which organisms can live medically, 119°C and 1.2 atm, specifically 121°C. , the mycelial mat can be inactivated by sterilizing at 1.5 atm for 30 minutes.
상기 초음파를 이용한 균사체 매트의 불활성화는 35~50Hz의 주파수 범위에서 살아있는 균사체를 증류수에 투입하고 2시간 동안 수행할 수 있다.Inactivation of the mycelium mat using ultrasound can be performed for 2 hours by adding live mycelium to distilled water in the frequency range of 35 to 50 Hz.
상기 화학적 처리 방식은 과산화수소(H2O2), 차아염소산소듐(NaClO), 수산화소듐(NaOH) 등을 이용하여 균사체 매트를 불활성화하는 방식일 수 있다.The chemical treatment method may be a method of inactivating the mycelium mat using hydrogen peroxide (H 2 O 2 ), sodium hypochlorite (NaClO), sodium hydroxide (NaOH), etc.
상기 과산화수소 용액은 효소와 반응하여 활성산소 또는 산소 라디칼을 발생하여 세포벽이나 세포막을 녹일 수 있는 물질로, 3%의 과산화수소 용액은 의료용으로 흔히 쓰이고 있다.The hydrogen peroxide solution is a substance that can dissolve cell walls or cell membranes by reacting with enzymes to generate active oxygen or oxygen radicals, and a 3% hydrogen peroxide solution is commonly used for medical purposes.
본 발명에서의 과산화수소 용액을 이용하는 처리 방식에서 과산화수소의 농도는 과산화 수소 전체 용액 부피 대비 5~30%일 수 있으며, 균사체 매트를 1분~2시간 동안 25~60 ℃ 온도 조건에서 상기 용액에 침지하여 수행될 수 있다. 이때, 과산화수소의 농도는 전체 용액 부피 대비 10~30%라면 초음파 처리가 과산화수소 용액 처리 이전에 1시간 이상으로 수행되어야 한다.In the treatment method using a hydrogen peroxide solution in the present invention, the concentration of hydrogen peroxide may be 5 to 30% of the total volume of the hydrogen peroxide solution, and the mycelium mat is immersed in the solution at a temperature of 25 to 60 ° C. for 1 minute to 2 hours. It can be done. At this time, if the concentration of hydrogen peroxide is 10 to 30% of the total solution volume, ultrasonic treatment must be performed for more than 1 hour before treating the hydrogen peroxide solution.
상기 차아염소산소듐은 락스의 주 성분으로 알려져 있으며, 용도에 따라 희석하여 살균을 목적으로 사용될 수 있다.Sodium hypochlorite is known as the main ingredient of bleach, and can be diluted depending on the intended use and used for sterilization.
본 발명에서의 차아염소산소듐 용액을 이용하는 처리 방식에서 차아염소산산소듐의 농도는 전체 용액 부피 대비 0~30% 일 수 있으며, 균사체 매트를 1분~2시간 동안 25~60 ℃ 온도 조건에서 상기 용액에 침지하여 수행될 수 있다. 이때, 균사체를 불활성화 하기 위해서는 차아염소산소듐이 5% 이상 포함된 용액을 이용하여 1시간 이상 초음파처리를 하여 침지하거나, 초음파 처리 없이는 5% 이상의 차아염소산소듐 용액에서 2시간 이상 침지하는 것이 바람직하다.In the treatment method using the sodium hypochlorite solution in the present invention, the concentration of sodium hypochlorite may be 0 to 30% of the total solution volume, and the mycelium mat is treated with the solution at a temperature of 25 to 60 ° C for 1 minute to 2 hours. It can be performed by immersion in . At this time, in order to inactivate the mycelium, it is preferable to immerse in a solution containing more than 5% sodium hypochlorite by ultrasonic treatment for more than 1 hour, or to immerse in a solution containing more than 5% sodium hypochlorite for more than 2 hours without ultrasonic treatment. .
본 발명에서는 균사체 매트에 다당류 용액이 침투하도록 하는 제2 단계가 포함될 수 있는데, 여기에서 균사체의 키틴은 상대적으로 음이온을 띄고, 상기 다당류는 상대적으로 양이온을 띄므로, 상기 다당류는 정전기적 인력을 통해 균사체 매트를 가교하는 역할을 할 수 있다.The present invention may include a second step of allowing the polysaccharide solution to penetrate the mycelium mat, where the chitin of the mycelium is relatively anionic and the polysaccharide is relatively cationic, so the polysaccharide is absorbed through electrostatic attraction. It can play a role in cross-linking the mycelium mat.
또한, 상기 다당류 용액은 키토산(chitosan), 카파-카라기난(k-carrageenan), 아이오타-카라기난(I-carrageenan), 람다-카라기난(L-carrageenan), 구아검(Guar gum), 잔탄(xanthan), 아라비아 검(Gum Arabic), 펙틴(pectin), 펩톤(peptone), 곤약(konjac), 덱스트란(dextran), 헤파린(heparin) 및 후코이단(fucoidan)으로 이루어진 군에서 선택되는 어느 하나 이상을 포함할 수 있다.In addition, the polysaccharide solution includes chitosan, kappa- carrageenan , iota-carrageenan, l -carrageenan, l -carrageenan, guar gum, and xanthan. , Gum Arabic, pectin, peptone, konjac, dextran, heparin, and fucoidan. You can.
본 발명에서는 불활성화된 균사체 매트에 키토산(chitosan) 및 아디프산(adipic acid)을 침투시킬 수 있는데, 단순히 키토산 및 아디프산을 침투시킨 후 단순 건조한 후에 하는 가열 압착은 키토산의 아민기(amine group)와 아디프산의 카르복실기(carboxyl group) 사이에서 일어날 수 있는 결합인 아미드(amide) 결합을 통한 가교 처리(cross-linking)하기에는 부적합할 수 있다.In the present invention, chitosan and adipic acid can be infiltrated into the inactivated mycelium mat. Heat pressing after simply infiltrating chitosan and adipic acid and drying is performed to remove the amine group of chitosan. It may be unsuitable for cross-linking through an amide bond, which is a bond that can occur between adipic acid and the carboxyl group of adipic acid.
따라서, 본 발명에서는 상기 다당류 용액이 침투된 균사체 매트에 타라(tara) 추출물로부터 유래한 탄닌을 포함하는 용액이 침투하도록 하는 제3 단계가 포함될 수 있다.Therefore, the present invention may include a third step of allowing a solution containing tannin derived from tara extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated.
상기 타라(tara) 추출물로부터 유래한 탄닌의 갈롤기는 약염기성의 조건에서 산화가 일어나며 퀴논을 형성할 수 있으며, 산화된 갈롤기의 퀴논은 키토산과 균사체 매트에 포함되어 있는 친핵성 작용기(아민기, 티올기)와 반응하여 친핵성 첨가반응이 일어나거나 탈수축합 반응으로 이민결합 형성 등의 공유결합을 할 수 있다.The gallol group of the tannin derived from the tara extract can be oxidized under weakly basic conditions to form quinone, and the quinone of the oxidized gallol group is a nucleophilic functional group (amine group, A nucleophilic addition reaction can occur by reacting with a thiol group, or a covalent bond such as an imine bond can be formed through a dehydration condensation reaction.
상기 제3단계에서 사용되는 타라(tara) 추출물로부터 유래한 탄닌을 포함하는 용액은 완충제 등을 이용하여 그 pH를 7.5 내지 11.5로 조절하는 것을 특징으로 할 수 있다. 상기 타라(tara) 추출물로부터 유래한 탄닌의 pH는 7.5 내지 11.5, 바람직하게는 8~11, 더욱 바람직하게는 9~10 일 수 있다.The solution containing tannin derived from the tara extract used in the third step may be characterized in that its pH is adjusted to 7.5 to 11.5 using a buffer or the like. The pH of the tannin derived from the tara extract may be 7.5 to 11.5, preferably 8 to 11, and more preferably 9 to 10.
상기 타라(tara) 추출물로부터 유래한 탄닌의 pH는 7.5~11.5인 것을 특징으로 할 수 있고, 조절된 pH가 7.5 미만일 경우에는 탄닌의 갈롤기의 산화를 통한 퀴논의 형성이 적어져 균사체의 가교 처리가 충분하기 못할 수 있고, 조절된 pH가 11.5를 초과할 경우에는 타라(tara) 추출물로부터 유래한 탄닌이 강한 염기성 조건에서 에스테르기(-COO-)가 끊어지면서 가교결합을 잃을 수 있는 문제가 발생할 수 있다.The pH of the tannin derived from the tara extract can be characterized as being 7.5 to 11.5, and when the adjusted pH is less than 7.5, the formation of quinone through oxidation of the gallol group of tannin is reduced, resulting in cross-linking treatment of the mycelium. may not be sufficient, and if the adjusted pH exceeds 11.5, a problem may occur in which tannin derived from tara extract may lose cross-linking as the ester group (-COO-) is broken under strong basic conditions. You can.
상기와 같이 탄닌산의 pH가 7.5 내지 11.5의 범위에서 조절하여 가교반응을 최적화함으로써, 균사체 매트를 가죽으로 제조하였을 때 상기 범위에서 인장강도 및 인장신률이 현저히 향상되었음을 확인할 수 있었다(실시예 1~3, 실험예 1 및 실험예 2).By optimizing the crosslinking reaction by adjusting the pH of tannic acid in the range of 7.5 to 11.5 as described above, it was confirmed that the tensile strength and tensile elongation were significantly improved in the above range when the mycelium mat was manufactured into leather (Examples 1 to 3 , Experimental Example 1 and Experimental Example 2).
상기 완충제는 수산화칼륨(KOH), 수산화소듐(NaOH), 탄산수소소듐(NaHCO3), bis-tris propane 완충제, BES 완충제(N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), MOPS 완충제(3-(N-morpholino)propanesulfonic acid), HEPES 완충제(2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES 완충제(N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonicd acid), MOBS 완충제(4-(N-Morpholino)butanesulfonic acid), TRIS 완충제(Tris(hydroxymethyl)aminomethane), DIPSO 완충제(3-(N,N-Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid), PBS 완충제(Phosphate-buffered saline) 및 글라이신(glycine)으로 이루어진 군에서 선택된 어느 하나 이상일 수 있으며, 가장 바람직하게는 수산화소듐(NaOH)이 사용될 수 있지만, 이에 한정되지 않으며 pH를 변화시킬 수 있는 통상적으로 사용되는 완충제는 모두 사용 가능하다.The buffering agents include potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium hydrogen carbonate (NaHCO 3 ), bis-tris propane buffer, BES buffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), and MOPS. Buffer (3-(N-morpholino)propanesulfonic acid), HEPES buffer (2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid), TES buffer (N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid) acid), MOBS buffer (4-(N-Morpholino)butanesulfonic acid), TRIS buffer (Tris(hydroxymethyl)aminomethane), DIPSO buffer (3-(N,N-Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid ), PBS buffer (Phosphate-buffered saline), and glycine (glycine). Most preferably, sodium hydroxide (NaOH) can be used, but is not limited to this and can change the pH. All commonly used buffering agents can be used.
또한, 본 발명은 상기 제3 단계 이후, 균사체 매트를 가소제 용액으로 가소 처리하는 제4 단계를 더 포함할 수 있다.In addition, the present invention may further include a fourth step of plasticizing the mycelium mat with a plasticizer solution after the third step.
본 발명에서 사용된 용어 "가소제(plasticize)"는 물질의 점성을 줄이거나 소성을 줄이는 첨가제로써, 고분자의 연화점, 유리 전이점, 열적, 기계적 성질 등의 물리적 속성을 변화시키기 위해 추가되는 물질을 의미할 수 있으며, 플라스틱의 제조에 통상적으로 사용되는 물질일 수 있다.The term "plasticizer" used in the present invention refers to an additive that reduces the viscosity or plasticity of a material and is added to change physical properties such as softening point, glass transition point, thermal and mechanical properties of a polymer. It may be a material commonly used in the manufacture of plastic.
또한, 상기 가소제 용액은 에틸렌 글리콜(ehylene glycol), 에틸렌 글리세롤(ehylene glycerol), 글리세롤(glycerol), 폴리에틸렌글리콜(polyehylene glycerol, PEG), 폴리프로필렌글리콜(polypropylene glycol, PPG), 폴리소르베이트(Polysorbate), 사이클로덱스트린(cyclodextrin) 라벤더 오일(lavender oil), 피마자 오일(castor oil), 및 시남알데하이드(cinnamaldeyde)로 이루어진 군에서 선택되는 어느 하나 이상을 포함할 수 있다.In addition, the plasticizer solution includes ethylene glycol, ethylene glycerol, glycerol, polyethylene glycerol (PEG), polypropylene glycol (PPG), and polysorbate. , cyclodextrin, lavender oil, castor oil, and cinnamaldehyde.
본 발명의 구체적인 일 실시예에서, pH가 조절된 타라(tara) 추출물로부터 유래한 탄닌을 포함하는 인조가죽 가교용 조성물을 사용하여 균사체 매트 기반의 가죽 샘플을 제조하였고, 제조한 가죽의 인장강도 및 인장신율을 측정하였다(실험예1, 실험예 2).In a specific embodiment of the present invention, a mycelium mat-based leather sample was prepared using a composition for cross-linking artificial leather containing tannin derived from a pH-adjusted tara extract, and the tensile strength and tensile strength of the produced leather were measured. Tensile elongation was measured (Experimental Example 1, Experimental Example 2).
이하, 본 발명을 실시예 및 실험예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail through examples and experimental examples.
다만, 하기 실시예 및 실험예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예 및 실험예에 의하여 한정되는 것은 아니다.However, the following examples and experimental examples are merely illustrative of the present invention, and the content of the present invention is not limited by the following examples and experimental examples.
제조예: 균사체 매트(mat)의 추출Preparation example: Extraction of mycelium mat
<종균 배양><Spring culture>
PDA(potato dextrose agar)를 90 mm 페트리 디쉬(petri dish)에 분주하여 5분간 굳힌 후 PDA 배지를 준비하였다.PDA (potato dextrose agar) was dispensed into a 90 mm Petri dish and allowed to harden for 5 minutes to prepare a PDA medium.
무균대에서 목질계 버섯(Ganoderma sp., Fomitella Sp. Inonotus sp. 등) 균사체의 절편을 잘라내 PDA 배지에 이식하여 28 ℃에서 7일간 배양기에서 배양하였다.Fragments of lignocellulosic mushroom ( Ganoderma sp., Fomitella Sp. Inonotus sp., etc.) mycelium were cut from the sterile zone, transplanted into PDA medium, and cultured in an incubator at 28°C for 7 days.
PDA 배지에서 배양한 균주의 절편을 크기가 10mm2가 되도록 5개로 잘라 YPDB(potato dextrose broth containing 0.5% yeast extract) 액체배지 500 mL에 접종하여 180 rpm으로 교반하면서, 25 ℃에서 7일간 종균을 배양하였다.Cut the fragments of the strain cultured in PDA medium into 5 pieces with a size of 10mm 2 and inoculate them in 500 mL of YPDB (potato dextrose broth containing 0.5% yeast extract) liquid medium and culture the seeds at 25°C for 7 days while stirring at 180 rpm. did.
<액체 배양><Liquid culture>
25 ℃에서 덱스트로스(dextrose) 40 g, 효모 추출물(yeast extract) 20 g 및 구아검(guar-gum) 20 g을 증류수 920mL에 혼합하여 영양성분 조성물을 준비하였다. 또한, 황산마그네슘(MgSO4) 0.5g, 탄산칼슘(CaCO3) 0.5g, 인산칼륨(KH2PO4) 0.5g 및 염화칼슘(CaCl2) 0.5g을 25℃에서 증류수 998mL에 용해하여 무기염류 조성물을 준비하였다.A nutritional composition was prepared by mixing 40 g of dextrose, 20 g of yeast extract, and 20 g of guar gum with 920 mL of distilled water at 25°C. Additionally, 0.5 g of magnesium sulfate (MgSO 4 ), 0.5 g of calcium carbonate (CaCO 3 ), and 0.5 g of potassium phosphate (KH 2 PO 4 ). And 0.5 g of calcium chloride (CaCl 2 ) was dissolved in 998 mL of distilled water at 25°C to prepare an inorganic salt composition.
상기 영양성분 조성물 및 무기염류 조성물을 혼합하고, 교반 장치(DAIHAN scientific, HT-120DX)를 통해 25 ℃에서 200rpm의 속도로 10분간 교반하여 2L의 배지 조성물을 준비하였다.The nutrient composition and the inorganic salt composition were mixed and stirred for 10 minutes at a speed of 200 rpm at 25° C. using a stirring device (DAIHAN scientific, HT-120DX) to prepare a 2 L medium composition.
상기 배지 조성물을 멸균기(autoclave)를 통해 132℃에서 5kgf/cm2의 증기압으로 25분간 멸균하였고, 멸균된 배지 조성물을 25 ℃까지 냉각시켜 반액상 배지를 준비하고, 1/2밧드에 1000 mL까지 채워 넣었다.The medium composition was sterilized through an autoclave at 132°C and a vapor pressure of 5kgf/cm 2 for 25 minutes, and the sterilized medium composition was cooled to 25°C to prepare a semi-liquid medium, adding up to 1000 mL in a 1/2 bag. Filled it in.
상기 종균 배양 단계에서 25 ℃에서 7일간 배양된 종균을 포함하는 조성물 200 mL를 상기 반액상 배지 1000 mL에 접종한 후, 필터 및 통풍구가 있는 뚜껑을 덮어 28 ℃, 습도 90% 조건에서 4주간 암기에서 배양하였고, 살아있는 균사체 매트 300 g을 추출하였다.In the seed culture step, 200 mL of the composition containing the seed cultured for 7 days at 25 ℃ was inoculated into 1000 mL of the semi-liquid medium, then covered with a lid with a filter and a vent and darkened for 4 weeks at 28 ℃ and 90% humidity. was cultured, and 300 g of live mycelium mat was extracted.
실시예 1: 식물유래 탄닌을 활용한 균사체 매트 기반 대체가죽의 제조 - pH 8 조건Example 1: Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 8 conditions
제조예에서 추출된 균사체 매트를 60 ℃ 조건에서 30% 과산화수소 400 mL에 침지하여, 60 ℃의 온도로 35 kHz로 2시간 동안 초음파 처리를 하였다.The mycelium mat extracted in the preparation example was immersed in 400 mL of 30% hydrogen peroxide at 60°C and sonicated at 35 kHz for 2 hours at a temperature of 60°C.
25 ℃에서 키토산 8 g, 아디프산 8 g 및 증류수를 혼합하여 2%(w/v) 키토산 용액 400 mL를 제조한 후, 상기 키토산 용액에 상기 초음파 처리된 균사체 매트를 25 ℃에서 1일간 침지처리 하였다.After preparing 400 mL of 2% (w/v) chitosan solution by mixing 8 g of chitosan, 8 g of adipic acid, and distilled water at 25 ° C, the sonicated mycelium mat was immersed in the chitosan solution for 1 day at 25 ° C. processed.
25 ℃에서 Tara tannin(Ormotan T社, SILVATEAM) 4 g을 증류수 400 mL과 혼합하여 Tara tannin 용액(농도: 10 g/L)을 제조하여 pH가 7임을 확인한 후, 수산화소듐(NaOH) 수 80 mg 과 혼합하여 pH를 8로 조절하였다.Prepare a Tara tannin solution (concentration: 10 g/L) by mixing 4 g of Tara tannin (Ormotan T, SILVATEAM) with 400 mL of distilled water at 25°C. After confirming that the pH is 7, add 80 mg of sodium hydroxide (NaOH). The pH was adjusted to 8 by mixing.
이후, 상기 키토산 용액에 침지처리 된 균사체 매트를 상기 pH가 8로 조절된 Tara tannin 용액에 25 ℃에서 2시간 동안 침지하였다.Thereafter, the mycelium mat immersed in the chitosan solution was immersed in the Tara tannin solution whose pH was adjusted to 8 at 25°C for 2 hours.
폴리에틸렌글리콜(poly-ethylene glycol, PEG) 60 mL을 증류수 340 mL과 25 ℃에서 혼합하여 15% 폴리에틸렌글리콜 용액 400 mL를 제조한 후, 상기 Tara tannin 용액에 침지 처리된 균사체 매트를 상기 제조된 15% 폴리에틸렌글리콜 용액 400 mL에 침지처리 하고, 25 ℃에서 6시간 동안 200 rpm으로 교반하였다.60 mL of poly-ethylene glycol (PEG) was mixed with 340 mL of distilled water at 25°C to prepare 400 mL of a 15% polyethylene glycol solution, and then the mycelium mat immersed in the Tara tannin solution was mixed with the prepared 15% polyethylene glycol solution. It was immersed in 400 mL of polyethylene glycol solution and stirred at 200 rpm for 6 hours at 25°C.
상기 폴리에틸렌글리콜(poly-ethylene glycol, PEG) 용액에 침지 처리된 균사체 매트를 40 ℃에서 24시간 이상 건조하여 수분을 제거한 후 90 ℃에서 98 MPa의 압력으로 20초 동안 열 압착 장치(custom village, CDH-4050)를 이용하여 열 압착하여, 가로 25 cm, 세로 20 cm, 두께 0.3 cm인 균사 가죽을 제조하였다.The mycelium mat soaked in the poly-ethylene glycol (PEG) solution was dried at 40°C for more than 24 hours to remove moisture, and then heat-pressed at 90°C at a pressure of 98 MPa for 20 seconds (custom village, CDH). -4050) was used to produce mycelial leather measuring 25 cm wide, 20 cm long, and 0.3 cm thick.
상기의 실험과정을 반복하여 가로 25 cm, 세로 20 cm, 두께 0.3 cm인 균사 가죽 샘플을 5개를 준비하였다.By repeating the above experimental process, five mycelial leather samples measuring 25 cm wide, 20 cm long, and 0.3 cm thick were prepared.
실시예 2: 식물유래 탄닌을 활용한 균사체 매트 기반 대체가죽의 제조 - pH 9 조건Example 2: Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 9 conditions
실시예 1과 동일한 방법으로 실험을 수행하되, Tara tannin 용액을 수산화소듐(NaOH) 0.8 g과 혼합하여 pH를 9로 조절한 것에 균사체 매트를 침지하였다. The experiment was performed in the same manner as in Example 1, except that the mycelium mat was immersed in a Tara tannin solution mixed with 0.8 g of sodium hydroxide (NaOH) to adjust the pH to 9.
실시예 3: 식물유래 탄닌을 활용한 균사체 매트 기반 대체가죽의 제조 - pH 11 조건Example 3: Preparation of mycelium mat-based alternative leather using plant-derived tannin - pH 11 conditions
실시예 1과 동일한 방법으로 실험을 수행하되, Tara tannin 용액을 수산화소듐(NaOH) 2 g과 혼합하여 pH를 9로 조절한 것에 균사체 매트를 침지하였다.The experiment was performed in the same manner as in Example 1, except that the mycelium mat was immersed in a Tara tannin solution mixed with 2 g of sodium hydroxide (NaOH) to adjust the pH to 9.
비교예 1: 키토산 용액으로만 침지처리한 균사체 매트 기반 대체가죽의 제조Comparative Example 1: Preparation of mycelium mat-based alternative leather immersed only in chitosan solution
제조예에서 추출된 균사체 매트를 60 ℃ 조건에서 30% 과산화수소 400 mL에 침지하여, 60 ℃의 온도로 35 kHz로 2시간 동안 초음파 처리를 하였다.The mycelium mat extracted in the preparation example was immersed in 400 mL of 30% hydrogen peroxide at 60°C and sonicated at 35 kHz for 2 hours at a temperature of 60°C.
25 ℃에서 키토산 8g, 아디프산 8g 및 증류수를 혼합하여 2% 키토산 용액 400 mL를 제조한 후, 상기 키토산 용액에 상기 초음파 처리된 균사체 매트를 25 ℃에서 1일간 침지처리 하였다.400 mL of a 2% chitosan solution was prepared by mixing 8 g of chitosan, 8 g of adipic acid, and distilled water at 25°C, and then the sonicated mycelium mat was immersed in the chitosan solution for 1 day at 25°C.
폴리에틸렌글리콜(poly-ethylene glycol, PEG) 60 mL을 증류수 340 mL과 25 ℃에서 혼합하여 15% 폴리에틸렌글리콜 용액 400 mL를 제조한 후, 상기 키토산 용액에 침지 처리된 균사체 매트를 상기 제조된 15% 폴리에틸렌글리콜 용액 400 mL에 침지처리 하고, 25 ℃에서 6시간 동안 200rpm으로 교반하였다.60 mL of poly-ethylene glycol (PEG) was mixed with 340 mL of distilled water at 25°C to prepare 400 mL of a 15% polyethylene glycol solution, and then the mycelium mat immersed in the chitosan solution was mixed with the 15% polyethylene prepared above. It was immersed in 400 mL of glycol solution and stirred at 200 rpm for 6 hours at 25°C.
상기 폴리에틸렌글리콜(poly-ethylene glycol, PEG) 용액에 침지 처리된 균사체 매트를 40 ℃에서 24시간 이상 건조하여 수분을 제거한 후 90 ℃에서 98 MPa의 압력으로 20초 동안 열 압착 장치(custom village, CDH-4050)를 이용하여 열 압착하여, 가로 25 cm, 세로 20 cm, 두께 0.3 cm인 균사 가죽을 제조하였다.The mycelium mat soaked in the poly-ethylene glycol (PEG) solution was dried at 40°C for more than 24 hours to remove moisture, and then heat-pressed at 90°C at a pressure of 98 MPa for 20 seconds (custom village, CDH). -4050) was used to produce mycelial leather measuring 25 cm wide, 20 cm long, and 0.3 cm thick.
상기의 실험과정을 반복하여 가로 25 cm, 세로 20 cm, 두께 0.3 cm인 균사 가죽 샘플을 5개를 준비하였다. The above experimental process was repeated to prepare five mycelial leather samples measuring 25 cm wide, 20 cm long, and 0.3 cm thick.
비교예 2: 식물유래 탄닌을 활용한 균사체 매트 기반 대체가죽의 제조 - pH 7 조건Comparative Example 2: Manufacturing of mycelium mat-based alternative leather using plant-derived tannin - pH 7 conditions
실시예 1과 동일한 방법으로 실험을 수행하되, 수산화소듐(NaOH) 10 mg 과 혼합하여 pH를 7로 조절하는 과정으로 대체하였다.The experiment was performed in the same manner as in Example 1, except that the pH was adjusted to 7 by mixing with 10 mg of sodium hydroxide (NaOH).
비교예 3: 식물유래 탄닌을 활용한 균사체 매트 기반 대체가죽의 제조 - pH 12 조건Comparative Example 3: Manufacturing of mycelium mat-based alternative leather using plant-derived tannin - pH 12 conditions
실시예 1과 동일한 방법으로 실험을 수행하되, 수산화소듐(NaOH) 4 g 과 혼합하여 pH를 12로 조절하는 과정으로 대체하였다.The experiment was performed in the same manner as in Example 1, except that the pH was adjusted to 12 by mixing with 4 g of sodium hydroxide (NaOH).
실험예 1: 인장강도 측정Experimental Example 1: Tensile strength measurement
tara tannin을 이용한 균사체 매트 기반의 대체가죽 제조에 있어서, tara tannin의 pH를 조절하였을 때의 인장강도 향상을 확인하기 위해, 실시예 1~3, 비교예 1~3에서 제조된 균사 가죽 샘플의 인장강도를 측정하였다.In the production of mycelium mat-based alternative leather using tara tannin, in order to confirm the improvement in tensile strength when the pH of tara tannin was adjusted, the tensile strength of the mycelium leather samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured. The intensity was measured.
인장강도는 인장시험기(QMESYS 社)를 사용하여 실시예 1~3, 비교예 1~3에서 제조된 균사가죽 샘플을 인장시험기에 물려서 100mm/min으로 인장하여 가죽 샘플이 파단할 때의 최대 인장강도(N)을 구한 후, 실시예 1~3, 비교예 1~3에서 각 샘플 5개의 평균 인장강도 값을 구했고, 비교예 1의 평균 인장강도 값을 1로 하였을 때, 상대적인 인장강도의 크기를 하기의 표 1에 나타냈다.The tensile strength is the maximum tensile strength when the leather sample breaks by placing the mycelial leather samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 using a tensile tester (QMESYS) and pulling at 100 mm/min. After calculating (N), the average tensile strength value of each of the five samples in Examples 1 to 3 and Comparative Examples 1 to 3 was obtained, and when the average tensile strength value of Comparative Example 1 was set to 1, the relative tensile strength was It is shown in Table 1 below.
그 결과, 표 1 및 도 1에 나타난 것과 같이, 키토산 용액으로만 침지처리(비교예 1)를 했거나, tara tannin의 pH를 7 또는 12로 조절(비교예 2, 비교예 3)한 것에 비하여, tara tannin의 pH를 8, 9 또는 11로 조절하였을 때(실시예 1~3)의 인장강도가 현저히 향상되었음을 확인할 수 있었다.As a result, as shown in Table 1 and Figure 1, compared to immersion treatment with only the chitosan solution (Comparative Example 1) or adjusting the pH of tara tannin to 7 or 12 (Comparative Examples 2 and 3), It was confirmed that when the pH of tara tannin was adjusted to 8, 9, or 11 (Examples 1 to 3), the tensile strength was significantly improved.
분류classification 침지처리 용액 조건Immersion treatment solution conditions 인장강도
(상대값)tensile strength
(relative value) 		인장강도
(단위: N)tensile strength
(Unit: N)
실시예 1Example 1 tara tannin의 pH를 8로 조절Adjust the pH of tara tannin to 8 1.561.56 218.21218.21
실시예 2Example 2 tara tannin의 pH를 9로 조절Adjust the pH of tara tannin to 9 1.641.64 235.19235.19
실시예 3Example 3 tara tannin의 pH를 11로 조절Adjust the pH of tara tannin to 11 1.601.60 229.15229.15
비교예 1Comparative Example 1 키토산 용액에만 침지Immerse only in chitosan solution 1One 143.22143.22
비교예 2Comparative Example 2 tara tannin의 pH를 7로 조절Adjust the pH of tara tannin to 7 0.910.91 130.54130.54
비교예 3Comparative Example 3 tara tannin의 pH를 12로 조절Adjust the pH of tara tannin to 12 0.630.63 89.9389.93
실험예 2: 인장신율 측정 tara tannin을 이용한 균사체 매트 기반의 대체가죽 제조에 있어서, tara tannin의 pH를 조절하였을 때의 인장신율의 향상을 확인하기 위해, 실시예 또는 비교예에서 제조된 균사 가죽 샘플의 인장신율을 측정하였다. Experimental Example 2: Measurement of tensile elongation In the production of alternative leather based on mycelium mat using tara tannin, mycelium leather samples prepared in Examples or Comparative Examples were used to confirm the improvement in tensile elongation when the pH of tara tannin was adjusted. The tensile elongation was measured.
인장신율은 각 분류군(하기의 표 2에 기재된 실시예 또는 비교예)의 균사 가죽 샘플을 5개씩 취하여 중앙에 표점을 표시하고 인장시험기(QMESYS 社)에 물리고(클램프 간격 40 mm) 인장속도 100 mm/min으로 인장하여 시험편이 파단할 때까지 최대 중량을 측정하였다. 인장신율은 아래 식 1에 따라서 계산하여 나타냈고, 각 샘플 5개의 평균 신율을 구하였다.Tensile elongation was measured by taking five mycelial leather samples from each taxonomic group (examples or comparative examples shown in Table 2 below), marking the center with a mark, and testing them in a tensile tester (QMESYS) (clamp spacing 40 mm) at a tensile speed of 100 mm. The maximum weight was measured until the test specimen broke by tensioning at /min. The tensile elongation was calculated and expressed according to Equation 1 below, and the average elongation of each sample of five was obtained.
(식 1) L = (L1-L0)/L0 (L: 인장신율 %, L0: 시험전 표점간의 거리, L1: 시험후 파단할 때의 표점간 거리 또는 균사가죽의 표피 또는 기포가 파단된 때의 표점 간 거리)(Equation 1) L = (L 1 -L 0 )/L 0 (L: Tensile elongation %, L 0 : Distance between gauges before test, L 1 : Distance between gauges when breaking after test or skin of mycelium leather or Distance between gauges when bubbles are broken)
비교예 1의 인장신율의 평균 인장신율 값을 1로 하였을 때, 상대적인 인장신율의 크기를 하기의 표 2에 나타냈다.When the average tensile elongation value of Comparative Example 1 was set to 1, the relative tensile elongation magnitude is shown in Table 2 below.
그 결과, 표 2 및 도 2에 나타난 것과 같이, 키토산 용액으로만 침지처리(비교예 1)를 했거나, tara tannin의 pH를 7 또는 12로 조절(비교예 2, 비교예 3)한 것에 비하여, tara tannin의 pH를 8, 9 또는 11으로 조절하였을 때(실시예 1~3)의 인장신율이 현저히 향상되었음을 확인할 수 있었다.As a result, as shown in Table 2 and Figure 2, compared to immersion treatment with only the chitosan solution (Comparative Example 1) or adjusting the pH of tara tannin to 7 or 12 (Comparative Examples 2 and 3), It was confirmed that when the pH of tara tannin was adjusted to 8, 9, or 11 (Examples 1 to 3), the tensile elongation was significantly improved.
분류classification 침지처리 용액 조건Immersion treatment solution conditions 인장신율
(상대값)tensile elongation
(relative value) 		인장신율
(단위: %)tensile elongation
(unit: %)
실시예 1Example 1 tara tannin의 pH를 8로 조절Adjust the pH of tara tannin to 8 1.481.48 44.3844.38
실시예 2Example 2 tara tannin의 pH를 9로 조절Adjust the pH of tara tannin to 9 1.501.50 45.3145.31
실시예 3Example 3 tara tannin의 pH를 11로 조절Adjust the pH of tara tannin to 11 1.381.38 42.8142.81
비교예 1Comparative Example 1 키토산 용액에만 침지Immerse only in chitosan solution 1One 31.0531.05
비교예 2Comparative Example 2 tara tannin의 pH를 7로 조절Adjust the pH of tara tannin to 7 0.870.87 26.8226.82
비교예 3Comparative Example 3 tara tannin의 pH를 12로 조절Adjust the pH of tara tannin to 12 0.490.49 15.3415.34
본 발명은 동물가죽 및 인조가죽을 대체할 수 있는 친환경 가죽 소재를 제조기 위한 방법에 관한 기술로서, 친환경적인 대체 소재 산업 분야에 매우 유용하다.The present invention is a technology for manufacturing an eco-friendly leather material that can replace animal leather and artificial leather, and is very useful in the eco-friendly alternative material industry.

Claims (10)

  1. 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌(tannin)을 포함하는 균사체 매트(mat) 기반의 인조가죽 가교용 조성물로서,A composition for crosslinking artificial leather based on a mycelium mat containing tannin derived from an extract of Caesalpinia spinosa ,
    상기 탄닌(tannin)의 pH는 7.5 내지 11.5인 것을 특징으로 하는, 균사체 매트(mat) 기반의 인조가죽 가교용 조성물.A composition for crosslinking artificial leather based on mycelium mat, characterized in that the pH of the tannin is 7.5 to 11.5.
  2. 제1항에 있어서,According to paragraph 1,
    상기 탄닌(tannin)의 pH는 8 내지 11인 것을 특징으로 하는, 균사체 매트(mat) 기반의 인조가죽 가교용 조성물.A composition for crosslinking artificial leather based on mycelium mat, characterized in that the pH of the tannin is 8 to 11.
  3. 제1항에 있어서,According to paragraph 1,
    상기 탄닌(tannin)의 pH는 9 내지 10인 것을 특징으로 하는, 균사체 매트(mat) 기반의 인조가죽 가교용 조성물.A composition for crosslinking artificial leather based on mycelium mat, characterized in that the pH of the tannin is 9 to 10.
  4. 균사체 매트를 불활성화 시키는 제1 단계;A first step of inactivating the mycelium mat;
    상기 균사체 매트에 다당류 용액이 침투하도록 하는 제2 단계; 및A second step of allowing the polysaccharide solution to penetrate the mycelium mat; and
    상기 다당류 용액이 침투된 균사체 매트에 타라(Caesalpinia spinosa) 추출물에서 유래한 탄닌을 포함하는 용액이 침투하도록 하는 제3 단계;를 포함하는 균사체 매트를 이용하여 가죽을 제조하는 방법.A method of producing leather using a mycelium mat comprising a third step of allowing a solution containing tannin derived from a tara ( Caesalpinia spinosa ) extract to penetrate into the mycelium mat into which the polysaccharide solution has been infiltrated.
  5. 제4항에 있어서,According to paragraph 4,
    상기 제3 단계의 상기 탄닌을 포함하는 용액은 pH는 7.5 내지 11.5인 것을 특징으로 하는, 균사체 매트를 이용하여 가죽을 제조하는 방법.A method of producing leather using a mycelium mat, wherein the solution containing the tannin in the third step has a pH of 7.5 to 11.5.
  6. 제4항에 있어서,According to paragraph 4,
    상기 제3 단계의 상기 탄닌을 포함하는 용액은 pH는 8 내지 11인 것을 특징으로 하는, 균사체 매트를 이용하여 가죽을 제조하는 방법.A method of producing leather using a mycelium mat, wherein the solution containing the tannin in the third step has a pH of 8 to 11.
  7. 제4항에 있어서,According to paragraph 4,
    상기 다당류 용액은 키토산(chitosan), 카파-카라기난(k-carrageenan), 아이오타-카라기난(I-carrageenan), 람다-카라기난(L-carrageenan), 구아검(Guar gum), 잔탄(xanthan), 아라비아 검(Gum Arabic), 펙틴(pectin), 펩톤(peptone), 곤약(konjac), 덱스트란(dextran), 헤파린(heparin) 및 후코이단(fucoidan)으로 이루어진 군에서 선택되는 어느 하나 이상인, 균사체 매트를 이용하여 가죽을 제조하는 방법.The polysaccharide solution includes chitosan, kappa-carrageenan ( k -carrageenan), iota-carrageenan ( I -carrageenan), lambda-carrageenan ( L -carrageenan), guar gum, xanthan, and arabic. Using a mycelium mat that is at least one selected from the group consisting of gum Arabic, pectin, peptone, konjac, dextran, heparin, and fucoidan. How to manufacture leather.
  8. 제4항에 있어서,According to paragraph 4,
    상기 균사체 매트를 불활성화 하는 것은 멸균, 초음파 처리, 또는 화학적 처리를 통해해서 수행되는 것을 특징으로 하는, 균사체 매트를 이용하여 가죽을 제조하는 방법.A method of producing leather using a mycelium mat, characterized in that inactivating the mycelium mat is performed through sterilization, sonication, or chemical treatment.
  9. 제4항에 있어서,According to paragraph 4,
    상기 제3 단계 이후, 균사체 매트를 가소제 용액으로 가소 처리하는 제4 단계를 더 포함하는, 균사체 매트를 이용하여 가죽을 제조하는 방법.After the third step, a method for producing leather using a mycelium mat further comprising a fourth step of plasticizing the mycelium mat with a plasticizer solution.
  10. 제9항에 있어서,According to clause 9,
    상기 가소제 용액은 에틸렌 글리콜(ehylene glycol), 에틸렌 글리세롤(ehylene glycerol), 글리세롤(glycerol), 폴리에틸렌글리콜(polyehylene glycerol, PEG), 폴리프로필렌글리콜(polypropylene glycol, PPG), 폴리소르베이트(Polysorbate), 사이클로덱스트린(cyclodextrin) 라벤더 오일 (lavender oil), 피마자 오일 (castor oil), 및 시남알데하이드(cinnamaldeyde)중 선택되는 어느 하나 이상인, 균사체 매트를 이용하여 가죽을 제조하는 방법.The plasticizer solution includes ethylene glycol, ethylene glycerol, glycerol, polyethylene glycerol (PEG), polypropylene glycol (PPG), polysorbate, and cyclo A method of producing leather using mycelium mat, which is at least one selected from cyclodextrin lavender oil, castor oil, and cinnamaldehyde.
PCT/KR2023/006047 2022-05-06 2023-05-03 Method for manufacturing mycelium into leather using plant-derived polyphenol group WO2023214798A1 (en)

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