WO2017179849A1 - Method for preparing green tea having reduced caffeine content by using supercritical extraction system - Google Patents
Method for preparing green tea having reduced caffeine content by using supercritical extraction system Download PDFInfo
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- WO2017179849A1 WO2017179849A1 PCT/KR2017/003728 KR2017003728W WO2017179849A1 WO 2017179849 A1 WO2017179849 A1 WO 2017179849A1 KR 2017003728 W KR2017003728 W KR 2017003728W WO 2017179849 A1 WO2017179849 A1 WO 2017179849A1
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- green tea
- caffeine
- extraction system
- supercritical extraction
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- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 244000269722 Thea sinensis Species 0.000 title claims abstract description 90
- 235000009569 green tea Nutrition 0.000 title claims abstract description 83
- 229960001948 caffeine Drugs 0.000 title claims abstract description 75
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000194 supercritical-fluid extraction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 11
- 150000001413 amino acids Chemical class 0.000 abstract description 10
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 abstract description 8
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 abstract description 7
- 235000005487 catechin Nutrition 0.000 abstract description 7
- 229950001002 cianidanol Drugs 0.000 abstract description 7
- 235000013616 tea Nutrition 0.000 abstract description 7
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 235000006708 antioxidants Nutrition 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 description 9
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000002292 Radical scavenging effect Effects 0.000 description 4
- 238000010835 comparative analysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Chemical compound C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 description 2
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229930013915 (+)-catechin Natural products 0.000 description 1
- 235000007219 (+)-catechin Nutrition 0.000 description 1
- 235000007246 (+)-epicatechin Nutrition 0.000 description 1
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 description 1
- 229930014124 (-)-epigallocatechin gallate Natural products 0.000 description 1
- 235000004911 (-)-epigallocatechin gallate Nutrition 0.000 description 1
- LSHVYAFMTMFKBA-UHFFFAOYSA-N ECG Natural products C=1C=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-UHFFFAOYSA-N 0.000 description 1
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010029216 Nervousness Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- VFSWRBJYBQXUTE-UHFFFAOYSA-N epi-Gallocatechin 3-O-gallate Natural products Oc1ccc2C(=O)C(OC(=O)c3cc(O)c(O)c(O)c3)C(Oc2c1)c4cc(O)c(O)c(O)c4 VFSWRBJYBQXUTE-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 235000019520 non-alcoholic beverage Nutrition 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F3/00—Tea; Tea substitutes; Preparations thereof
- A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
- A23F3/20—Removing unwanted substances
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F3/00—Tea; Tea substitutes; Preparations thereof
- A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
- A23F3/22—Drying or concentrating tea extract
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F5/00—Coffee; Coffee substitutes; Preparations thereof
- A23F5/02—Treating green coffee; Preparations produced thereby
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2300/00—Processes
- A23V2300/38—Multiple-step
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2300/00—Processes
- A23V2300/44—Supercritical state
Definitions
- It relates to a method for producing green tea having a reduced caffeine content using a supercritical extraction system.
- Tea is one of the world's three major non-alcoholic beverages. Tea contains various useful ingredients, and as various pharmacological effects have been scientifically identified, functional ingredients are extracted from tea leaves as well as beverages, and are being spotlighted as functional materials such as health functional foods, medicines, and cosmetics. Since green tea contains caffeine, it is less preferred by caffeine-sensitive consumers such as pregnant women, children, and the elderly. Compared to the overseas tea market, the reality is that Korea has few low caffeine products such as low caffeine green tea and low caffeine black tea. Caffeine is a kind of alkaloid. It is contained in coffee, tea, etc. When caffeine is absorbed by the human body, it acts on the central nervous system and wakes up the mind and reduces fatigue.
- caffeine is a substance that can cause nervousness, nausea and dizziness in people who do not fit their body.
- this patent only the caffeine component is analyzed by analyzing the method of preparing low-caffeine green tea using a supercritical extractor and analyzing the prepared low-caffeine green tea by catechin / caffeine, antioxidant activity, free amino acid, polyphenol content, and sensory test. We would like to propose a technique to be removed.
- An object of the present invention is to provide a method for producing a low-caffeine green tea in which only a caffeine content is specifically 80% or more removed compared to a general green tea product using a supercritical extraction system.
- a method for producing green tea having a reduced caffeine content using a supercritical extraction system comprising: mixing coarsely ground green tea with spirits (step 1); Reacting the mixed green tea at room temperature (step 2); Removing alcohol from the reacted green tea / alcohol mixture (step 3); Removing the caffeine component from the green tea / drink mixture from which the spirit was removed (step 4); It provides a method for producing green tea having a reduced caffeine content using a supercritical extraction system comprising the step (step 5) of drying the green tea / alcohol mixture from which the caffeine is removed.
- the alcohol is preferably pretanol A.
- the pretanol A is preferably added to about 100ml ⁇ 1000ml per 1kg green tea powder.
- the temperature of the second step is preferably 10 ⁇ 50 °C.
- the supercritical fluid is carbon dioxide
- the extraction temperature is 40 ⁇ 80 °C
- the extraction pressure is 100 bar ⁇ 500 bar
- the supercritical fluid provided 50ml It is preferable to extract caffeine for 2 to 4 hours at / hr ⁇ 300ml / hr.
- the drying of the green tea and alcohol mixture is preferably carried out for 4-6 hours at a temperature of 30 ⁇ 80 °C.
- the present invention uses a supercritical extraction system to remove low levels of caffeine, free amino acids, antioxidants and the like, while only removing caffeine content by more than 80%, compared to general green tea products. It can contribute to the creation of new tea consumption market in Korea and to increase income of related enterprises (farms).
- Figure 1 shows the overall manufacturing method for producing low caffeine green tea using a supercritical extraction system.
- Figure 2 shows the results of analyzing the caffeine content of the normal green tea and low caffeine green tea by HPLC.
- Figure 3 shows the results of analyzing the catechin content of ordinary green tea and low caffeine green tea by HPLC.
- Figure 4 shows the results of analyzing the free amino acid content of the normal green tea and low caffeine green tea with a free amino acid analyzer.
- Figure 5 shows the results of a comparative analysis of the total polyphenol content of normal green tea and low caffeine green tea.
- the present invention comprises the steps of mixing the crude green tea with alcohol (step 1), reacting the mixed green tea at room temperature (step 2), removing the alcohol from the reaction green tea / alcohol mixture (step 3) Second, comprising the step of removing the caffeine component (step 4) and drying the caffeine-free green tea / alcohol mixture (step 5) using the supercritical extraction system of the green tea / alcohol mixture from which the spirit is removed
- step 1 the crude green tea with alcohol
- step 2 reacting the mixed green tea at room temperature
- step 3 Second, comprising the step of removing the caffeine component (step 4) and drying the caffeine-free green tea / alcohol mixture (step 5) using the supercritical extraction system of the green tea / alcohol mixture from which the spirit is removed
- step 5 Provided is a method for producing green tea having a reduced caffeine content using a critical extraction system.
- the alcohol is generally fermented with a starch-containing water or sugar-containing water and distilled to 85 ° C or higher alcohol content. Since the ratio of ethanol is 95%, it may be 100ml to 1000ml per kg of green tea. It is not limited.
- the supercritical extraction system may have a pressure of 100 bar to 500 bar, but is not limited thereto.
- the amount of supercritical carbon dioxide used in the supercritical extraction system may be 50 ml to 300 ml per hour, the supercritical extraction temperature may be 40 °C to 80 °C, but is not limited thereto.
- the temperature for reacting the mixed green tea may be 10 ° C to 50 ° C, but is not limited thereto.
- the drying temperature of the green tea and spirit mixture from which the caffeine is removed may be 30 ° C. to 80 ° C., but is not limited thereto.
- a milled green tea powder was used to provide a general tea green tea raw material.
- a mixture of green tea and alcohol was put in a cloth bag for herbal medicine extraction to remove some alcohol by applying physical force.
- Carbon dioxide which was secured for food processing, was used as a supercritical fluid.
- the extraction temperature was 80 ° C.
- the extraction pressure was 400 bar
- the supercritical fluid supply amount was 200 ml / hr for 3 hours.
- the sample was dried in a drying oven at 60 ° C. for 5 hours to volatilize all of the remaining alcohol in the sample, and reduced the water content of the product to 10% or less.
- the catechin / caffeine contents of the low caffeine green tea prepared in Example 1 and regular green tea were analyzed.
- the column used for analysis was Tosho (ODS-80Tm. 4.6 * 150 mm), the flow rate was 1 mL / min, and the injection volume was 10 uL.
- ODS-80Tm. 4.6 * 150 mm The column used for analysis was Tosho (ODS-80Tm. 4.6 * 150 mm)
- the flow rate was 1 mL / min
- the injection volume was 10 uL.
- a low caffeine green tea was produced in the case of caffeine content is reduced by 87.2% caffeine as compared to the general green tea as shown in FIG.
- the polyphenol content of the low caffeine green tea prepared in Example 1 and general green tea was analyzed. Polyphenol content was measured by the Folin-Denis method. As a result, as shown in FIG. 5, the total polyphenol content was reduced by 5.8% to 93.37 mg / g of ordinary green tea and 87.92 mg / g of low caffeine green tea.
- Example 2 The content of free amino acids of low caffeine green tea and normal green tea prepared in Example 1 was analyzed.
- a free amino acid analyzer (Sykam S7130 Amino acid reagent organizer, Germany) was used, and UV / VIS detector 400 nm (1.0 AU) and 570 nm (1.0 AU) were detected.
- UV / VIS detector 400 nm (1.0 AU) and 570 nm (1.0 AU) were detected.
- the total free amino acid concentration as shown in Figure 4 was reduced by 7% compared to the general green tea.
- the antioxidant activity (DPPH) of the low caffeine green tea prepared in Example 1 and ordinary green tea was analyzed and shown in Table 1 below.
- 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity was measured according to the method of Blois.
- the radicals of DPPH decreased slightly by 1.56% compared to the results of analysis of the antioxidant activity (DPPH) of normal green tea and low caffeine green tea.
- ABSTS Antioxidant Activity
- FRAP antioxidant activity
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Tea And Coffee (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The present invention relates to a method for preparing a low caffeine green tea of which the caffeine has been reduced, and the development of a method for preparing a low caffeine green tea, the method minimizing the loss of catechin, free amino acids, antioxidant ingredients and the like while specifically removing, by using a supercritical extraction system, 87.4% of only a caffeine content, in comparison with a general green tea product, can contribute to the creation of a new domestic tea consumption market and an increase in income of related companies (farmhouses).
Description
초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조 방법에 관한 것이다.It relates to a method for producing green tea having a reduced caffeine content using a supercritical extraction system.
차(tea)는 오래전부터 널리 음용해온 역사가 깊은 기호 음료로서 세계 3대 비알콜성 음료중의 하나이다. 차에는 다양한 유용성분이 함유되어 있으며, 여러 가지 약리적인 효능이 과학적으로 규명되어짐에 따라 음료뿐만 아니라 차 잎으로부터 기능성 성분을 추출하여 건강기능식품, 의약품, 화장품 등의 기능성 소재로 각광받고 있다. 녹차의 경우 카페인이라는 성분이 함유되어 있기 때문에 임산부, 어린이, 노약자 등 카페인에 민감한 소비자들의 경우는 선호도가 떨어진다. 해외 차 시장에 비해 우리나라의 경우 저카페인 녹차, 저카페인 홍차 등 저카페인 다류 제품이 거의 없는 것이 현실이다. 카페인은 알칼로이드(alkaloid)의 일종으로 , 커피, 차 등에 함유되어 있으며, 카페인이 인체에 흡수되면 중추신경계에 작용하여 정신을 각성시키고 피로를 줄이는 등의 효과가 있지만, 장기간 다량을 복용할 경우 카페인 중독을 야기할 수 있으며, 카페인이 몸에 맞지 않는 사람의 경우 신경과민, 매스꺼움, 어지러움증을 유발할 수 있는 물질이기 때문에 인식이 부정적이다. 본 특허에서는 초임계 추출기를 활용한 저카페인 녹차를 제조하는 방법과 제조된 저카페인 녹차를 카테킨/카페인, 항산화 활성, 유리아미노산, 폴리페놀 함량, 관능검사 등의 분석을 통하여 카페인 성분만 특이적으로 제거되는 기술을 제안하고자 한다.Tea is one of the world's three major non-alcoholic beverages. Tea contains various useful ingredients, and as various pharmacological effects have been scientifically identified, functional ingredients are extracted from tea leaves as well as beverages, and are being spotlighted as functional materials such as health functional foods, medicines, and cosmetics. Since green tea contains caffeine, it is less preferred by caffeine-sensitive consumers such as pregnant women, children, and the elderly. Compared to the overseas tea market, the reality is that Korea has few low caffeine products such as low caffeine green tea and low caffeine black tea. Caffeine is a kind of alkaloid. It is contained in coffee, tea, etc. When caffeine is absorbed by the human body, it acts on the central nervous system and wakes up the mind and reduces fatigue. This is a negative perception because caffeine is a substance that can cause nervousness, nausea and dizziness in people who do not fit their body. In this patent, only the caffeine component is analyzed by analyzing the method of preparing low-caffeine green tea using a supercritical extractor and analyzing the prepared low-caffeine green tea by catechin / caffeine, antioxidant activity, free amino acid, polyphenol content, and sensory test. We would like to propose a technique to be removed.
본 발명의 목적은 초임계 추출 시스템을 이용하여 일반 녹차 제품과 비교하여 카페인 함량만 특이적으로 80% 이상 제거되는 저카페인 녹차를 제조하는 방법을 제공하고자 한다.An object of the present invention is to provide a method for producing a low-caffeine green tea in which only a caffeine content is specifically 80% or more removed compared to a general green tea product using a supercritical extraction system.
본 발명의 일 측면에 따른 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차 제조방법으로서, 조분쇄된 녹차를 주정과 혼합하는 단계(1단계); 상기 혼합된 녹차를 실온에서 반응하는 단계(2단계); 상기 반응된 녹차/주정 혼합물에서 주정을 제거하는 단계(3단계); 상기 주정이 제거된 녹차/주정 혼합물을 초임계 추출 시스템을 이용하여 카페인 성분을 제거하는 단계(4단계); 상기 카페인이 제거된 녹차/주정 혼합물을 건조하는 단계(5단계)를 포함하는 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차 제조방법을 제공한다.A method for producing green tea having a reduced caffeine content using a supercritical extraction system according to an aspect of the present invention, comprising: mixing coarsely ground green tea with spirits (step 1); Reacting the mixed green tea at room temperature (step 2); Removing alcohol from the reacted green tea / alcohol mixture (step 3); Removing the caffeine component from the green tea / drink mixture from which the spirit was removed (step 4); It provides a method for producing green tea having a reduced caffeine content using a supercritical extraction system comprising the step (step 5) of drying the green tea / alcohol mixture from which the caffeine is removed.
*본 발명의 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법에 있어서, 상기 주정은 프레타놀A인 것이 바람직하다.In the method for producing green tea having reduced caffeine content using the supercritical extraction system of the present invention, the alcohol is preferably pretanol A.
본 발명의 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법에 있어서, 상기 프레타놀A는 녹차 조분 1kg 당 100ml~1000ml 정도 첨가된 것이 바람직하다.In the method for producing green tea having a reduced caffeine content using the supercritical extraction system of the present invention, the pretanol A is preferably added to about 100ml ~ 1000ml per 1kg green tea powder.
본 발명의 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법에 있어서, 상기 2단계의 온도는 10~50℃인 것이 바람직하다.In the method for producing green tea having reduced caffeine content using the supercritical extraction system of the present invention, the temperature of the second step is preferably 10 ~ 50 ℃.
본 발명의 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법에 있어서, 상기 초임계유체는 이산화탄소이고 추출 온도는 40~80℃, 추출 압력은 100 bar ~ 500 bar이며 초임계유체 제공량 50ml/hr~300ml/hr에서 2~4시간 동안 카페인을 추출하는 것이 바람직하다. In the method for producing green tea having reduced caffeine content using the supercritical extraction system of the present invention, the supercritical fluid is carbon dioxide, the extraction temperature is 40 ~ 80 ℃, the extraction pressure is 100 bar ~ 500 bar and the supercritical fluid provided 50ml It is preferable to extract caffeine for 2 to 4 hours at / hr ~ 300ml / hr.
본 발명의 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법에 있어서, 상기 녹차와 주정 혼합물의 건조는 온도 30~80℃에서 4~6시간 동안 실시되는 것이 바람직하다.In the method for producing green tea having reduced caffeine content using the supercritical extraction system of the present invention, the drying of the green tea and alcohol mixture is preferably carried out for 4-6 hours at a temperature of 30 ~ 80 ℃.
본 발명은 초임계 추출 시스템을 이용하여 일반 녹차 제품과 비교하여 카페인 함량만이 특이적으로 80% 이상 제거하면서 카테킨, 유리아미노산, 항산화 성분 등의 소실을 최소화 하는 저카페인 녹차 제조방법의 개발을 통하여 국내에 신규 차 소비 시장 생성 및 관련 기업(농가)의 소득증가에 기여할 수 있다.The present invention uses a supercritical extraction system to remove low levels of caffeine, free amino acids, antioxidants and the like, while only removing caffeine content by more than 80%, compared to general green tea products. It can contribute to the creation of new tea consumption market in Korea and to increase income of related enterprises (farms).
도 1은 초임계 추출 시스템을 이용하여 저카페인 녹차를 생산하는 전체적인 제조방법을 나타낸다.Figure 1 shows the overall manufacturing method for producing low caffeine green tea using a supercritical extraction system.
도 2는 일반 녹차와 저카페인 녹차의 카페인 함량을 HPLC로 분석한 결과를 나타낸다.Figure 2 shows the results of analyzing the caffeine content of the normal green tea and low caffeine green tea by HPLC.
도 3은 일반 녹차와 저카페인 녹차의 카테킨 함량을 HPLC로 분석한 결과를 나타낸다.Figure 3 shows the results of analyzing the catechin content of ordinary green tea and low caffeine green tea by HPLC.
도 4는 일반 녹차와 저카페인 녹차의 유리아미노산 함량을 유리아미노산 분석기로 분석한 결과를 나타낸다.Figure 4 shows the results of analyzing the free amino acid content of the normal green tea and low caffeine green tea with a free amino acid analyzer.
도 5는 일반 녹차와 저카페인 녹차의 총 폴리페놀 함량을 비교 분석한 결과를 나타낸다.Figure 5 shows the results of a comparative analysis of the total polyphenol content of normal green tea and low caffeine green tea.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 조분쇄된 녹차를 주정과 혼합하는 단계(1단계), 상기 혼합된 녹차를 실온에서 반응하는 단계(2단계), 상기 반응된 녹차/주정 혼합물에서 주정을 제거하는 단계(3단계), 상기 주정이 제거된 녹차/주정 혼합물을 초임계 추출 시스템을 이용하여 카페인 성분을 제거하는 단계(4단계) 및 상기 카페인이 제거된 녹차/주정 혼합물을 건조하는 단계(5단계)를 포함하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차 제조방법을 제공한다.The present invention comprises the steps of mixing the crude green tea with alcohol (step 1), reacting the mixed green tea at room temperature (step 2), removing the alcohol from the reaction green tea / alcohol mixture (step 3) Second, comprising the step of removing the caffeine component (step 4) and drying the caffeine-free green tea / alcohol mixture (step 5) using the supercritical extraction system of the green tea / alcohol mixture from which the spirit is removed Provided is a method for producing green tea having a reduced caffeine content using a critical extraction system.
본 발명에 의하면 상기 주정은 일반적으로 전분이 함유된 물료 또는 당분이 함유된 물료를 발효시켜 알코올분 85℃도 이상으로 증류한 것으로 에탄올의 비율이 95%이므로 녹차 1kg 당 100ml 내지는 1000ml 일 수 있으나, 이에 한정되지는 않는다. According to the present invention, the alcohol is generally fermented with a starch-containing water or sugar-containing water and distilled to 85 ° C or higher alcohol content. Since the ratio of ethanol is 95%, it may be 100ml to 1000ml per kg of green tea. It is not limited.
본 발명에 의하면, 상기 초임계 추출 시스템은 압력이 100 bar 내지는 500 bar 일 수 있으나, 이에 한정되는 것은 아니다.According to the present invention, the supercritical extraction system may have a pressure of 100 bar to 500 bar, but is not limited thereto.
또한, 본 발명은 초임계 추출 시스템에서 사용되는 초임계 이산화탄소의 제공량이 시간당 50 ml 내지는 300 ml 일 수 있으며, 초임계 추출 온도는 40℃ 내지는 80℃ 일 수 있으나, 이에 한정되는 것은 아니다.In addition, the present invention, the amount of supercritical carbon dioxide used in the supercritical extraction system may be 50 ml to 300 ml per hour, the supercritical extraction temperature may be 40 ℃ to 80 ℃, but is not limited thereto.
본 발명에 의하면, 상기 혼합된 녹차를 반응하는 온도는 10℃ 내지는 50℃ 일 수 있으나, 이에 한정되는 것은 아니다.According to the present invention, the temperature for reacting the mixed green tea may be 10 ° C to 50 ° C, but is not limited thereto.
본 발명에 의하면, 상기 카페인이 제거된 녹차와 주정 혼합물의 건조 온도는 30℃ 내지는 80℃ 일 수 있으나, 이에 한정되는 것은 아니다.According to the present invention, the drying temperature of the green tea and spirit mixture from which the caffeine is removed may be 30 ° C. to 80 ° C., but is not limited thereto.
이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 다만 하기의 실시예는 본 발명의 내용을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to help understand the present invention. However, the following examples are merely to illustrate the content of the present invention is not limited to the scope of the present invention. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
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실시예Example
1> 1>
초임계Supercritical
추출 시스템을 이용한 Extraction system
저카페인Low Caffeine
녹차 제조 방법 Green Tea Manufacturing Method
1-1. 1-1.
조분쇄된Crushed
녹차 준비 Green tea preparation
카페인 성분을 효과적으로 제거하기 위하여 조분쇄된 녹차 조분을 사용하였으며, 일반적인 녹차 티백 원료를 제공받아 사용하였다.In order to effectively remove the caffeine component was used a milled green tea powder, was used to provide a general tea green tea raw material.
1-2. 녹차와 주정 혼합 및 반응1-2. Green Tea and Alcohol Mixture and Reaction
녹차 조분의 카페인을 효과적으로 제거하기 위하여 식품첨가용 에탄올인 프레타놀A를 녹차 조분 1 kg 당 500 ml을 첨가한 후 혼합하였다. 이 혼합물을 골고루 섞어준 후 실온(1~35℃)에서 2시간 동안 반응하였다.In order to effectively remove caffeine from green tea powder, 500 ml of green tea meal was added to Pretanol A, a food-added ethanol, and mixed. The mixture was mixed evenly and reacted at room temperature (1 ~ 35 ° C.) for 2 hours.
1-3. 녹차와 주정 혼합액에서 일부 주정 제거1-3. Remove some alcohol from green tea and alcohol mixture
녹차와 주정 혼합물을 한약재 추출용 천 주머니에 넣고 물리적인 힘을 가하여 일부 주정을 제거하였다.A mixture of green tea and alcohol was put in a cloth bag for herbal medicine extraction to remove some alcohol by applying physical force.
1-4. 1-4.
초임계Supercritical
추출 시스템을 이용한 추출 Extraction Using Extraction System
식품 가공용으로 안전성이 기 확보된 이산화탄소를 초임계유체로 사용하였으며, 추출 온도는 80℃, 추출 압력은 400 bar, 초임계유체 제공량은 200 ml/hr로 3시간동안 추출하였다.Carbon dioxide, which was secured for food processing, was used as a supercritical fluid. The extraction temperature was 80 ° C., the extraction pressure was 400 bar, and the supercritical fluid supply amount was 200 ml / hr for 3 hours.
1-5. 건조과정1-5. Drying process
상기 초임계 추출이 완료된 시료를 60℃의 건조 오븐에서 5시간동안 건조시켜 시료에 남아있는 주정을 모두 휘발 시켰으며, 제품의 수분함량을 10 % 이하로 감소시켰다.After the supercritical extraction was completed, the sample was dried in a drying oven at 60 ° C. for 5 hours to volatilize all of the remaining alcohol in the sample, and reduced the water content of the product to 10% or less.
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실시예Example
2> 2>
HPLC를HPLC
이용한 Used
저카페인Low Caffeine
녹차의 카테킨/카페인 함량 분석 Analysis of Catechin / Caffeine Content in Green Tea
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 카테킨/카페인 함량을 비교 분석 하였다. 분석에 사용된 컬럼은 Tosho (ODS-80Tm. 4.6 * 150 mm), flow rate는 1 mL/min, injection volume은 10 uL로 하였다. 그 결과, 카페인 함량의 경우 도 2와 같이 일반 녹차에 비하여 87.2%의 카페인이 감소된 저카페인 녹차가 생산되었다. 카테킨 함량의 경우 도 3과 같이 일반 녹차와 비교하여 (+)-catechin는 26.7%, (-)-epigallocatechin는 55.9%, (+)-epicatechin는 47.0%, (-)-epigallocatechin gallate는 13.8%, (-)-epicatechin gallate는 27.3% 각각 감소하였으며, 총 카테킨 함량은 23.1% 감소하였다.The catechin / caffeine contents of the low caffeine green tea prepared in Example 1 and regular green tea were analyzed. The column used for analysis was Tosho (ODS-80Tm. 4.6 * 150 mm), the flow rate was 1 mL / min, and the injection volume was 10 uL. As a result, a low caffeine green tea was produced in the case of caffeine content is reduced by 87.2% caffeine as compared to the general green tea as shown in FIG. In the case of catechin content, (+)-catechin 26.7%, (-)-epigallocatechin 55.9%, (+)-epicatechin 47.0%, (-)-epigallocatechin gallate 13.8%, (-)-epicatechin gallate decreased by 27.3% and total catechin content decreased by 23.1%.
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실시예Example
3> 3>
저카페인Low Caffeine
녹차의 총 폴리페놀 함량 비교 분석 Comparative Analysis of Total Polyphenol Contents in Green Tea
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 폴리페놀 함량을 비교분석 하였다. 폴리페놀 함량은 Folin-Denis법으로 측정하였다. 그 결과, 도 5와 같이 총 폴리페놀 함량은 일반 녹차 93.37 mg/g, 저카페인 녹차 87.92 mg/g로 5.8% 감소하였다.The polyphenol content of the low caffeine green tea prepared in Example 1 and general green tea was analyzed. Polyphenol content was measured by the Folin-Denis method. As a result, as shown in FIG. 5, the total polyphenol content was reduced by 5.8% to 93.37 mg / g of ordinary green tea and 87.92 mg / g of low caffeine green tea.
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실시예Example
4> 4>
저카페인Low Caffeine
녹차의 Green tea
유리아미노산Free amino acids
함량 비교 분석 Content comparison analysis
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 유리아미노산 함량을 비교분석 하였다. 분석에는 유리아미노산 분석기(Sykam S7130 Amino acid reagent organizer, Germany)를 사용하였으며, UV/VIS detector 400 nm(1.0 AU)와 570 nm(1.0 AU)로 검출하였다. 그 결과, 도 4와 같이 총 유리아미노산 농도는 일반 녹차에 비하여 7% 감소하였다. The content of free amino acids of low caffeine green tea and normal green tea prepared in Example 1 was analyzed. For analysis, a free amino acid analyzer (Sykam S7130 Amino acid reagent organizer, Germany) was used, and UV / VIS detector 400 nm (1.0 AU) and 570 nm (1.0 AU) were detected. As a result, the total free amino acid concentration as shown in Figure 4 was reduced by 7% compared to the general green tea.
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실시예Example
5> 5>
저카페인Low Caffeine
녹차의 항산화 활성( Antioxidant Activity of Green Tea (
DPPHDPPH
, ,
ABTSABTS
, ,
FRAPFRAP
) 비교 분석) comparison analysis
카페인을 줄인 녹차의 항산화 활성(Antioxidant Activity of Green Tea with Caffeine Reduction
DPPHDPPH
) 분석) analysis
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 항산화 활성(DPPH)을 비교 분석 하여 표 1에 나타내었다. 1,1-Diphenyl-2-picrylhydrazyl(DPPH) 라디칼 소거활성은 Blois의 방법에 따라 측정하였다. 그 결과, 표 1와 같이 DPPH의 라디칼이 감소하는 정도는 일반 녹차와 저카페인 녹차의 항산화 활성(DPPH)을 분석한 결과에 비하여 1.56% 유의적으로 소폭 감소하였다.The antioxidant activity (DPPH) of the low caffeine green tea prepared in Example 1 and ordinary green tea was analyzed and shown in Table 1 below. 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity was measured according to the method of Blois. As a result, as shown in Table 1, the radicals of DPPH decreased slightly by 1.56% compared to the results of analysis of the antioxidant activity (DPPH) of normal green tea and low caffeine green tea.
| Extracts(μg/mL)Extracts (μg / mL) | Relative activity (%)Relative activity (%) | |
| 일반녹차General Green Tea | 저카페인 녹차Low Caffeine Green Tea | |
| 5050 | 11.69±1.9411.69 ± 1.94 | 11.21±1.4111.21 ± 1.41 |
| 100100 | 22.21±2.3222.21 ± 2.32 | 20.68±1.6820.68 ± 1.68 |
| 200200 | 35.94±0.9135.94 ± 0.91 | 32.40±2.9032.40 ± 2.90 |
| 500500 | 38.50±0.4838.50 ± 0.48 | 36.58±0.3836.58 ± 0.38 |
| 1,0001,000 | 40.24±0.5240.24 ± 0.52 | 38.68±1.0038.68 ± 1.00 |
카페인을 줄인 녹차의 항산화 활성(ABTS) 분석Antioxidant Activity (ABTS) Analysis of Green Tea with Caffeine Reduction
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 항산화 활성(ABTS)을 비교 분석 하여 표 2에 나타내었다. ABTS 라디칼 소거활성은 cation decolorization assay의 방법에 따라 측정하였다. 그 결과, 표 2와 같이 ABTS 라디칼이 감소하는 정도는 일반 녹차에 비하여 0.86% 유의적으로 소폭 감소하였다.Comparative analysis of the antioxidant activity (ABTS) of the low caffeine green tea prepared in Example 1 and the general green tea is shown in Table 2. ABTS radical scavenging activity was measured according to the method of cation decolorization assay. As a result, as shown in Table 2, the decrease of the ABTS radicals was significantly decreased by 0.86% compared to the general green tea.
| Extracts(μg/mL)Extracts (μg / mL) | Relative activity (%)Relative activity (%) | |
| 일반녹차General Green Tea | 저카페인 녹차Low Caffeine Green Tea | |
| 5050 | 11.25±0.7711.25 ± 0.77 | 9.92±0.699.92 ± 0.69 |
| 100100 | 22.74±1.4422.74 ± 1.44 | 20.00±1.6320.00 ± 1.63 |
| 200200 | 42.17±2.3142.17 ± 2.31 | 38.85±2.6838.85 ± 2.68 |
| 500500 | 84.54±0.4384.54 ± 0.43 | 77.31±1.3377.31 ± 1.33 |
| 1,0001,000 | 93.39±0.1193.39 ± 0.11 | 92.52±0.2992.52 ± 0.29 |
카페인을 줄인 녹차의 항산화 활성(FRAP) 분석Antioxidant Activity (FRAP) Analysis of Green Tea with Caffeine Reduction
실시예 1에서 제작된 저카페인 녹차와 일반 녹차의 항산화 활성(FRAP)을 비교 분석 하여 표 3에 나타내었다. Ferric-reducing antioxidant potential(FRAP)법에 의한 환원 활성은 Benzie와 Strain의 방법에 의해 측정하였다. 그 결과, 표 3와 같이 FRAP 활성은 일반 녹차에 비하여 8.2% 유의적으로 소폭 감소하였다.The antioxidant activity (FRAP) of the low caffeine green tea prepared in Example 1 and regular green tea was analyzed and shown in Table 3. Reducing activity by Ferric-reducing antioxidant potential (FRAP) was measured by Benzie and Strain. As a result, as shown in Table 3, FRAP activity was slightly decreased by 8.2% compared to normal green tea.
| Extracts(μg/mL)Extracts (μg / mL) | FeSO4, μMFeSO 4 , μM | |
| 일반녹차General Green Tea | 저카페인 녹차Low Caffeine Green Tea | |
| 5050 | 14.80±4.1814.80 ± 4.18 | 9.66±0.699.66 ± 0.69 |
| 100100 | 33.04±0.9733.04 ± 0.97 | 28.72±0.8728.72 ± 0.87 |
| 200200 | 68.93±1.4968.93 ± 1.49 | 61.99±0.9661.99 ± 0.96 |
| 500500 | 114.95±1.12114.95 ± 1.12 | 107.50±4.49107.50 ± 4.49 |
| 1,0001,000 | 156.39±4.45156.39 ± 4.45 | 143.50±2.76143.50 ± 2.76 |
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.Having described the specific part of the present invention in detail, it is obvious to those skilled in the art that such a specific description is only a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (6)
- 조분쇄된 녹차를 주정과 혼합하는 단계(1단계);Mixing the coarsely ground green tea with spirits (step 1);상기 녹차와 주정 혼합물을 실온에서 반응하는 단계(2단계);Reacting the green tea and alcohol mixture at room temperature (step 2);상기 반응물에서 일부 주정을 제거하는 단계(3단계);Removing some alcohol from the reactants (step 3);상기 일부 주정이 제거된 반응물을 초임계 추출 시스템을 이용하여 카페인을 선택적으로 제거하는 단계(4단계); 및 Selectively removing caffeine using a supercritical extraction system of the reactant from which some alcohol has been removed (step 4); And상기 카페인이 제거된 녹차와 주정 혼합물을 건조하는 단계(5단계)를 포함하는 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.Method for producing green tea with reduced caffeine content using a supercritical extraction system, characterized in that it comprises the step (step 5) of drying the caffeine-free green tea and alcohol mixture.
- 제 1항에 있어서, The method of claim 1,상기 주정은 프레타놀A인 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.The ethanol is a method for producing green tea reduced caffeine content using a supercritical extraction system, characterized in that the pretanol A.
- 제 2항에 있어서, The method of claim 2,상기 프레타놀A는 녹차 조분 1kg 당 100ml~1000ml 정도 첨가된 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.The pretanol A is a method for producing green tea having a reduced caffeine content using a supercritical extraction system, characterized in that added to about 100ml ~ 1000ml per 1kg of green tea powder.
- 제 1항에 있어서, The method of claim 1,상기 2단계의 온도는 10~50℃인 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.The temperature of the second step is a method for producing green tea reduced caffeine content using a supercritical extraction system, characterized in that 10 ~ 50 ℃.
- 제 1항에 있어서, The method of claim 1,상기 초임계유체는 이산화탄소이고 추출 온도는 40~80℃, 추출 압력은 100 bar ~ 500 bar이며 초임계유체 제공량 50ml/hr~300ml/hr에서 2~4시간 동안 카페인을 추출하는 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.The supercritical fluid is carbon dioxide, the extraction temperature is 40 ~ 80 ℃, the extraction pressure is 100 bar ~ 500 bar and supercritical fluid, characterized in that extracted caffeine for 2-4 hours at 50ml / hr ~ 300ml / hr Method for producing green tea with reduced caffeine content using a critical extraction system.
- 제 1항에 있어서, The method of claim 1,상기 녹차와 주정 혼합물의 건조는 온도 30~80℃에서 4~6시간 동안 실시되는 것을 특징으로 하는 초임계 추출 시스템을 이용한 카페인 함량이 감소된 녹차의 제조방법.Drying of the green tea and alcohol mixture is a method for producing green tea having a reduced caffeine content using a supercritical extraction system, characterized in that carried out for 4-6 hours at a temperature of 30 ~ 80 ℃.
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| KR20070078527A (en) * | 2006-01-27 | 2007-08-01 | 초임계연구소 주식회사 | Caffeine-Free Tea Making Method Using Supercritical Carbon Dioxide |
| KR20090010172A (en) * | 2006-03-23 | 2009-01-29 | 허발사이언스 싱가포르 피티이 리미티드 | Extracts and Methods Including Green Tea Species |
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| KR20140132130A (en) * | 2013-05-07 | 2014-11-17 | 한국식품연구원 | Extracts of Green Tea comprising Low caffeine having antioxidant activity Using Ultrasonic waves and preparing method thereof |
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| KR20070045137A (en) * | 2005-10-26 | 2007-05-02 | 고려대학교 산학협력단 | Method for producing green tea powder without caffeine and green tea powder prepared by the method |
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