KR970007197B1 - Lakes method for coloring material extracted from phellodendron amurense ruprecht - Google Patents

Lakes method for coloring material extracted from phellodendron amurense ruprecht Download PDF

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KR970007197B1
KR970007197B1 KR1019940010084A KR19940010084A KR970007197B1 KR 970007197 B1 KR970007197 B1 KR 970007197B1 KR 1019940010084 A KR1019940010084 A KR 1019940010084A KR 19940010084 A KR19940010084 A KR 19940010084A KR 970007197 B1 KR970007197 B1 KR 970007197B1
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water
pigment
burberry
collagen
soluble
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KR950032484A (en
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장일선
이성호
이영익
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주식회사 태평양
한동근
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006Preparation of organic pigments

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a process for obtaining a yellow pigment used for cosmetic compositions which exhibit excellent color stability, spreadability, light stability, skin feel and stability against acids/base. The yellow pigment is produced by the following steps: dissoving berberine (a pigment extracted from phellodendron) in alcohol, water or their mixture; mixing and agitating the solution with water-soluble and animal collagen solution with pH7.0-9.0 to absorb berberine in the collagen; immobilizing the absorbed berberine by adding polyvalent metal ion to form a lake.

Description

황백나무로부터 추출한 색소의 레이크화 방법Laking Method of Pigment Extracted from Yellow Tree

본 발명은 황백나무에서 추출한 색소인 버버린(BERBERINE) 색소를 레이크화하는 방법에 관한 것이며, 보다 상세하게는 알칼리로 처리한 수용성 동물 콜라겐에 버버린 색소를 흡착시켜 레이크화하므로써 색상효과, 사용감, 색소 분산성, 광안정성, 피부염착배제 및 산 알칼리에 대한 안정성이 뛰어난 화장료용 안료인 황색계의 색소를 얻는 방법에 관한 것이다.The present invention relates to a method of rakeling a BERBERINE pigment, which is a pigment extracted from a yellow-white tree, and more specifically, by absorbing and quenching the burned pigment in an aqueous soluble animal collagen treated with alkali, color effect, feeling, It is related with the method of obtaining the yellow pigment | dye which is a pigment for cosmetics which is excellent in pigment dispersibility, photostability, skin dye excipient, and stability to acid alkali.

황백나무는 한국 전지역, 일본, 중국 등의 토양수분이 많거나 습도가 높은 산간의 계곡등지에 자생하는 낙엽성 교목으로 한방의약품의 윈료로 널리 이용되고 있으며, 그 효능으로는 건위, 강장, 수렴 및 소화제로서 쓰이며 민간에서는 복통의 묘약으로 쓰이며 눈의 충혈, 결막염 등의 세안약으로 쓰이고 있다.Hwangbaek tree is a deciduous tree growing in mountain valleys with high soil moisture or high humidity in all areas of Korea, Japan, China, etc., and is widely used as a wince for herbal medicines. It is used as an extinguishing agent and used as a potion for abdominal pain in the private sector, and as a face wash such as eye redness and conjunctivitis.

본 발명자들은 버버린 색소 자체의 우수한 색감을 유지하면서 천연색소의 단점인 산, 알칼리 및 광에 대한 불안정성, 피부염착성을 개선하고 분산성을 개량하기 위하여 연구를 거듭한 결과, 버버린 색소을 알칼리로 처리한 수용성 콜라겐에 흡착시켜 고정화하면 상기한 목적을 달성할 수 있을 뿐만 아니라 수용성 콜라겐에 의한 피부노화 지연의 효과도 얻을 수 있음을 발견하고 본 발명을 완성하기에 이르렀다.The present inventors have conducted research to improve the dispersibility and skin instability of acid, alkali and light, which are disadvantages of natural pigments, and to improve dispersibility while maintaining excellent color of the burberry pigment itself. The present invention has been found to be accomplished by adsorbing and immobilizing a water-soluble collagen to achieve the above object as well as the effect of delaying skin aging due to water-soluble collagen.

따라서, 본 발명의 목적은 버버린 색소를 레이크화하는 방법을 제공하는 것이다.It is therefore an object of the present invention to provide a method for raking the burberry pigment.

본 발명의 다른 목적은 알코올류, 물 또는 그들의 혼합물에 황백-추출 색소인 버버린을 녹인 용액과 pH 7.0∼9.0으로 조정한 수용성 동물 콜라겐 용액을 혼합 교반하여 버버린을 수용성 동물 콜라겐에 흡착시킨 후, 다가 금속염의 금속이온을 첨가하여 고정화시킴을 특징으로 하는 황백-추출 색소의 레이크화 방법을 제공하는 것이다.Another object of the present invention is to adsorb the aqueous solution to the water-soluble animal collagen by mixing and stirring a solution of the yellow-white extraction pigment Burberry in alcohol, water or a mixture thereof and a water-soluble animal collagen solution adjusted to pH 7.0-9.0 It is to provide a method for lakekwang yellow- extraction pigments, characterized in that the immobilized by the addition of a metal ion of a polyvalent metal salt.

이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 방법에 따르면, 폴리펩티드 구조를 갖는 동물성 단백질인 콜라겐을 알칼리 처리하여 상기의 황백-추출 색소(이하 버버린이라 한다)를 흡착시킨 후, 레이크화하여 고정화시키는 단계로 이루어진 버버린의 레이크화 방법에 관한 것이다. 본 발명의 방법에 의하면, 버버린 색소 자체의 우수한 색감을 유지하면서 산, 알칼리와 광에 대한 불안정성이 개선되고, 피부염착성이 배제되며 수상 및 유상에서의 분산성이 우수하고, 사용감도 우수할 뿐만 아니라 수용성 동물 콜라겐에 의한 피부노화 지연효과도 나타내는 황색계열의 레이크화 버버린 색소를 얻을 수 있다.According to the method of the present invention, the Burberry's raking is made by adsorbing collagen, which is an animal protein having a polypeptide structure, by alkali treatment to adsorb the yellowish white-extracting pigment (hereinafter referred to as Burberry), followed by raking and immobilization. It is about a method. According to the method of the present invention, the instability to acids, alkalis and light is improved while maintaining the excellent color of the burberry pigment itself, the skin dyeability is excluded, the dispersibility in the water and oil phases is excellent, and the usability is also excellent. On the other hand, yellowish lake-burning burberry pigment | dye which also shows the skin aging delay effect by water-soluble animal collagen can be obtained.

콜라겐은 체내 단백질의 일종으로서 피부의 노화상태를 알리는 지수의 역할을 한다. 젊은 사람의 콜라겐은 수분을 많이 함유하고 있어서 탄력적이고 매끄러운 피부상태를 유지하나 나이가 들어감에 따라 콜라겐 섬유간의 가교결합이 많아지고 함수량이 떨어지므로 거칠고 주름진 피부로 변해간다. 따라서 폴리펩티드 구조를 갖는 수용성 동물 콜라겐을 이용하여 레이크화한 버버린 색소는 콜라겐에 의한 피부노화 지연효과도 나타낸다.Collagen is a protein in the body that serves as an index of skin aging. Collagen in young people contains a lot of moisture, so it maintains elastic and smooth skin condition, but as it ages, the cross-linkage between collagen fibers increases and the water content decreases, which leads to rough and wrinkled skin. Therefore, the Burberry pigment | dye which was laked using the water-soluble animal collagen which has a polypeptide structure also exhibits the effect of delaying skin aging by collagen.

본 발명에서 사용 가능한 수용성 동물 콜라겐으로는 어린 송아지의 피부에서 추출해낸 아테로콜라겐, 이 아테로콜라겐의 아미노기의 수소를 숙시닐기로 치환시킨 아테로콜라겐 SS 및 아테로콜라겐의 아미노기의 수소 하나를 미리스토일기로 치환시킨 후 또다른 수소를 숙시닐기로 치환시켜 얻은 아테로콜라겐 MS(이상 일본 Koken사 제품)를 예시할 수 있다. 이들 제품은 피부 활성 효과를 나타내며 무색 무취의 투명한 용액으로서 우수한 보습효과를 갖는다.As the water-soluble animal collagen that can be used in the present invention, atherocollagen extracted from the skin of a young calf, atherocollagen SS in which hydrogen of the amino group of the atherocollagen is substituted with succinyl group, and hydrogen of the amino group of atherocollagen are previously It can be exemplified by atherocollagen MS (produced by Koken, Japan) obtained by substituting a stoyl group and then replacing another hydrogen with a succinyl group. These products have a skin-activating effect and have a good moisturizing effect as a colorless, odorless and clear solution.

본 발명의 방법을 상세히 설명하면 다음과 같다.The method of the present invention is described in detail as follows.

황백-추출색소는 황백을 4∼5mm로 세절하고, 황백 1kg에 대해 70% 에탄올 수용액 5ℓ를 가해 수욕상에서 3시간 동안 추출한 다음, 추출액을 여과하고 농축한 후, 70% 에탄올 수용액에 녹여 일주일간 냉침하여 숙성시켜서 제조한다.The yellowish white-extracted pigment is sliced into 4-5mm of yellow white, and 5L of 70% ethanol aqueous solution is added to 1kg of yellow white, extracted for 3 hours in a water bath. The extract is filtered and concentrated, and then dissolved in 70% ethanol aqueous solution for 1 week. It is prepared by aging.

에탄올, 프로판올, 이소프로판올 등과 같은 알코올류, 물 또는 그의 혼합물에 상기 버버린을 투입하여 잘 저어 포화용액을 만든다. 한편 알칼리, 예를 들면 수산화나트륨을 소량 가하여 pH를 등전점 이상 즉 7.0∼9.0으로 조정한 콜라겐 수용액을 상기 포화용액에 가하여 교반시켜서 버버린과 이온결합이 되도록 반응을 실시한다.The burberry is added to alcohols such as ethanol, propanol, isopropanol, water or a mixture thereof to stir well to form a saturated solution. On the other hand, a small amount of alkali, for example, sodium hydroxide, is added to the saturated solution, and the collagen aqueous solution whose pH is adjusted to the isoelectric point, that is, 7.0 to 9.0 is added to the saturated solution, followed by stirring to react with the burberry.

이어서 상기 혼합물을 흡착공정을 거치도록 한다. 흡착공정은, 버버린, 콜라겐의 염류와 동일한 당량으로 이온결합 반응을 할 수 있는 수용성 다가 금속염, 예를들면, 염화칼슘, 황산알루미늄, 염화바륨 등을 과량의 물에 넣어 교반시켜 다가 금속염이 물에 녹아 해리되게 한 후, 상기 혼합물을 첨가하여 해리된 금속이온이 버버린과 이온결합되어 있는 콜라겐중의 미반응된 이온과 이온결합반응을 하도록 하여 콜라겐과 버버린을 고정시키므로써 수행할 수 있다. 이어 생성 첨가물을 여과, 세척하고 건조시켜서 레이크화 색소를 얻을 수 있다.The mixture is then subjected to an adsorption process. The adsorption process involves the addition of water-soluble polyvalent metal salts, such as calcium chloride, aluminum sulfate, and barium chloride, which can undergo ion-bonding reactions in the same amount as the salts of burberry and collagen. After melting and dissociating, the mixture may be added to cause the dissociated metal ions to undergo an ionic bond reaction with unreacted ions in the collagen that is ionically bonded to the burberry, thereby fixing the collagen and the burberry. The resulting additives can then be filtered, washed and dried to give the laked pigment.

본 발명의 방법에서 버버린을 용해시키기 위하여 사용되는 용매는 바람직하게는 물과 알코올류와의 혼합물이며, 이 경우 양자간의 혼합비율은 70 : 30∼30 : 70의 범위내에 있다.The solvent used to dissolve the burberry in the process of the present invention is preferably a mixture of water and alcohols, in which case the mixing ratio between them is in the range of 70:30 to 30:70.

또 버버린과 수용성 동물 콜라겐과의 당량비는 약 1 : 1∼5의 범위내에 있고, 수용성 동물 콜라겐과 수용성 다가 금속염의 당량비는 약 1 : 1의 범위내에 있다.Moreover, the equivalent ratio of burberry to water-soluble animal collagen is in the range of about 1: 1 to 5, and the equivalent ratio of water-soluble animal collagen and water-soluble polyvalent metal salt is in the range of about 1: 1.

본 발명의 방법에 의해 만들어진 레이크화 황색계 안료는 기존의 황백-추출 색소에 비해 다음과 같은 장점을 갖고 있다 : 첫째, 버버린 자체를 물이나 유기용제에 녹여 사용하였을 때에는 어둡고 둔탁한 바람직하지 못한 색감을 띄나 레이크화된 안료는 선명하고 아름다운 색감을 갖는다. 둘째, 본 발명에 의해 레이크화된 버버린 색소는 레이크화되지 않은 버버린에 비하여 수분산성 및 유분산성이 뛰어나며 색소끼리 뭉치는 현상도 없다. 셋째, 본 발명의 방법을 통해 제조된 레이크화 색소는 레이크화되지 않은 버버린에 비해 색상변화가 없다. 넷째, 기름이나 물에 용출되지 않으며 또한 피부에 염착되지도 않는다. 다섯째, 추출된 그 대로의 버버린이 빛에 아주 약한 것과는 달라 본 발명의 레이크화된 버버린 색소는 일광에 대해 매우 안정하다. 여섯째, 콜라겐의 노화 지연효과 및 특유의 사용감을 갖게되어 부드럽고 피부친화력이 우수하다.The laked yellow pigment produced by the method of the present invention has the following advantages over the conventional yellowish white-extracted pigments: Firstly, when the burberry itself is dissolved in water or an organic solvent, it is dark and dull undesirable color. The pigmented lake has a vivid and beautiful color. Second, the Burberry pigment rake by the present invention is excellent in water dispersibility and oil dispersibility compared to the unlaked Burberry, and there is no phenomenon that the pigments are aggregated. Third, the rake pigmented pigment produced by the method of the present invention has no color change compared to the unburned burberry. Fourth, it does not dissolve in oil or water and does not dye on the skin. Fifth, unlike the extracted Burberry, which is very weak to light, the raked Burberry pigment of the present invention is very stable against sunlight. Sixth, collagen has a aging retardation effect and a unique feeling of use, it is soft and skin-friendly.

이하 각종 예를 들어 본 발명을 보다 상세히 설명하지만 본 발명이 이들 예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to various examples, but the present invention is not limited only to these examples.

실시예 1Example 1

물과 에탄올의 중량비가 70 : 30인 혼합물 300g에 1g의 버버린을 넣고 잘 녹였다. 또한 시판중인 수용성동물 콜라겐(2%; 아테로콜라겐 SS : 일본 Koken사 제품) 20g을 200g의 물에 분산시킨 후, 가성소다를 소량 가하여 pH가 약 80이 되도록 하였다. 상기 두용액을 혼합하고 잘 교반 시켜주었다. 그리고 과량의 가온된 물(50cc)에 황산알미늄(Al2(SO4)3, 16-8 H2O) 4g을 넣어 30분 가량 교반시킨 후, 여기에 미리 교반시켜 놓은 색소화 콜라겐과의 혼합용액을 첨가하여 생성되는 침전물을 여과, 세척 및 건조하여 버버린 색소의 레이크를 제조하였다.1 g of Burberry was added to 300 g of a mixture of water and ethanol having a weight ratio of 70:30, and dissolved well. In addition, 20 g of a commercially available water-soluble animal collagen (2%; atherocollagen SS: manufactured by Koken, Japan) was dispersed in 200 g of water, and a small amount of caustic soda was added to have a pH of about 80. The two solutions were mixed and stirred well. 4 g of aluminum sulfate (Al 2 (SO 4 ) 3 , 16-8 H 2 O) was added to excess warm water (50 cc) and stirred for about 30 minutes, followed by mixing with the pre-stirred pigmented collagen. The resulting precipitate was filtered, washed and dried by addition of a solution to prepare a lake of discarded pigment.

실험예Experimental Example

상기 실시예에서와 같이 제조한 본 발명의 레이크화 버버린 안료와 기존의 버러린 안료, 시코닌 및 적색 202호의 물성을 하기 표 1에 기재된 항목에 대해 다음과 같은 방법으로 측정하였다.The physical properties of the laked Burberry pigment of the present invention prepared as in the above Example and the conventional Burrard pigment, Siconin and Red No. 202 were measured by the following method for the items listed in Table 1 below.

(1) 광안정성 : pH 7.0인 소량의 폴리옥시에칠렌소르비탄라우릴 에스테르를 함유한 수용액에 적량의 시료를 넣어 분산시킨 뒤, 양지 및 응달에서 분산된 시료를 각각 며칠동안 계속 방치하면서 색상변화(L*, a*및 b*)를 스펙트로가드 II 색상계(SpectrogradTMII color System; Pacific Scientific Co.; 미국)를 사용하여 측정하고,에 따라 ΔE값을 계산하여, ΔE≤1.0인 경우 극히 양호(◎), 1.0ΔE≤2.0인 경우 양호(○), 2.0ΔE≤2.5인 경우 보통(△), 2.5ΔE인 경우 불량(×)으로 평가한 후, 그 결과를 표 1에 나타내었다.(1) Light stability: After dispersing a small amount of sample in an aqueous solution containing a small amount of polyoxyethylene sorbitan lauryl ester having a pH of 7.0, and changing the color by continuously leaving the sample dispersed in sun and shade for several days. L *, a * and b *) to guard spectrometer II colorimeter (color Spectrograd TM II system; using a Pacific Scientific Co .; USA), it is measured, ΔE values are calculated according to the following results: ΔE ≤ 1.0, extremely good (◎), 1.0 ΔE ≤ 2.0 good (○), 2.0 ΔE ≤ 2.5 normal (△), 2.5 ΔE bad (×) After the evaluation, the results are shown in Table 1.

(2) 산 알칼리에 대한 안정성 : pH 4.0∼10.0인 위와같온 수용액에 시료를 적량 넣고 흔들어 분산시킨 후, 시료분산액의 색상변화(L*, a*및 b*)를 스팩로가드TMII 색상계(SpectrogradTMII color System; Pacific Scientific Co.; 미국)를 사용하여 측정하고, pH 4.0에서와 pH 10.0에서의 ΔE값을에 따라 계산하여, ΔE0.5인 경우 극히 양호(◎), 5.0≤ΔE≤1.0인 경우 양호(○), 1.0ΔE≤1.5인 경우 보통(△), 1.5ΔE인 경우 불량(×)으로 평가한 후, 그 결과를 표 1에 나타내었다.(2) Stability against acid alkali: After appropriately placing the sample in the above aqueous solution with pH 4.0-10.0 and shaking to disperse, the color change (L * , a * and b * ) of the sample dispersion was measured using a SparrowGuard TM II color system. (Spectrograd II color system; Pacific Scientific Co .; USA) and measured ΔE values at pH 4.0 and at pH 10.0 ΔE0.5 for very good (◎), 5.0≤ΔE≤1.0 for good (○), 1.0ΔE≤1.5 for normal (△), 1.5ΔE for poor (×) The results are shown in Table 1 below.

(3) 피부염착에 대한 안정성 : 용해 또는 분산가능한 매질에 시료를 각각 동일함량씩 분산시켜 소량을 피부에 도포한 후 2시간이 경과 뒤 세척을 한 후의 색차(L*, a*및 b*; ΔE=(ΔL*)2+(Δa*)2+(Δb*)2)를 크로마 메타(색차 분석기, Minolta, 미국)를 사용하여 측정하고, ΔE값에 따라, ΔE1.0인 경우 극히 양호(◎), 1.0≤ΔE≤2.0인 경우 양호(○), 2.0ΔE≤4.0인 경우 보통(△), 40ΔE인 경우 불량(×)으로 평가한 후, 그 결과를 표 1에 나타내었다.(3) Stability against Skin Dyeing: Color difference after washing for 2 hours after applying small amount to the skin by dispersing the sample in dissolvable or dispersible medium in equal amounts each (L * , a * and b * ; ΔE = (ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ) was measured using chroma meta (color difference analyzer, Minolta, USA) and, depending on the ΔE value, extremely good for ΔE1.0 (◎) After evaluation as good ((circle)) when 1.0 <= (DELTA) E <= 2.0, normal ((triangle | delta)) when 2.0 (DELTA) E <= 4.0, and bad (x) when 40 (DELTA) E, the result is shown in Table 1.

(4) 분상성 : 시료를 물이나 기름속에서 동일한 조건하에 분산시켜 현미경으로 분산정도를 관찰한 후, 하기 평가 기준에 따라 평가하고 그 결과를 표 1에 나타내었다.(4) Phase separation: The sample was dispersed in water or oil under the same conditions, and the degree of dispersion was observed under a microscope. The result was evaluated according to the following evaluation criteria and the results are shown in Table 1.

[평가기준][Evaluation standard]

◎ : 극히 양호, ○ : 양호, △ : 보통, × : 불량.◎: extremely good, ○: good, △: normal, ×: poor.

[표 1] TABLE 1

상기 표 2의 결과로부터 본 발명의 방법에 의해 제조된 레이크화 버버린 색소가 광안정성, 산과 알칼리에 대한 안정성, 피부염착에의 배제 및 분산성에 기존의 색소들에 비해 우수함을 알 수 있다.From the results of Table 2, it can be seen that the laked-burberry pigment prepared by the method of the present invention is superior to the conventional pigments in light stability, stability against acids and alkalis, exclusion and dispersibility in skin dyeing.

Claims (4)

알코올류, 물 또는 그들의 혼합물에 황백-추출 색소인 버버린을 녹인 용액과 pH 7.0∼9.0으로 조정한 수용성 동물 콜라겐 용액을 혼합 교반하여 버버린을 수용성 동물 콜라겐에 흡착시킨 후, 다가 금속염을 첨가하여 고정화시킴을 특징으로 하는 황백-추출 색소의 레이크화 방법.After mixing and stirring alcohol solution, water or mixture thereof, the solution of Burberry, which is a white-white extract pigment, and water-soluble animal collagen solution adjusted to pH 7.0-9.0, adsorbing the Burberry to water-soluble animal collagen, and then adding polyvalent metal salt A method for lakeking a white-white extract pigment, characterized by immobilization. 제1항에 있어서, 물과 알코올류과의 혼합비율을 70 : 30∼30 : 70으로 하는 방법.The method according to claim 1, wherein the mixing ratio of water and alcohols is 70: 30-30: 70. 제1항에 있어서, 황백-추출 색소와 수용성 동물 콜라겐과의 당량비는 1 : 1∼5임을 특징으로 하는 방법.The method according to claim 1, wherein the equivalence ratio of the yellowish white-extracted pigment to the water-soluble animal collagen is 1: 1-5. 제1항에 있어서, 수용성 동물 콜라겐과 수용성 다가 금속염의 당량비는 1 : 1임을 특징으로 하는 방법.The method according to claim 1, wherein the equivalent ratio of water-soluble animal collagen and water-soluble polyvalent metal salt is 1: 1.
KR1019940010084A 1994-05-09 1994-05-09 Lakes method for coloring material extracted from phellodendron amurense ruprecht KR970007197B1 (en)

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