KR20020012580A - Utilization of microemulsions in fermentation processes - Google Patents
Utilization of microemulsions in fermentation processes Download PDFInfo
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- KR20020012580A KR20020012580A KR1020017015012A KR20017015012A KR20020012580A KR 20020012580 A KR20020012580 A KR 20020012580A KR 1020017015012 A KR1020017015012 A KR 1020017015012A KR 20017015012 A KR20017015012 A KR 20017015012A KR 20020012580 A KR20020012580 A KR 20020012580A
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- acid
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- emulsion
- alcohol
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- 238000000855 fermentation Methods 0.000 title claims abstract description 32
- 230000004151 fermentation Effects 0.000 title claims abstract description 32
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Classifications
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
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- 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
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
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- 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
- C12N1/26—Processes using, or culture media containing, hydrocarbons
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/56—Glucosides; Mucilage; Saponins
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Abstract
본 발명은 발효 공정에서의 수중유 에멀션의 용도에 관한 것으로서, 상기 에멀션은, 적어도 물, 유화제, 및 a) 지방산 알킬 에스테르 및/또는 b) 식물 유래의 트리글리세리드로 구성되는 군으로부터 선택되는 하나 이상의 화합물을 함유하는 오일상을 함유하며, 에멀션은 1 내지 100 nm의 소적 크기를 가진다.The present invention relates to the use of an oil-in-water emulsion in a fermentation process, wherein the emulsion is at least one selected from the group consisting of water, emulsifiers, and a) fatty acid alkyl esters and / or b) triglycerides derived from plants. It contains an oil phase containing, the emulsion has a droplet size of 1 to 100 nm.
Description
본 발명은 마이크로에멀션의 발효 공정에서의 용도에 관한 것이다.The present invention relates to the use of the microemulsion in the fermentation process.
미생물 공정은, 복합 천연물 및 다른 유기 화합물의 합성에서 증가추세로 사용된다. 그러한 공정은 미생물, 특히 박테리아 또는 곰팡이가 관여하는 혐기 또는 호기 조건 하에서의 전이/전환을 수반한다. 미생물학적 공정을 위한 각종 용어-언제나 명확하게 구분되는 것은 아니지만(예컨대, 생전이, 생물 전환, 발효)-가 숙련가에 의해 사용된다. 용어 "발효"는, 본 명세서에서는, 미생물, 바람직하게는 박테리아가 화학적 화합물의 전환 또는 합성 사용되는 공정에 대하여 사용된다.Microbial processes are increasingly used in the synthesis of complex natural products and other organic compounds. Such processes involve the transfer / conversion under anaerobic or aerobic conditions involving microorganisms, in particular bacteria or fungi. Various terms for microbiological processes—although not clearly distinguishable at all times (eg, biotransition, bioconversion, fermentation) —are used by the skilled person. The term "fermentation" is used herein for processes in which microorganisms, preferably bacteria, are used for the conversion or synthesis of chemical compounds.
발효 공정의 발생 및 최적화에서 중요한 요소는 특히 미생물 형질 전환이 일어나는 반응 매질이다. 일반적으로 수용액 또는 수성 분산액인 반응 매질은 무엇보다도 공정의 수율 및 효율에 영향을 준다. 미생물은 목적 생성물로의 대사가 성공적으로 진행하는 것을 가능하게 할 영양소로서 탄소, 질소 및 결합된 형태의 특정 미량 원소, 예를 들어, 칼슘, 철, 인 또는 아연을 필요로 한다. 또한, 온도 및 pH는, 특정의, 일반적으로 협소한 범위로 일정하게 유지되어야 한다. 더욱 구체적인 것은, 문헌[W. Crueger/A. Crueger,Biotechnologie-Lehrbuch der angewandten Mikrobioliogie, 제 2 판, 1984, R.Oldenbourg Verlag]에서 찾을 수있다. 상기 문헌의 제 5 장에서는, 특히 발효의 기본에 대해 다루었다. 따라서, 상기 참고 문헌은 또한 엄밀하게는 본 발명의 기재에 속한다. 고에너지 당 및 그의 유도체 외에, 천연 지방 및 그의 유도체, 예컨대 글리세롤, 글리세리드, 지방산 또는 지방산 에스테르가 다수의 공정에서 미생물을 위한 영양소로서 추가로 사용된다. 물론, 배양 배지는, 미생물의 대사에 악영향을 끼칠 수 있는 임의의 첨가물을 함유하지 않을 수 있다.An important factor in the generation and optimization of the fermentation process is in particular the reaction medium in which microbial transformation takes place. The reaction medium, which is usually an aqueous solution or an aqueous dispersion, first of all influences the yield and efficiency of the process. Microorganisms require carbon, nitrogen and certain trace elements in the combined form, such as calcium, iron, phosphorus or zinc, as nutrients that will enable successful metabolism to the desired product. In addition, the temperature and pH should be kept constant in a specific, generally narrow range. More specifically, W. Crueger / A. Crueger, Biotechnologie-Lehrbuch der angewandten Mikrobioliogie , 2nd edition, 1984, R. Ollbourg Verlag. In Chapter 5 of this document, in particular, the basics of fermentation are discussed. Thus, the above references also strictly belong to the description of the present invention. In addition to high energy sugars and derivatives thereof, natural fats and derivatives thereof such as glycerol, glycerides, fatty acids or fatty acid esters are further used as nutrients for microorganisms in many processes. Of course, the culture medium may not contain any additives that may adversely affect the metabolism of microorganisms.
예를 들어, DE 37 38 812 A1 호에는, 칸디다 트로피칼리스(Candida tropicalis) 균주의 박테리아가 메틸 라우레이트를 목적 카르복실산으로 전환시키는, α,ω-디카르복실산의 제조를 위한 미생물 공정이 기재되었다. 상기 전환은 30℃에서 pH 6.0의 수성 배지에서 수행된다. 미생물 외에, 배지는 에너지원으로서의 글루코오스, 유화제로서의 에톡실화 소르비탄 모노올레에이트, 효모 추출물, 옥수수 침지액(corn steep liquor) 및 무기물 N 및 P원을 함유한다. 이어서 메틸 라우레이트가 배지에 첨가된다. 상기 문헌에는 발효기 안에 형성되거나 또는 메틸라우레이트가 발효 브로쓰에 첨가되는 에멀션의 유형에 대한 언급이 없다. EP 0 535 939 A1호에는, 적절한 미생물이 에너지원으로서의 당 및 무기 또는 유기 질소원, 및 지방산 메틸 에스테르의 존재 하에 수성 배양 배지에서 목적 고도불포화 지방산을 생산하는 ω-9-고도불포화 지방산의 제조 공정이 기재되었다.For example, DE 37 38 812 A1 discloses a microbial process for the preparation of α, ω-dicarboxylic acids in which bacteria of the Candida tropicalis strain convert methyl laurate to the desired carboxylic acid. Described. The conversion is carried out in aqueous medium at pH 6.0 at 30 ° C. In addition to microorganisms, the medium contains glucose as an energy source, ethoxylated sorbitan monooleate as an emulsifier, yeast extract, corn steep liquor and inorganic N and P sources. Methyl laurate is then added to the medium. The document makes no mention of the type of emulsion formed in the fermentor or in which methyllaurate is added to the fermentation broth. EP 0 535 939 A1 discloses a process for producing ω-9-unsaturated fatty acids in which suitable microorganisms produce the desired polyunsaturated fatty acids in an aqueous culture medium in the presence of sugars and inorganic or organic nitrogen sources as energy sources, and fatty acid methyl esters. Described.
그러나, 다른 공지된 공정은, 에너지원으로 상기에 기재된 유형의 지방 화합물만을 사용한다. 상기와 같은 지방 화합물은 일반적으로 당, 전분 및 유사 화합물보다 저렴하므로 특히 경제적으로 이익이다. Park 등(Park 등, Journal ofFermentation and Bioengineering, 제 82 권, 2 호, 183 - 186, 1996)에는 스트렙토마이시스 프라디아에(Streptomyces fradiae) 균주의 미생물을 평지씨유가 약 60 g/l의 개시량으로 단독 탄소원으로서 존재하는 수성 배지에서 사용하는 틸로신의 제조를 위한 발효 방법이 기재되어 있다.However, other known processes use only fatty compounds of the type described above as energy sources. Such fatty compounds are particularly economically beneficial as they are generally less expensive than sugars, starches and similar compounds. Park et al. (Park et al., Journal of Fermentation and Bioengineering, Vol. 82, No. 2, 183-186, 1996) reported that the rapeseed oil contained an intake of about 60 g / l of microorganisms of Streptomyces fradiae strains. A fermentation method for the production of tyrosine for use in an aqueous medium present as the sole carbon source is described.
발효 공정에서, 배지 또는 발효 브로쓰 중의 산소 함량 또한 중요한 역할을 한다. 호기성 공정에서, 산소는 기질로서의 역할을 한다. 중요한 점은, 기체상으로부터 미생물을 함유하는 액체상으로의 산소의 이동이 특정 공정을 위해 충분히 일어날 수 있는지의 여부이다. 중요한 파라미터는, 일반적으로 산소 이동 효율 kLa(참고: Crueger, 제 5 장, 71 쪽, 이하 쪽 참조)을 통해 간접적으로 측정되는 특별한 교환 표면이다. 최적 산소 주입의 조정은 전형적으로 발효 브로쓰를 교반함으로써 달성되며, 산소 또는 공기가 액체와 혼합되고, 따라서 기체 교환은 계면에서 일어난다. 그러나, Park 등에 의해 수행된 바와 같이, 격렬한 교반에 의한 에너지의 상당한 기계적인 투입은 배양물의 일부를 파괴할 수 있어, 공정의 수율을 감소시킨다. 또한, 죽은 미생물들은 그 자체가 더 분해되어, 형성된 분해 생성물을 통해 배양액이 독성화될 수 있어, 경제적인 제조가 불가능하다. Goma 및 Rols의 저서(G.Goma, J.L.Rols, Biotech. Let., Vol. 13, No. 1, 7 ~ 12 쪽, 1991)로부터, 항생제 제조를 위한 발효 공정에서의 대두유의 사용이, 산소 이동 효율 kLa의 향상을 가져오고, 이것은 동일한 에너지 투입(교반)에 대해 전체적으로 공정 수율의 향상에 이를 수 있는 것이 공지되었다.In the fermentation process, the oxygen content in the medium or fermentation broth also plays an important role. In aerobic processes, oxygen serves as the substrate. The important point is whether the transfer of oxygen from the gas phase to the liquid phase containing the microorganisms can occur sufficiently for a particular process. An important parameter is the special exchange surface, which is usually measured indirectly via the oxygen transfer efficiency k La (see Crueger, Chapter 5, p. 71, cf.). Adjustment of the optimum oxygen injection is typically achieved by stirring the fermentation broth, where oxygen or air is mixed with the liquid, and thus gas exchange takes place at the interface. However, as performed by Park et al., Significant mechanical input of energy by vigorous agitation can destroy part of the culture, reducing the yield of the process. In addition, dead microorganisms are further degraded by themselves, and the culture solution can be toxic through the formed degradation products, making economic production impossible. From the work of Goma and Rols (G.Goma, JLRols, Biotech. Let., Vol. 13, No. 1, pages 7 to 12, 1991), the use of soybean oil in the fermentation process for the preparation of antibiotics, oxygen transfer efficiency It is known that this results in an improvement in k La , which can lead to an overall improvement in process yield for the same energy input (stirring).
현재, 본 발명으로 해결하고자 하는 문제는, 발효 공정을 향상시켜, 한편으로는 저렴한 탄소원을 사용할 수 있고, 다른 한편으로는 미생물이 교반에 의한 허용되지 않는 극심한 기계적인 스트레스에 노출되지 않고도 미생물에게 충분한 산소 공급이 보장되도록 하는 것이다. 수율의 감소 없이 발효 공정에서의 에너지의 기계적 투입을 최소화하는 방법이 발견되었다. 바람직하게는, 감소된 에너지 투입에도 불구하고 수율이 증가할 것이다.At present, the problem to be solved by the present invention is to improve the fermentation process, on the one hand it is possible to use an inexpensive carbon source, and on the other hand it is sufficient for microorganisms without exposure to unacceptable extreme mechanical stress by agitation. To ensure an oxygen supply. A method has been found to minimize the mechanical input of energy in the fermentation process without reducing the yield. Preferably, the yield will increase despite the reduced energy input.
특별한 미세-소적 수중유(o/w) 에멀션의 사용이 상기 언급된 문제를 해결할 수 있음을 발견했다.It has been found that the use of special micro-drop oil-in-water (o / w) emulsions can solve the above mentioned problems.
제 1 구현예에서, 본 발명은, 발효 공정에서의 o/w 에멀션의 용도에 관한 것이며, 상기 에멀션은 적어도 물, 유화제 및 오일상을 함유하며, 오일상은 하기로 구성되는 군으로부터의 하나 이상의 화합물을 함유하며:In a first embodiment, the invention relates to the use of an o / w emulsion in a fermentation process, said emulsion containing at least water, an emulsifier and an oil phase, wherein the oil phase is at least one compound from the group consisting of Contains:
a) 지방산 알킬 에스테르 및/또는a) fatty acid alkyl esters and / or
b) 식물 유래의 트리글리세리드b) triglycerides derived from plants
에멀션은 1 내지 100 nm의 소적 크기를 갖는다:The emulsion has a droplet size of 1 to 100 nm:
본 발명에 따른 에멀션은 특히 그의 소적 미세성을 특징으로 한다. 그들은 비혼화성 액체 둘 이상, 및 비이온성 계면활성제 하나 이상 또는 바람직하게는 두 개의 소수성 잔기를 함유하는 이온성 계면활성제 하나의, 육안으로는 균일하며, 광학적으로는 투명하고, 종종 점성이 낮고, 열역학적으로 안정한 혼합물로 정의되는 소위 마이크로에멀션이다. 마이크로에멀션의 형성에는, 오일/물 계면 장력이 값 0에 가까운 상황이 수반된다. 하나 이상의 비이온성 계면활성제 외에,일반적으로 다른 조-계면활성제가 첨가되어야 이러한 특별한 유형의 에멀션이 완성된다 [참고 문헌: "Introduction to Colloid and Surface Chemistry", D.J. Shaw, Butterworth, 1992, 269 ~ 270 쪽]. 본 발명에 따라 사용되는 에멀션의 소적 크기는, 1 내지 100 nm 범위, 바람직하게는 10 내지 80 nm의 범위, 더욱 바람직하게는 10 내지 30 nm의 범위이다. 오일 소적의 미세함은 오일 및 수 상 사이에 넓은 표면을 초래하여, 영양 물질을 함유하는 오일상 및 수성상에 존재하는 미생물들 사이의 빠른 접촉을 제공한다. 또한 넓은 표면은 기체, 특히 산소 및 이산화탄소의 교환을 간소화한다. 더욱이, 에멀션 및 그에 따른 전체 발효 매질의 점도가 감소한다. 결과적으로, 발효 매질의 교반 속도를 현저히 감소시킬 수 있어, 발효 공정의 수율이 증가될 수 있다.The emulsions according to the invention are particularly characterized by their droplet fineness. They are visually uniform, optically clear, often low viscosity, thermodynamic, of at least two immiscible liquids, and at least one nonionic surfactant or at least one ionic surfactant containing preferably two hydrophobic moieties. It is a so-called microemulsion that is defined as a stable mixture. Formation of the microemulsion involves the situation where the oil / water interface tension is close to the value zero. In addition to one or more nonionic surfactants, other co-surfactants are generally added to complete this particular type of emulsion [Ref. To "Introduction to Colloid and Surface Chemistry", D.J. Shaw, Butterworth, 1992, pp. 269-270]. The droplet size of the emulsions used according to the invention is in the range from 1 to 100 nm, preferably in the range from 10 to 80 nm, more preferably in the range from 10 to 30 nm. The fineness of the oil droplets results in a large surface between the oil and the water phases, providing a quick contact between the microorganisms present in the oil and aqueous phases containing the nutrient substances. The large surface also simplifies the exchange of gases, in particular oxygen and carbon dioxide. Moreover, the viscosity of the emulsion and thus the entire fermentation medium is reduced. As a result, the stirring speed of the fermentation medium can be significantly reduced, so that the yield of the fermentation process can be increased.
본 발명에 따라, 마이크로에멀션은 미생물을 함유하며 다른 보조제 및 첨가제를 임의함유하는 수성 발효 매질에 첨가된다. 이 공정의 자세한 점, 더 구체적으로는 에멀션의 첨가 속도 및 첨가량은, 선택된 미생물 균주 및 발효 공정에 의해 결정되며, 숙련가에 의해 특별한 상황에 맞게 채택될 수 있다.According to the invention, microemulsions are added to an aqueous fermentation medium containing microorganisms and optionally containing other auxiliaries and additives. The details of this process, more specifically the rate and amount of addition of the emulsion, are determined by the chosen microbial strain and fermentation process and can be adapted to the particular situation by the skilled person.
물 외에, 마이크로에멀션은 a) 지방산 알킬 에스테르 및 b) 천연 식물 오일 및 그의 유도체의 군으로부터의 화합물을 함유하는 오일 상을 함유한다. 군 a) 및 b) 는, 발효 공정에 사용되는 박테리아를 위한 영양소, 즉 에너지원으로서 작용할 수 있지만, 생물 전환에 의해 수득되는 생성물을 위한 개시 물질(기질)이 될 수도 있는 소수성, 수불용성 또는 실질적으로 수불용성인 화합물이다.In addition to water, the microemulsions contain an oil phase containing compounds from the group of a) fatty acid alkyl esters and b) natural plant oils and derivatives thereof. Groups a) and b) are hydrophobic, water insoluble or substantially capable of serving as nutrients for the bacteria used in the fermentation process, ie energy sources, but may also be starting materials (substrates) for products obtained by bioconversion. It is a compound which is water insoluble.
군 a) 의 적합한 메틸 에스테르는, 특히 탄소수 7 내지 23의 포화, 불포화,선형 또는 분지형의 지방산으로부터 유도된다. 다시 말하면, 이는 하기 화학식 I의 화합물이다:Suitable methyl esters of group a) are especially derived from saturated, unsaturated, linear or branched fatty acids having 7 to 23 carbon atoms. In other words, it is a compound of formula
[식 중, R1는 C6-22알킬기이며, R2는 C1-4알킬기이다]. 메틸 및 에틸기가 바람직하다. 메틸 에스테르가 성분 a) 로서 특히 바람직하다. 화학식 I의 에스테르 또는 메틸 에스테르는 공지된 방법, 예를 들어, 트리글리세리드와 메탄올의 에스테르교환 반응 및 그에 이은 증류로 수득할 수 있다. 적합한 지방산은 카프로산, 헵탄산, 카프릴산, 펠라곤산, 카프르산, 운데칸산, 라우르산, 트리데칸산, 미리스트산, 펜타데칸산, 팔미트산, 헵타데칸산, 스테아르산, 노나데칸산, 아라크산 및 베헨산이다. 불포화된 대표적인 것은 예를 들어, 라우롤레산, 미리스톨레산, 팔미톨레산, 페트로셀라이드산, 올레산, 엘라이드산, 리시놀레산, 리놀레산, 리놀라이드산, 리놀렌산, 가돌레산, 아라키돈산 및 에루크산이다. 상기 산들의 메틸 에스테르들의 혼합물 또한 적합하다. 메틸 올레에이트, 메틸 팔미테이트, 메틸 스테아레이트 및/또는 메틸 펠라르고네이트로 구성되는 군으로부터의 메틸 에스테르를 함유하는 마이크로에멀션을 사용하는 것이 특히 바람직하다. 그러나, 예를 들어, 아마인유, 코코넛유, 야자유, 야자핵유, 올리브유, 피마자유, 평지씨유, 참깨유, 대두유 또는 해바라기유(평지씨유 및 해바라기유의 경우, 신생 및 노화 식물)로부터 수득가능한 천연 지방산 혼합물 기재의 메틸 에스테르 또한 사용될수 있다.[ Wherein , R 1 is a C 6-22 alkyl group and R 2 is a C 1-4 alkyl group]. Methyl and ethyl groups are preferred. Methyl esters are particularly preferred as component a). Esters or methyl esters of formula I can be obtained by known methods, for example by transesterification of triglycerides with methanol followed by distillation. Suitable fatty acids include caproic acid, heptanoic acid, caprylic acid, pelagonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, Nonadecanoic acid, arachic acid and behenic acid. Unsaturated representatives are, for example, lauroleic acid, myristoleic acid, palmitoleic acid, petroleic acid, oleic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, linolenic acid, gadoleic acid, arachidonic acid and Erucic acid. Mixtures of methyl esters of these acids are also suitable. Particular preference is given to using microemulsions containing methyl esters from the group consisting of methyl oleate, methyl palmitate, methyl stearate and / or methyl pelargonate. However, for example, obtainable from linseed oil, coconut oil, palm oil, palm kernel oil, olive oil, castor oil, rapeseed oil, sesame oil, soybean oil or sunflower oil (for rapeseed oil and sunflower oil, newborn and aging plants) Methyl esters based on natural fatty acid mixtures may also be used.
적합한 군 b) 화합물은 식물 유래의 천연 오일이다. 이들은 본질적으로, 글리세롤이 항상 비교적 긴 사슬인 지방산으로 완전히 에스테르화된 트리글리세리드 혼합물이다. 특히 적합한 식물유는, 땅콩유, 코코넛유, 아마인유, 야자유, 올리브유, 야자핵유, 피마자유, 평지씨유, 참깨유, 대두유 및 해바라기유로 구성되는 군으로부터 선택된다.Suitable group b) compounds are plant-derived natural oils. These are essentially triglyceride mixtures in which glycerol is fully esterified with fatty acids which are always relatively long chains. Particularly suitable vegetable oils are selected from the group consisting of peanut oil, coconut oil, linseed oil, palm oil, olive oil, palm kernel oil, castor oil, rapeseed oil, sesame oil, soybean oil and sunflower oil.
땅콩유는, 평균적으로(지방산 기준) 54 중량%의 올레산, 24 중량%의 리놀레산, 1 중량%의 리놀렌산, 1 중량%의 아라크산, 10 중량%의 팔미트산 및 4 중량%의 스테아르산을 함유하며, 2 내지 3℃의 융점을 가진다. 아마인유는 전형적으로 5 중량%의 팔미트산, 4 중량%의 스테아르산, 22 중량%의 올레산, 17 중량%의 리놀레산 및 52 중량%의 리놀렌산을 함유하며, 155 내지 205의 요오드 값을 가지고, 188 내지 196의 비누화 값을 가지며, 약 -20℃의 융점을 가진다. 코코넛유는 약 0.2 내지 1중량%의 헥산산, 5 내지 8 중량%의 옥탄산, 6 내지 9 중량%의 데칸산, 45 내지 51 중량%의 라우르산, 16 내지 19 중량%의 미리스트산, 9 내지 11 중량%의 팔미트산, 2 내지 3 중량%의 스테아르산, 0.5 중량% 미만의 베헨산, 8 내지 10 중량%의 올레산 및 1 중량% 이하의 리놀레산을 지방산 성분으로서 함유한다. 이는 7.5 내지 9.5의 요오드 값, 0.88 내지 0.90의 비누화 값 및 20 내지 23℃의 융점을 가진다. 올리브유는 올레산을 주로 함유한다[참고 문헌: Lebensmittelchem. Gerichtl. Chem., 39, 112 ∼ 114, 1985). 야자유는 지방산 성분으로서 약 2 중량%의 미리스트산, 42 중량%의 팔미트산, 5 중량%의 스테아르산, 41 중량%의 올레산, 10 중량%의 리놀레산을 함유한다. 야자핵유는 전형적으로 그의 지방산 스펙트럼과 관련해 하기 조성을 갖는다: 9 중량%의 카프로/카프릴/카프르산, 50 중량%의 라우르산, 15 중량%의 미리스트산, 7 중량%의 팔미트산, 2 중량%의 스테아르산, 15 중량%의 올레산 및 1 중량%의 리놀레산. 평지씨유는 전형적으로 약 48 중량%의 에루크산, 15 중량%의 올레산, 14 중량%의 리놀레산, 8 중량%의 리놀렌산, 5 중량%의 에이코센산, 3 중량%의 팔미트산, 2 중량%의 헥사데켄산 및 1 중량%의 도코사디에노산을 지방산 성분으로서 함유한다. 신생 식물로부터의 평지씨유는 불포화 성분이 풍부하다. 여기에서의 전형적인 지방산 성분은 0.5 중량%의 에루크산, 63 중량%의 올레산, 20 중량%의 리놀레산, 9 중량%의 리놀렌산, 1 중량%의 에이코센산, 4 중량%의 팔미트산, 2 중량%의 헥사데센산 및 1 중량%의 도코사디에노산이다. 피마자유의 80 내지 85 중량%은 리시놀레산의 글리세리드로 구성된다. 또한 피마자유는 올레산의 글리세리드 약 7 중량%, 리놀레산의 글리세리드 3 중량% 및 팔미트 및 스테아르산의 글리세리드 약 2 중량%를 함유한다. 대두유 중의 총 지방산의 55 내지 65 중량%는, 고도불포화산, 더욱 구체적으로는 리놀레 및 리놀렌산이다. 해바라기유의 경우도 비슷하여, 그의 전형적인 지방산 스펙트럼-총 지방산 기준-은, 하기와 같다: 약 1 중량%의 미리스트산, 3 내지 10 중량%의 팔미트산, 14 내지 65 중량%의 올레산 및 20 내지 75 중량%의 리놀레산.Peanut oil, on average (based on fatty acids), contains 54% by weight of oleic acid, 24% by weight of linoleic acid, 1% by weight of linolenic acid, 1% by weight of arachic acid, 10% by weight of palmitic acid and 4% by weight of stearic acid. It has a melting point of 2-3 ℃. Flaxseed oil typically contains 5% by weight palmitic acid, 4% by weight stearic acid, 22% by weight oleic acid, 17% by weight linoleic acid and 52% by weight linolenic acid and has an iodine value of 155-205, It has a saponification value of 188 to 196 and a melting point of about -20 ° C. Coconut oil contains about 0.2 to 1 wt% hexanoic acid, 5 to 8 wt% octanoic acid, 6 to 9 wt% decanoic acid, 45 to 51 wt% lauric acid, 16 to 19 wt% myristic acid , 9-11 wt% palmitic acid, 2-3 wt% stearic acid, less than 0.5 wt% behenic acid, 8-10 wt% oleic acid and up to 1 wt% linoleic acid as fatty acid components. It has an iodine value of 7.5 to 9.5, a saponification value of 0.88 to 0.90 and a melting point of 20 to 23 ° C. Olive oil contains mainly oleic acid. See also Lebensmittelchem. Gerichtl. Chem., 39, 112-114, 1985). Palm oil contains about 2% by weight of myristic acid, 42% by weight of palmitic acid, 5% by weight of stearic acid, 41% by weight of oleic acid, and 10% by weight of linoleic acid as fatty acid components. Palm kernel oil typically has the following composition in relation to its fatty acid spectrum: 9% by weight of capro / capryl / capric acid, 50% by weight of lauric acid, 15% by weight of myristic acid, 7% by weight of palmitic acid , 2 wt% stearic acid, 15 wt% oleic acid and 1 wt% linoleic acid. Rapeseed oil is typically about 48% by weight erucic acid, 15% by weight oleic acid, 14% by weight linoleic acid, 8% by weight linolenic acid, 5% by weight eicosane acid, 3% by weight palmitic acid, 2% by weight % Of hexadecanoic acid and 1% by weight of docosadienoic acid are contained as fatty acid components. Rapeseed oil from young plants is rich in unsaturated components. Typical fatty acid components here are 0.5% by weight erucic acid, 63% by weight oleic acid, 20% by weight linoleic acid, 9% by weight linolenic acid, 1% by weight eicosane acid, 4% by weight palmitic acid, 2% by weight % Hexadecenoic acid and 1% docosadienoic acid. 80-85% by weight of castor oil consists of glycerides of ricinoleic acid. Castor oil also contains about 7% by weight of glycerides of oleic acid, 3% by weight of glycerides of linoleic acid and about 2% by weight of glycerides of palmitic and stearic acid. 55-65% by weight of total fatty acids in soybean oil are polyunsaturated acids, more specifically linoleic and linolenic acid. Similarly for sunflower oil, its typical fatty acid spectrum—total fatty acid basis—is as follows: about 1% by weight of myristic acid, 3 to 10% by weight of palmitic acid, 14 to 65% by weight of oleic acid and 20 To 75% by weight of linoleic acid.
트리글리세리드의 지방산 성분에 대한 상기 모든 값 데이터는, 원료의 품질에 의존적이며, 따라서 다양할 수 있다. 코코넛유, 해바라기유 및/또는 평지씨유로부터 선택된 b) 영양소 군을 함유하는 마이크로에멀션이 특히 바람직하다.All of the above value data for the fatty acid component of triglycerides depends on the quality of the raw material and can therefore vary. Particular preference is given to microemulsions containing b) a nutrient group selected from coconut oil, sunflower oil and / or rapeseed oil.
본 발명에 따라 사용되는 마이크로에멀션의 중요한 구성 성분은, 사용되는 유화제 및 유화제 계이다. 비이온성 유화제, 더 구체적으로는 에톡실화 지방 알콜 및 지방산이 유화제로서 바람직하게 사용된다.Important components of the microemulsion used according to the invention are the emulsifiers and emulsifier systems used. Nonionic emulsifiers, more specifically ethoxylated fatty alcohols and fatty acids, are preferably used as emulsifiers.
본 발명에 따른 교시에서의 지방 알콜 에톡실레이트는 하기 화학식 II에 상응한다:Fatty alcohol ethoxylates in the teachings according to the invention correspond to formula II:
[식 중, R3는 탄소수 6 내지 24의 선형, 분지형, 포화 또는 불포화 알킬기이며, n은 1 내지 50의 수이다]. n이 1 내지 35, 더 특별하게는 1 내지 15인 화학식 II의 화합물이 특히 바람직하다. 화학식 II 의 다른 특히 바람직한 화합물은 R3가 탄소수 16 내지 22의 알킬기인 것이다.[Wherein, R 3 is a linear, branched, saturated or unsaturated alkyl group having 6 to 24 carbon atoms, n is a number from 1 to 50]. Particular preference is given to compounds of the formula II wherein n is 1 to 35, more particularly 1 to 15. Another particularly preferred compound of Formula (II) is one in which R 3 is an alkyl group having 16 to 22 carbon atoms.
화학식 II의 화합물은 산성 또는 염기성 촉매의 임의 존재 하에, 가압 하 지방 알콜과 에틸렌 옥시드의 반응의 의해 공지된 방식으로 수득된다. 전형적인 예는 카프로익 알콜, 카프릴 알콜, 2-에틸 헥실 알콜, 카프릭 알콜, 라우릴 알콜, 이소트리데실 알콜, 미리스틸 알콜, 세틸 알콜, 팔미톨레일 알콜, 스테아릴 알콜, 이소스테아릴 알콜, 올레일 알콜, 엘라이딜 알콜, 페트로셀리닐 알콜, 리놀릴 알콜, 리놀레닐 알콜, 엘라에오스테아릴 알콜, 아라킬 알콜, 가돌레일 알콜, 베헤닐알콜, 에루실 알콜 및 브라시딜 알콜, 및 예를 들어 Roelen의 옥소합성으로부터의 알데히드 또는 오일 및 지방 기재의 공업용 메틸 에스테르의 고압 수소화에서 및 불포화 지방 알콜의 이량체화에서의 단량체 분획으로 수득되는 그들의 공업용 혼합물이다. 탄소수 12 내지 18의 공업용 지방 알콜, 예를 들어 코코넛유, 야자유, 야자핵유 또는 수지(獸脂) 지방 알콜이 바람직하다.Compounds of formula (II) are obtained in a known manner by reaction of fatty alcohols with ethylene oxide under pressure in the presence of an acidic or basic catalyst. Typical examples are caproic alcohol, capryl alcohol, 2-ethyl hexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitole alcohol, stearyl alcohol, isostearyl alcohol , Oleyl alcohol, erylidyl alcohol, petroselinyl alcohol, linolyl alcohol, linoleyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and examples Aldehydes from the oxosynthesis of Roelen or their industrial mixtures obtained as monomer fractions in high pressure hydrogenation of oil and fat based industrial methyl esters and in dimerization of unsaturated fatty alcohols. Industrial fatty alcohols having 12 to 18 carbon atoms are preferred, such as coconut oil, palm oil, palm kernel oil or resin fatty alcohols.
유화제 또는 유화제 성분으로서도 또한 사용될 수 있는 지방산 에톡실레이트는, 바람직하게는 하기 화학식 III에 상응한다:Fatty acid ethoxylates, which may also be used as emulsifiers or emulsifier components, preferably correspond to formula III:
[식 중, R4는 탄소수 12 내지 22의 선형 또는 분지형 알킬기이며, m은 5 내지 50, 바람직하게는 15 내지 35의 수이다]. 전형적인 예는, 20 내지 30 몰의 에틸렌 옥시드를, 라우르산, 이소트리데칸산, 미리스트산, 팔미트산, 팔미톨레산, 스테아르산, 이소스테아르산, 올레산, 엘라이드산, 페트로셀산, 리놀레산, 리놀렌산, 엘라에오스테아르산, 아라크산, 가돌레산, 베헨산 및 에루크산, 및 예를 들어, 천연 지방 및 오일의 가압 가수분해에서 또는 Roelen의 옥소합성으로부터의 알데히드의 환원에서 수득되는 그들의 공업적 혼합물 상에 부가한 생성물이다. 바람직하게는 20 내지 30 몰의 에틸렌 옥시드를 C16-18지방산에 부가한 생성물이 사용된다.[Wherein, R 4 is a linear or branched alkyl group having 12 to 22 carbon atoms, and m is 5 to 50, preferably 15 to 35]. Typical examples include 20 to 30 moles of ethylene oxide such as lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elideic acid, and petroleum acid. Obtained by linoleic acid, linolenic acid, elaostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, and, for example, by pressurized hydrolysis of natural fats and oils or by reduction of aldehydes from the oxosynthesis of Roelen Product added to their industrial mixture. Preferably a product is used in which 20 to 30 moles of ethylene oxide are added to the C 16-18 fatty acid.
유화제로서도 사용될 수 있는 부분 글리세리드는 바람직하게는 하기 화학식IV에 상응한다:Partial glycerides which can also be used as emulsifiers preferably correspond to formula IV:
[식 중, COR5는 탄소수 12 내지 22의 선형 또는 분지형 아실기이며, x, y 및 z는 함께 0을 나타내거나, 또는 1 내지 50, 바람직하게는 15 내지 35의 수를 나타낸다]. 본 발명의 목적에 적합한 부분 글리세리드의 전형적인 예는, 라우르산 모노글리세리드, 코코넛 지방산 모노글리세리드, 팔미트산 모노글리세리드, 스테아르산 모노글리세리드, 이소스테아르산 모노글리세리드, 올레산 모노글리세리드, 및 수지 지방산 모노글리세리드, 및 5 내지 50, 바람직하게는 20 내지 30 몰의 에틸렌 옥시드와의 그의 부가 생성물이다. 바람직하게는, 모노글리세리드, 또는 COR5는 탄소수 16-18의 선형 아실기인 모노글리세리드 IV 를 주로 많이 함유하는 공업적 모노/디글리세리드 혼합물이 사용된다.[Wherein, COR 5 is a linear or branched acyl group having 12 to 22 carbon atoms, and x, y and z together represent 0 or 1 to 50, preferably 15 to 35]. Typical examples of partial glycerides suitable for the purposes of the present invention include lauric acid monoglycerides, coconut fatty acid monoglycerides, palmitic acid monoglycerides, stearic acid monoglycerides, isostearic acid monoglycerides, oleic acid monoglycerides, and resin fatty acid monoglycerides. And addition products thereof with 5 to 50, preferably 20 to 30 moles of ethylene oxide. Preferably, the monoglyceride, or COR 5 is the industrially mono / diglyceride mixture containing mainly a lot of linear acyl monoglyceride IV with a carbon number of 16-18 is used.
다른 적합한 유화제는, 예를 들어 하나 이상의 하기 군으로부터의 비이온성 계면활성제이다:Other suitable emulsifiers are, for example, nonionic surfactants from one or more of the following groups:
(I) 2 내지 30 몰의 에틸렌 옥시드 및/또는 0 내지 5 몰의 프로필렌 옥시드를 탄소수 8 내지 22의 선형 지방 알콜 상에 부가한 생성물;(I) the product of adding 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto a linear fatty alcohol having 8 to 22 carbon atoms;
(II) 탄소수 6 내지 22의 포화 및 불포화 지방산의 글리세롤 모노에스테르및 디에스테르, 및 소르비탄 모노에스테르 및 디에스테르, 및 그들의 에틸렌 옥시드 부가생성물;(II) glycerol monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms, and sorbitan monoesters and diesters, and their ethylene oxide adducts;
(III) 알킬기의 탄소수가 8 내지 22인 알킬 모노- 및 올리고글리코시드 및 그들의 에톡실화 유사체;(III) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms of alkyl groups and their ethoxylated analogs;
(IV) 15 내지 60 몰의 에틸렌 옥시드를 피마자유 및/또는 수소화 피마자유 상에 부가한 생성물;(IV) the product of adding 15 to 60 moles of ethylene oxide onto castor oil and / or hydrogenated castor oil;
(V) 폴리올 에스테르, 특히, 폴리글리세롤 에스테르, 예컨대 폴리글리세롤 폴리리시놀레에이트 또는 폴리글리세롤 폴리-12-히드록시스테아레이트. 상기 부류의 몇몇으로부터의 화합물의 혼합물도 적합하다:(V) polyol esters, in particular polyglycerol esters, such as polyglycerol polylysinoleate or polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes are also suitable:
(VI) 2 내지 15 몰의 에틸렌 옥시드를 피마자유 및/또는 수소화 피마자유 상에 부가한 생성물;(VI) the product of adding 2 to 15 moles of ethylene oxide onto castor oil and / or hydrogenated castor oil;
(VII) 선형, 분지형, 불포화 또는 포화 C6-22지방산, 리시놀레산 및 12-히드록시스테아르산과, 글리세롤, 폴리글리세롤, 펜타에리트리톨, 디펜타에리트리톨, 당 알콜(예를 들어, 소르비톨) 및 폴리글리코시드(예를 들어, 셀룰로오스) 기재의 부분 에스테르;(VII) linear, branched, unsaturated or saturated C 6-22 fatty acids, ricinoleic acid and 12-hydroxystearic acid with glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol ) And partial esters based on polyglycosides (eg cellulose);
(VIII) 울 왁스 알콜;(VIII) wool wax alcohols;
(XI) 폴리알킬렌 글리콜.(XI) polyalkylene glycols.
에틸렌 옥시드 및/또는 프로필렌 옥시드를 지방산의 글리세롤 모노- 및 디에스테르 및 소르비탄 모노- 및 디에스테르 또는 피마자유 상에 부가한 생성물은공지된 시판 생산물이다. 이들은, 평균 알콕실화도가 에틸렌 옥시드 및/또는 프로필렌 옥시드의 양과 부가 반응이 일어나는 기질량 사이 비에 상응하는 균질 혼합물이다.The product of the addition of ethylene oxide and / or propylene oxide onto glycerol mono- and diesters of fatty acids and sorbitan mono- and diesters or castor oil is a known commercial product. These are homogeneous mixtures in which the average alkoxylation degree corresponds to the ratio between the amount of ethylene oxide and / or propylene oxide and the base mass at which the addition reaction takes place.
군 (III)의 유화제, 즉 알킬 글리코시드를 사용하는 것이 특히 바람직하다. 알킬 및 알케닐 올리고글리코시드는 하기 화학식 V에 상응하는 비이온성 계면활성제로 공지되었다:Particular preference is given to using emulsifiers of group (III), ie alkyl glycosides. Alkyl and alkenyl oligoglycosides are known as nonionic surfactants corresponding to formula (V):
[식 중, R6는 탄소수 4 내지 22의 알킬 및/또는 알케닐 라디칼이며, G는 탄소수 5 또는 6의 당 단위이고, p 는 1 내지 10 의 수이다]. 이들은 제조적 유기 화학과 관련된 방법으로 수득될 수 있다. [Starch/Staerke 45, 281 (1993) 중의 Biermann 등, Cosm. Toil. 108, 89 (1993) 중의 B. Salka, 및 SOEFW-Journal, 8 호 598 (1995) 중의 J. Kahre 등의 개요 문헌]을 상기 주제에 대하여 이용할 수 있는 광범위한 문헌의 대표적 문헌으로 언급할 수 있다.[Wherein R 6 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar unit having 5 or 6 carbon atoms and p is a number of 1 to 10]. These can be obtained by methods relating to preparative organic chemistry. Biermann et al., Cosm. In Starch / Staerke 45, 281 (1993). Toil. B. Salka in 108, 89 (1993), and J. Kahre et al. In SOEFW-Journal, 8, 598 (1995), may be cited as representative documents of a wide range of literature available on this subject.
알킬 및/또는 알케닐 올리고글리코시드는 탄소수 5 또는 6의 알도오스 또는 케토오스, 바람직하게는 글루코오스로부터 유도될 수 있다. 따라서, 바람직한 알킬 및/또는 알케닐 올리고글리코시드는 알킬 및/또는 알케닐 올리고글리코시드이다. 화학식 V 중의 지수 p는 올리고머화도(DP), 즉 모노- 및 올리고글리코시드의 분포를 나타내며, 1 내지 10의 수이다. 주어진 화합물 중의 p 는 항상 정수여야 하며, 특히 1 내지 6을 나타낼 수 있지만, 특정 알킬 올리고글리코시드에서의 값 p는 일반적으로 분수인 분석적으로 결정되는 계산치가다. 바람직하게는 올리고머화도 p의 평균이 1.1 내지 3.0인 알킬 및/또는 알케닐 올리고글리코시드가 사용된다. 1.7 미만, 더욱 특별하게는 1.2 내지 1.4의 올리고머화도를 가진 알킬 및/또는 알케닐 올리고글리코시드가 본 출원의 관점에서 바람직하다. 알킬 또는 알케닐 라디칼 R6는 탄소수 4 내지 11, 바람직하게는 8 내지 10의 1차 알콜로부터 유도될 수 있다. 전형적인 예는 부탄올, 카프로익 알콜, 카프릴릭 알콜, 카프릭 알콜 및 운데실 알콜, 및 예를 들어, 공업용 지방산 메틸 에스테르의 수소화 또는 Roelen의 옥소합성으로부터의 알데히드의 수소화에서 수득되는 그들의 공업적 혼합물이다. 증류에 의해 공업용 C8-18코코넛유 지방 알콜의 분리 중 첫 번째 수행으로 수득되며, 불순물로서 6 중량% 미만의 C12알콜을 함유할 수 있는 C8내지 C10의 사슬 길이를 가진 알킬 글리코시드(DP= 1 내지 3), 및 공업용 C9/11옥소알콜 기재의 알킬 올리고글리코시드(DP=1 내지 3)가 바람직하다. 또한, 알킬 또는 알케닐 라디칼 R6는 탄소수 12 내지 22, 바람직하게는 탄소수 12 내지 14의 1차 알콜로부터 유도될 수 있다. 전형적인 예는, 라우릴 알콜, 미리스틸 알콜, 세틸 알콜, 팔미톨레일 알콜, 스테아릴 알콜, 이소스테아릴 알콜, 올레일 알콜, 엘라이딜 알콜, 페트로셀리닐 알콜, 아르알킬 알콜, 가돌레일 알콜, 베헤닐 알콜, 에루실 알콜, 브라시딜 알콜 및 상기 기재한 바와 같이 수득할 수 있는 그들의 공업적 혼합물이다. 수소화 C12/14코코알콜 기재의 1 내지 3의 DP를 가진 알킬 올리고글루코시드가 바람직하다. 화학식 V의 알킬 글리코시드가 유화제로서 사용되면, 소량의 폴리히드록시카르복실산, 바람직하게는 시트르산을 제형 보조제로서 그들과 함께 사용하는 것이 유리할 수 있다. 이러한 경우, 폴리히드록시산은 0.1 내지 3.0 중량%, 바람직하게는 0.1 내지 1.0 중량%의 양으로 사용된다.Alkyl and / or alkenyl oligoglycosides may be derived from aldose or ketose, preferably glucose, having 5 or 6 carbon atoms. Thus, preferred alkyl and / or alkenyl oligoglycosides are alkyl and / or alkenyl oligoglycosides. The index p in formula V represents the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and is a number from 1 to 10. P in a given compound must always be an integer, and in particular can represent 1 to 6, but the value p for a particular alkyl oligoglycoside is an analytically determined calculation which is generally a fraction. Preferably alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0 are used. Alkyl and / or alkenyl oligoglycosides having an oligomerization degree of less than 1.7, more particularly 1.2 to 1.4, are preferred in view of the present application. The alkyl or alkenyl radicals R 6 can be derived from primary alcohols having 4 to 11 carbon atoms, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and their industrial mixtures obtained, for example, from hydrogenation of industrial fatty acid methyl esters or hydrogenation of aldehydes from the oxosynthesis of Roelen. to be. An alkyl glycoside having a chain length of C 8 to C 10 which is obtained by distillation as the first run of the separation of industrial C 8-18 coconut oil fatty alcohols and may contain less than 6% by weight of C 12 alcohols as impurities. (DP = 1 to 3), and alkyl oligoglycosides based on industrial C 9/11 oxoalcohol (DP = 1 to 3) are preferred. In addition, alkyl or alkenyl radicals R 6 may be derived from primary alcohols having 12 to 22 carbon atoms, preferably 12 to 14 carbon atoms. Typical examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitole alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ellidil alcohol, petrolininyl alcohol, aralkyl alcohol, gadoleyl alcohol, Behenyl alcohol, erucyl alcohol, brassidyl alcohol and their industrial mixtures obtainable as described above. Preference is given to alkyl oligoglucosides having 1 to 3 DPs based on hydrogenated C 12/14 cocoalcohols . If alkyl glycosides of the formula V are used as emulsifiers, it may be advantageous to use small amounts of polyhydroxycarboxylic acids, preferably citric acid, with them as formulation aids. In this case, the polyhydroxy acid is used in an amount of 0.1 to 3.0% by weight, preferably 0.1 to 1.0% by weight.
본 발명에 따라 사용되는 마이크로에멀션은 바람직하게는 20 내지 90 중량%의 물, 더욱 바람직하게는 30 내지 80 중량%, 가장 바람직하게는 30 내지 60 중량%의 물을 함유한다. 100 중량%를 맞추는 것은 오일상 및 유화제, 및 선택적으로는 다른 보조제 및 첨가제이다. 오일상 자체는 10 내지 80 중량, 더욱 바람직하게는 20 내지 70 중량%, 가장 바람직하게는 25 내지 55 중량의 양으로 존재한다. 바람직한 구현예에서, 오일상은 전적으로 성분 a) 또는 b) 또는 그 성분들의 혼합물만을 함유한다. 중량비 1:1로 오일상 및 수상을 함유하는 에멀션을 사용하는 것이 특히 바람직하다. 유화제 또는 유화제 계는 바람직하게는 10 내지 50 중량%, 더욱 바람직하게는 15 내지 45 중량%, 가장 바람직하게는 20 내지 40 중량%의 양으로 존재한다.The microemulsions used according to the invention preferably contain 20 to 90% by weight of water, more preferably 30 to 80% by weight and most preferably 30 to 60% by weight of water. Matching 100% by weight is an oil phase and an emulsifier, and optionally other auxiliaries and additives. The oily phase itself is present in an amount of 10 to 80 weights, more preferably 20 to 70 weight percent, most preferably 25 to 55 weights. In a preferred embodiment, the oil phase contains solely component a) or b) or a mixture of components. Particular preference is given to using emulsions containing oil phase and water phase in a weight ratio of 1: 1. The emulsifier or emulsifier system is preferably present in an amount of 10 to 50% by weight, more preferably 15 to 45% by weight and most preferably 20 to 40% by weight.
본 발명에 따라, 기재된 마이크로에멀션은 모든 종류의 발효 공정에 사용될 수 있다. 숙련가에게 공지된 임의의 각종 공정, 예를 들어 뱃치 또는 페드 뱃치 및 연속 발효가 이용될 수 있다. 또한, 숙련가에게 공지된 임의의 발효기 시스템도 사용될 수 있다. 구체적인 것은 [Crueger, 50 ∼ 70 쪽] 참조.더욱이, 마이크로에멀션의 사용이 특정 미생물에만 제한되지는 않는다. 반대로, 에멀션은 발효를 통한 숙련가에게 공지된 임의의 화합물의 제조 및 전환에 사용될 수 있다. 주로 항생제 합성에 사용되는 통상적인 발효 공정(참고: Crueger, 197 ∼ 242 쪽) 외에도, 기재된 에멀션은 또한 미생물 전환(생물 전환), 예를 들어, 스테로이드 및 스테롤, 항생제 및 살충제의 전환, 또는 비타민의 제조(참조: Crueger, 254 ∼ 273 쪽)에 사용하기에도 적합하다. 그러나, 기재된 에멀션은 바람직하게는 항생제, 예를 들어 세팔로스포린, 틸로신 또는 에리트로마이신의 제조를 위한 발효 공정에 사용된다.According to the invention, the described microemulsions can be used in all kinds of fermentation processes. Any of various processes known to the skilled person can be used, such as batch or fed batches and continuous fermentation. In addition, any fermenter system known to the skilled person can be used. For details see [Crueger, pp. 50-70]. Furthermore, the use of microemulsions is not limited to specific microorganisms. In contrast, emulsions can be used for the preparation and conversion of any compound known to the skilled person through fermentation. In addition to conventional fermentation processes (cf. Crueger, pp. 197-242), which are mainly used for antibiotic synthesis, the described emulsions can also be used for microbial transformation (bioconversion), for example, steroids and sterols, antibiotics and pesticides, or vitamins. It is also suitable for use in manufacture (cf. Crueger, pp. 254-273). However, the described emulsions are preferably used in fermentation processes for the preparation of antibiotics, for example cephalosporins, tyrosine or erythromycin.
일반적으로, 마이크로에멀션은 미생물 및 질소원 및 미량 원소 및 선택적으로는 다른 보조제, 특히 소포제를 함유하는 수성 발효 브로쓰에 적합하게 첨가된다. 적합한 질소원은, 예를 들어, 펩톤, 효모 또는 맥아 추출물, 옥수수 침지액, 요소 또는 레시틴이다. 미량 원소는 무기염, 예를 들어 질산나트륨 또는 질산칼륨, 질산암모늄, 황산암모늄, 황산철 등의 형태로 존재할 수 있다. 또한, 다른 첨가제, 예컨대 소포제 또는 질소원을 마이크로에멀션 자체에 첨가하는 것이 유리할 수 있다.In general, microemulsions are suitably added to aqueous fermentation broths containing microorganisms and nitrogen sources and trace elements and optionally other auxiliaries, in particular antifoaming agents. Suitable nitrogen sources are, for example, peptone, yeast or malt extracts, corn steep liquor, urea or lecithin. Trace elements can be present in the form of inorganic salts such as sodium or potassium nitrate, ammonium nitrate, ammonium sulfate, iron sulfate and the like. It may also be advantageous to add other additives such as antifoams or nitrogen sources to the microemulsion itself.
개시 물질을 혼합함으로써 각종 마이크로에멀션을 제조했다. 그들의 조성은 하기 표 1 에 나타냈다. 소적 크기는 Malvern Mastersizer 2000으로 측정했다. 에멀션은, 예를 들어 발효 공정을 위한 단독 영양원으로서 적합하며, 수성 발효 브로쓰에 직접 첨가될 수 있다.Various microemulsions were prepared by mixing the starting materials. Their composition is shown in Table 1 below. Droplet size was measured with a Malvern Mastersizer 2000. The emulsion is suitable, for example, as a sole nutrient for the fermentation process and can be added directly to the aqueous fermentation broth.
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