KR102633521B1 - Method for preparing antiseptic emulsifier based on polyglyceryl-n fatty acid ester - Google Patents
Method for preparing antiseptic emulsifier based on polyglyceryl-n fatty acid ester Download PDFInfo
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- polyglyceryl
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- stearate
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- capryloyl
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 34
- -1 fatty acid ester Chemical class 0.000 title claims abstract description 32
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 31
- 239000000194 fatty acid Substances 0.000 title claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002421 anti-septic effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 63
- HMFAWZAFJIXXDI-UHFFFAOYSA-N octanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCC HMFAWZAFJIXXDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003755 preservative agent Substances 0.000 claims abstract description 40
- 230000002335 preservative effect Effects 0.000 claims abstract description 35
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960002446 octanoic acid Drugs 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 13
- 239000008117 stearic acid Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010517 secondary reaction Methods 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 description 26
- 239000002537 cosmetic Substances 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 16
- 239000002202 Polyethylene glycol Substances 0.000 description 14
- 229920001223 polyethylene glycol Polymers 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 206010040914 Skin reaction Diseases 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 239000006071 cream Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000007794 irritation Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 230000035483 skin reaction Effects 0.000 description 6
- 231100000430 skin reaction Toxicity 0.000 description 6
- 231100000344 non-irritating Toxicity 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000036556 skin irritation Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 206010067484 Adverse reaction Diseases 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000006838 adverse reaction Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010015150 Erythema Diseases 0.000 description 2
- 208000002193 Pain Diseases 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000000774 hypoallergenic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 208000002029 allergic contact dermatitis Diseases 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 208000001875 irritant dermatitis Diseases 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HRDIQMHETSHVMC-UHFFFAOYSA-N octadecanoic acid;octanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O HRDIQMHETSHVMC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
- A61K2800/524—Preservatives
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Emergency Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Abstract
본 발명은 방부성 유화제의 기능을 지닌 폴리글리세릴-n 지방산에스테르 제조방법에 관한 것이다. 보다 상세하게는, 방부성능을 발휘하는 카프릴산 및 유화성능을 발휘하는 스테아르산을 폴리글리세릴-n 카프릴로일스테아레이트로 합성하여 방부성 유화제의 기능을 지닌 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법에 관한 것이다.
이를 위해 본 발명은 반응물인 글리세린에 수산화나트륨 0.2mol 및 프로필렌글라이콜 2mol을 반응용매로 하여 진공반응기에 투입하고, 110℃의 온도조건에서 1시간 동안 완전 용해시켜 1차반응물인 폴리글리세린(Polyglycerin)을 생성하는 1차반응단계; 1차반응단계로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 3시간 반응시켜 2차반응물인 폴리글리세릴 스테아레이트(Polyglyceryl stearate)를 합성하는 2차반응단계; 2차반응단계로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 2시간 동안 반응시켜 폴리글리세릴 카프릴로일스테아레이트(Polyglyceryl capryloyl stearate)를 합성하는 3차반응단계; 3차반응단계를 거쳐 수득된 폴리글리세릴 카프릴로일스테아레이트를 냉각시키는 냉각단계을 포함하는 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법을 제공한다.The present invention relates to a method for producing polyglyceryl-n fatty acid ester with the function of a preservative emulsifier. More specifically, caprylic acid, which exhibits preservative performance, and stearic acid, which exhibits emulsifying performance, are synthesized into polyglyceryl-n capryloyl stearate to produce a polyglyceryl-n fatty acid ester-based preservative that functions as a preservative emulsifier. It relates to a method for manufacturing emulsifiers.
For this purpose, in the present invention, 0.2 mol of sodium hydroxide and 2 mol of propylene glycol as reaction solvents are added to glycerin, the reactant, into a vacuum reactor, and completely dissolved for 1 hour at a temperature of 110°C to produce polyglycerin, the primary reactant. ) The first reaction step to produce; Stearic acid was added to the polyglycerin obtained from the first reaction step and reacted for 3 hours at a temperature of 180°C and a low vacuum of 1×10 -3 torr to produce polyglyceryl stearate, a secondary reactant. secondary reaction step to synthesize stearate; Caprylic acid was added to the polyglyceryl stearate obtained from the second reaction step and reacted at a temperature of 120°C and 1×10 -3 torr for 2 hours to produce polyglyceryl capryloylstearate ( Third reaction step to synthesize polyglyceryl capryloyl stearate; A method for producing a preservative emulsifier based on polyglyceryl-n fatty acid ester is provided, including a cooling step of cooling polyglyceryl capryloyl stearate obtained through a third reaction step.
Description
본 발명은 방부성 유화제의 기능을 지닌 폴리글리세릴-n 지방산에스테르 제조방법에 관한 것이다. 보다 상세하게는, 방부성능을 발휘하는 카프릴산 및 유화성능을 발휘하는 스테아르산을 폴리글리세릴-n 카프릴로일스테아레이트로 합성하여 방부성 유화제의 기능을 지닌 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법에 관한 것이다.The present invention relates to a method for producing polyglyceryl-n fatty acid ester with the function of a preservative emulsifier. More specifically, caprylic acid, which exhibits preservative performance, and stearic acid, which exhibits emulsifying performance, are synthesized into polyglyceryl-n capryloyl stearate to produce a polyglyceryl-n fatty acid ester-based preservative that functions as a preservative emulsifier. It relates to a method for manufacturing emulsifiers.
계면활성제는 한 분자 내에 물과 친화성을 가진 친수기와 오일과 친화성을 가진 친유기(소수기)을 모두 가진 화합물로서, 양친매성 특성으로 인하여 계면활성제 분자는 물과 오일의 계면에서 친수기는 물 방향으로 친유기는 오일 방향으로 자발적으로 일정한 방향성 배열을 하게 되고, 계면에 배열된 계면활성제는 계면장력 등의 계면의 물성을 현저하게 변화시킨다. 그리고 계면활성제는 물 등의 용매에서 자발적으로 마이셀, 라멜라 리퀴드 크리스탈 등의 자기 회합체를 형성한다. 이러한 계면활성 특성으로 인하여 계면활성제는 유화, 분산, 가용화, 습윤, 기포, 세정, 정전기 방지, 살균 등의 다양한 기능을 발휘함에 따라 가정용 및 산업용 세정제, 화장품, 식품, 의약품, 섬유처리제, 페인트, 농약, 제지, 윤활유, 플라스틱, 고분자중합제 등 광범위한 산업에 활용되고 있다. A surfactant is a compound that has both a hydrophilic group with affinity for water and a lipophilic group (hydrophobic group) with affinity for oil within one molecule. Due to its amphiphilic nature, the hydrophilic group is oriented toward the water at the interface between water and oil. The lipophilic groups spontaneously form a certain directional arrangement in the direction of the oil, and the surfactants arranged at the interface significantly change the physical properties of the interface, such as interfacial tension. And surfactants spontaneously form self-associations such as micelles and lamellar liquid crystals in solvents such as water. Due to these surfactant properties, surfactants exert various functions such as emulsification, dispersion, solubilization, wetting, foaming, cleaning, anti-static, and sterilization, and are used in household and industrial cleaners, cosmetics, food, pharmaceuticals, textile treatments, paints, and pesticides. It is used in a wide range of industries, including papermaking, lubricants, plastics, and polymer polymerization.
계면활성제는 친수기와 친유기의 조합으로 이루어져 있어 어떤 종류의 친수기와 친유기를 조합하는 가에 따라 매우 다양한 화학구조를 가진 계면활성제들이 자연계에 존재하거나 합성에 의해 만들어진다. 통상 소수기·친유기는 주로 긴 사슬형태의 탄화수소(-CH2-)계로 구성되고 친수기는 물과 이온-쌍극자 상호작용을 하는 이온성(음이온, 양이온, 양쪽성) 그룹 또는 물과 수소결합을 하는 비이온성 그룹으로 구성된다. 친수기로서 sulfate(-OSO3-), carboxylate(-COO-), quaternary ammonium(-N+) 같은 이온성 그룹은 물과 강력한 상호작용을 나타내어 계면활성이 높은 경향이 있으나, 이온성을 가진 친수기 그룹이 생체조직과 장기간 접촉 시 정전기적 상호작용(인력)으로 인해 생체조직에 안전성 문제가 우려된다. 따라서 식품, 화장품, 의약품 등 인체에 적용하는 제품에 계면활성제를 사용하는 경우에는 대개 비이온성 친수기를 가진 계면활성제를 우선적으로 활용하는 경향이 있다. Surfactants are composed of a combination of hydrophilic and lipophilic groups. Depending on the type of hydrophilic and lipophilic groups used, surfactants with very diverse chemical structures exist in nature or are created synthetically. Typically, hydrophobic and lipophilic groups are mainly composed of long-chain hydrocarbons (-CH 2 -), and hydrophilic groups are ionic (anion, cation, amphoteric) groups that have ion-dipole interactions with water or non-ionic groups that form hydrogen bonds with water. It is comprised of the Onsung Group. As hydrophilic groups, ionic groups such as sulfate (-OSO 3- ), carboxylate (-COO - ), and quaternary ammonium (-N + ) exhibit strong interaction with water and tend to have high surface activity. There are concerns about the safety of biological tissue due to electrostatic interaction (attractive force) when in contact with this biological tissue for a long period of time. Therefore, when surfactants are used in products applied to the human body, such as food, cosmetics, and pharmaceuticals, surfactants with nonionic hydrophilic groups tend to be used preferentially.
비이온성 친수기를 가진 대표적인 계면활성제는 친수기가 에틸렌옥사이드(ethylene oxide, -CH2CH2O-)의 중합체인 폴리옥시에틸렌(polyoxyethylene, POE)계 또는 폴리에틸렌글라이콜(polyethylene glycol, PEG)계 라고 불리는 비이온계면활성제이다. 단순히 에틸렌옥사이드의 중합도를 변화시킴에 따라 다양한 친수성 정도(HLB값)를 가진 비이온계면활성제들을 제조할 수 있어 그 응용분야는 세정제, 화장품, 식품, 의약품 등에 활발하게 사용되어 왔다. Representative surfactants with nonionic hydrophilic groups are called polyoxyethylene (POE) series or polyethylene glycol (PEG) series, in which the hydrophilic group is a polymer of ethylene oxide (-CH 2 CH 2 O-). It is called a non-ionic surfactant. By simply changing the degree of polymerization of ethylene oxide, nonionic surfactants with various degrees of hydrophilicity (HLB value) can be manufactured, and their application fields have been actively used in detergents, cosmetics, food, and pharmaceuticals.
하지만 에틸렌옥사이드의 안전성 문제, PEG(POE)계 계면활성제의 합성공정인 에톡시레이션(ethoxylation) 공정 중 생성되는 1,4-dioxane의 안전성 문제, 그리고 PEG(POE)계 계면활성제가 비록 비이온성이지만 장기간 사용 시 인체에 대한 안전성, 친화성 문제가 제기되고 있다. 특히 계면활성제의 인체 적용 시 특별한 주의가 요구되는 있는 화장품, 식품 등 분야에서 PEG 및 POE계 비이온계면활성제의 안전성 문제는 지속적으로 제기되고 있다. However, there are safety issues with ethylene oxide, safety issues with 1,4-dioxane produced during the ethoxylation process, which is a synthesis process for PEG (POE)-based surfactants, and even though PEG (POE)-based surfactants are nonionic. Issues regarding safety and compatibility with the human body are being raised during long-term use. In particular, safety issues with PEG and POE-based nonionic surfactants are continuously being raised in fields such as cosmetics and food, where special precautions are required when applying surfactants to the human body.
PEG 및 POE 계 비이온계면활성제의 안전성 문제에 대응하여 대안으로 제안된 비이온계면활성제가 글리세린(글리세롤) 중합체를 친수기로 사용한 폴리글리세린계 비이온계면활성제이나 합성 조건이 까다롭고 합성 표준화가 어려운 문제점이 있다.In response to the safety issues of PEG and POE-based nonionic surfactants, the nonionic surfactant proposed as an alternative is a polyglycerin-based nonionic surfactant that uses glycerin (glycerol) polymer as a hydrophilic group, but the synthesis conditions are difficult and synthesis standardization is difficult. There is.
현재까지 개발 시판 되고 있는 PEG 및 POE 계 비이온 계면활성제를 대체사용 가능한 유화제는 폴리글리세린 지방산에스테르 계면활성제가 사용되고 있으나 친유성 유화력에 비해 친수성 유화력이 강해 화장품 제형 유화시 친유성 유화제와 혼합하여 사용하는 실정이다.Polyglycerin fatty acid ester surfactants are used as emulsifiers that can replace PEG and POE-based nonionic surfactants that have been developed and sold to date. However, they have stronger hydrophilic emulsifying power than lipophilic emulsifying power, so they are used by mixing with lipophilic emulsifiers when emulsifying cosmetic formulations. This is the situation.
이러한 유화력이 감소되는 문제점은 글리세린의 탈수축합반응에 의한 폴리글리세린 합성시 발생하는 글리세린 중합체의 형태에 기인한다.This problem of reduced emulsifying power is due to the form of the glycerin polymer generated during polyglycerin synthesis through the dehydration condensation reaction of glycerin.
또한, 화장품 제형 제조시 첨가되는 방부제는 인체에 유해하며 경피 자극을 유발할 수 있고, 유화제형의 불완전성을 동반할 수 있다.In addition, preservatives added when manufacturing cosmetic formulations are harmful to the human body, may cause dermal irritation, and may be accompanied by imperfections in the emulsion formulation.
반면, 폴리글리세린은 자연 및 인체 친화성 관점에서 매우 우수한 친수기이며 폴리에틸렌글리콜(PEG) 대체 친수기로써 적용할 수 있다. On the other hand, polyglycerin is an excellent hydrophilic group in terms of nature and human compatibility and can be applied as an alternative hydrophilic group to polyethylene glycol (PEG).
이에 본 발명에서는 유화제 합성시 도입되는 종래 폴리에틸렌글라이콜 친수기를 폴리글리세린으로 대체 사용하여 상기 문제점을 개선하고자 한다.Accordingly, the present invention seeks to improve the above problems by replacing the conventional polyethylene glycol hydrophilic group introduced during emulsifier synthesis with polyglycerin.
한편, 화장품은 여러 화학 물질의 복합체로 수천 가지의 물질이 구성성분으로 사용되고 있다. 그 중 오일과 물을 주성분으로 하고, 미생물의 탄소원이 되는 glycerine이나 sorbitol 등, 질소원으로는 아미노산 유도체, 단백질 등 배합된 것이 많아 미생물의 급격한 증식을 일으켜 제품의 변질을 일으킬 가능성이 있다.Meanwhile, cosmetics are a complex of several chemical substances, and thousands of substances are used as components. Among them, oil and water are the main ingredients, and many contain glycerine and sorbitol, which serve as carbon sources for microorganisms, and amino acid derivatives and proteins as nitrogen sources, which may cause rapid growth of microorganisms and cause deterioration of the product.
따라서, 화장품 사용 중 오염되어 미생물이 일으키는 변패·변취로부터 화장품을 장시간 보호하기 위해 방부제는 필수적이다. 하지만, 방부제를 고농도로 사용할 경우 절대 안전하다고 볼 수 없으며, 인체 독성 또한 나타낼 가능성이 있기 때문에 국가에서 허용한도를 규정하고 있으며 화장품 사용에 있어서 피부자극의 요인으로 방부제가 주로 주목되고 있어, 최소의 피부 자극을 나타내면서 안전한 방부력을 내기 위한 여러 연구가 진행되고 있다.Therefore, preservatives are essential to protect cosmetics for a long time from spoilage and odor caused by microorganisms that become contaminated during use. However, when preservatives are used in high concentrations, they cannot be considered absolutely safe, and there is a possibility of toxicity to the human body, so the country regulates the allowable limit. Preservatives are mainly noted as a cause of skin irritation in the use of cosmetics, so there is a minimum risk of skin irritation. Several studies are being conducted to produce safe preservative properties while being irritating.
이에 본 발명에서는 PEG 및 POE 계열 비이온 계면활성제의 대체 및 화장품 방부제의 위험성 등으로부터 제기될 수 있는 상기 문제점의 극복을 위해 비이온 친수성 계면활성제의 유화력을 보유하면서 방부효능을 나타낼 수 있는 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제를 개발하였다. Accordingly, in the present invention, in order to replace PEG and POE series non-ionic surfactants and overcome the problems that may arise from the risks of cosmetic preservatives, polyglyceryl, which can exhibit preservative efficacy while retaining the emulsifying power of non-ionic hydrophilic surfactants, is used. -n A preservative emulsifier based on fatty acid ester was developed.
선행기술문헌 : KR 등록특허공보 제10-1503923호(2015.3.19.공고)Prior art literature: KR Registered Patent Publication No. 10-1503923 (announced on March 19, 2015)
현재까지 개발 시판 되고 있는 PEG 및 POE 계 비이온 계면활성제를 대체사용 가능한 유화제는 폴리글리세린 지방산에스테르 계면활성제가 사용되고 있으나 친유성 유화력에 비해 친수성 유화력이 강해 화장품 제형 유화시 친유성 유화제와 혼합하여 사용하는 실정이다. 이러한 유화력이 감소되는 문제점은 글리세린의 탈수축합반응에 의한 폴리글리세린 합성시 발생하는 글리세린 중합체의 형태에 기인한다.Polyglycerin fatty acid ester surfactants are used as emulsifiers that can replace PEG and POE-based nonionic surfactants that have been developed and sold to date. However, they have stronger hydrophilic emulsifying power than lipophilic emulsifying power, so they are used by mixing with lipophilic emulsifiers when emulsifying cosmetic formulations. This is the situation. This problem of reduced emulsifying power is due to the form of the glycerin polymer generated during polyglycerin synthesis through the dehydration condensation reaction of glycerin.
또한, 화장품 제형 제조시 첨가되는 방부제는 인체에 유해하며 경피 자극을 유발할 수 있고, 유화제형의 불완전성을 동반할 수 있다.In addition, preservatives added when manufacturing cosmetic formulations are harmful to the human body, may cause dermal irritation, and may be accompanied by imperfections in the emulsion formulation.
이에 본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로, 유화제 합성 시 도입되는 종래 폴리글리세린 친수기에 친유성 방부성능을 발휘할 수 있는 친유성 지방산을 추가 합성하여 종래 폴리글리세릴 지방산에스테르를 대체 사용할 수 있는 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법을 제공하는 데 그 목적이 있다.Accordingly, the present invention was developed to solve the above problems, and it can be used as an alternative to the conventional polyglyceryl fatty acid ester by additionally synthesizing a lipophilic fatty acid capable of exhibiting lipophilic preservative performance to the conventional polyglycerin hydrophilic group introduced during emulsifier synthesis. The purpose is to provide a method for producing a preservative emulsifier based on polyglyceryl-n fatty acid ester.
상기 목적을 달성하기 위해 안출된 본 발명에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법은 반응물인 글리세린에 수산화나트륨 0.2mol 및 프로필렌글라이콜 2mol을 반응용매로 하여 진공반응기에 투입하고, 110℃의 온도조건에서 1시간 동안 완전 용해시켜 1차반응물인 폴리글리세린(Polyglycerin)을 생성하는 1차반응단계; 1차반응단계로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 3시간 반응시켜 2차반응물인 폴리글리세릴 스테아레이트(Polyglyceryl stearate)를 합성하는 2차반응단계; 2차반응단계로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 2시간 동안 반응시켜 폴리글리세릴 카프릴로일스테아레이트(Polyglyceryl capryloyl stearate)를 합성하는 3차반응단계; 3차반응단계를 거쳐 수득된 폴리글리세릴 카프릴로일스테아레이트를 냉각시키는 냉각단계를 포함한다. In order to achieve the above object, the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to the present invention includes adding 0.2 mol of sodium hydroxide and 2 mol of propylene glycol as reaction solvents to glycerin as a reactant into a vacuum reactor, A first reaction step of producing polyglycerin, the first reactant, by complete dissolution for 1 hour at a temperature of 110°C; Stearic acid was added to the polyglycerin obtained from the first reaction step and reacted for 3 hours at a temperature of 180°C and a low vacuum of 1×10 -3 torr to produce polyglyceryl stearate, a secondary reactant. secondary reaction step to synthesize stearate; Caprylic acid was added to the polyglyceryl stearate obtained from the second reaction step and reacted at a temperature of 120°C and 1×10 -3 torr for 2 hours to produce polyglyceryl capryloylstearate ( Third reaction step to synthesize polyglyceryl capryloyl stearate; It includes a cooling step of cooling the polyglyceryl capryloyl stearate obtained through the third reaction step.
또한, 본 발명에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법은 2차반응단계는 1차반응단계로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정을 더 포함하고, 3차반응단계는 2차반응단계로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정을 더 포함하며, 1차반응단계에서 글리세린의 반응몰수는 2mol 내지 10mol이며, 2차반응단계에서 카프릴산의 반응몰수는 1mol 이며, 3차반응단계에서 스테아르산의 반응몰수는 1mol 인 것을 특징으로 한다. In addition, in the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to the present invention, the second reaction step is to add stearic acid to the polyglycerin obtained from the first reaction step at a temperature of 180°C and 1. ×10 -3 torr It further includes a dehydration and propylene glycol removal process to condense and remove the moisture and propylene glycol evaporated in the initial reaction stage where the reaction proceeds under low vacuum conditions, and the third reaction stage is a secondary reaction. Caprylic acid is added to the polyglyceryl stearate obtained from the reaction step, and the moisture and propylene glycol evaporated in the initial reaction step where the reaction proceeds at a temperature of 120°C and 1×10 -3 torr. It further includes a dehydration and propylene glycol removal process to remove by condensing, the reaction mole number of glycerin in the first reaction step is 2 mol to 10 mol, the reaction mole number of caprylic acid in the second reaction step is 1 mol, and the third reaction mole number is 1 mol. The reaction mole number of stearic acid in the reaction step is characterized in that it is 1 mol.
또한, 본 발명에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법은 1차반응단계 내지 3차반응단계을 거쳐 수득된 폴리글리세릴 카프릴로일스테아레이트는 폴리글리세릴-2 카프릴로일스테아레이트, 폴리글리세릴-4 카프릴로일스테아레이트, 폴리글리세릴-6 카프릴로일스테아레이트, 폴리글리세릴-8 카프릴로일스테아레이트, 폴리글리세릴-10 카프릴로일스테아레이트를 포함하는 것을 포함한다. In addition, in the method for producing a preservative emulsifier based on polyglyceryl-n fatty acid ester according to the present invention, polyglyceryl capryloyl stearate obtained through the first reaction step to the third reaction step is polyglyceryl-2 capryloyl stearate. , polyglyceryl-4 capryloyl stearate, polyglyceryl-6 capryloyl stearate, polyglyceryl-8 capryloyl stearate, polyglyceryl-10 capryloyl stearate. .
본 발명에 의하면 PEG(polyethylene glycol, 폴리에틸렌글라이콜) 및 POE(polyoxyethylene, 폴리옥시에틸렌) 계 비이온 계면활성제를 대체사용 가능한 유화제를 제공할 수 있도록 하는 데 그 효과가 있다.According to the present invention, it is effective to provide an emulsifier that can be used as an alternative to PEG (polyethylene glycol) and POE (polyoxyethylene) nonionic surfactants.
또한, 본 발명에 의하면 종래 경피자극을 유발할 수 있는 방부제 대체 방부성 유화제를 제공할 수 있도록 하는 데 그 효과가 있다. In addition, the present invention is effective in providing a preservative emulsifier that replaces conventional preservatives that can cause dermal irritation.
도 1은 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법의 개념도,
도 2는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법의 흐름도,
도 3 내지 도 4는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법을 거쳐 제조된 결과물 중 하나의 화합물에 대해 NMR 분광분석을 실시하고 분석결과를 도시한 도면,
도 5는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산 에스테르 기반 방부성 유화제 제조 방법에 따라 제조된 결과물의 유화테스트를 도시한 도면,
도 6은 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산 에스테르 기반 방부성 유화제 제조 방법에 따라 제조된 결과물에 대해 화장품방부력테스트에 사용하는 미생물들에 대한 항균력에 대한 평가를 실시하고 평가결과를 나타낸 그래프를 도시한 도면이다. 1 is a conceptual diagram of a method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention;
Figure 2 is a flow chart of a method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention;
Figures 3 and 4 are diagrams showing the results of NMR spectroscopic analysis on one of the compounds produced through the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention;
Figure 5 is a diagram showing an emulsification test of the result prepared according to the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention;
Figure 6 shows the evaluation results of antibacterial activity against microorganisms used in cosmetic preservative testing of the results prepared according to the method for producing a polyglyceryl-n fatty acid ester based preservative emulsifier according to a preferred embodiment of the present invention. This is a diagram showing a graph showing .
이하, 본 발명의 바람직한 실시예를 첨부된 도면들을 참조하여 상세히 설명한다. 우선 각 도면의 구성 요소들에 참조 부호를 부가함에 있어서, 동일한 구성 요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다. 또한, 이하에서 본 발명의 바람직한 실시예를 설명할 것이나, 본 발명의 기술적 사상은 이에 한정하거나 제한되지 않고 당업자에 의해 변형되어 다양하게 실시될 수 있음은 물론이다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. First, when adding reference signs to components in each drawing, it should be noted that the same components are given the same reference numerals as much as possible even if they are shown in different drawings. Additionally, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted. In addition, preferred embodiments of the present invention will be described below, but the technical idea of the present invention is not limited or restricted thereto, and of course, it can be modified and implemented in various ways by those skilled in the art.
도 1은 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법의 개념도이고, 도 2는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법의 흐름도이며, 도 3 내지 도 4는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법을 거쳐 제조된 결과물 중 하나의 화합물에 대해 NMR 분광분석을 실시하고 분석결과를 도시한 도면이고, 도 5는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산 에스테르 기반 방부성 유화제 제조 방법에 따라 제조된 결과물의 유화테스트를 도시한 도면이며, 도 6은 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산 에스테르 기반 방부성 유화제 제조 방법에 따라 제조된 결과물에 대해 화장품방부력테스트에 사용하는 미생물들에 대한 항균력에 대한 평가를 실시하고 평가결과를 나타낸 그래프를 도시한 도면이다. Figure 1 is a conceptual diagram of a method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention, and Figure 2 is a method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention. is a flow chart, and Figures 3 and 4 show NMR spectroscopic analysis was performed on one of the compounds produced through the polyglyceryl-n fatty acid ester-based preservative emulsifier manufacturing method according to a preferred embodiment of the present invention, and the analysis results were presented. Figure 5 is a diagram showing an emulsification test of the result prepared according to the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention, and Figure 6 is a preferred embodiment of the present invention. This is a diagram showing a graph showing the evaluation results after evaluating the antibacterial activity against microorganisms used in cosmetic preservative testing on the results prepared according to the polyglyceryl-n fatty acid ester-based preservative emulsifier manufacturing method according to the example. .
도 1 내지 도 2를 참조하면, 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법은 1차반응단계(S10), 2차반응단계(S20), 3차반응단계(S30), 냉각단계(S40)를 포함하여 구성된다. Referring to Figures 1 and 2, the method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention includes a first reaction step (S10), a second reaction step (S20), and a third reaction step. (S30) and a cooling step (S40).
1차반응단계(S10)는 반응물인 글리세린에 수산화나트륨 0.2mol 및 프로필렌글라이콜 2mol을 반응용매로 하여 진공반응기에 투입하고, 110℃의 온도조건에서 1시간 동안 완전 용해시켜 1차반응물인 폴리글리세린(Polyglycerin)을 생성하는 단계이다. In the first reaction step (S10), 0.2 mol of sodium hydroxide and 2 mol of propylene glycol as a reaction solvent are added to the reactant glycerin in a vacuum reactor, and completely dissolved for 1 hour at a temperature of 110°C to form the first reactant, poly. This is the step to produce glycerin (polyglycerin).
보다 구체적으로, 1차반응단계(S10)는 반응물인 글리세린 2mol 내지 10mol에 수산화나트륨 0.2mol 및 프로필렌글라이콜 2mol을 반응용매로 하여 진공반응기에 투입하고, 110℃의 온도조건에서 1시간 동안 완전 용해시켜 1차반응물인 폴리글리세린(Polyglycerin)을 생성하는 단계이다. More specifically, in the first reaction step (S10), 2 to 10 mol of glycerin as a reactant, 0.2 mol of sodium hydroxide and 2 mol of propylene glycol as a reaction solvent are added to a vacuum reactor, and completely incubated for 1 hour at a temperature of 110°C. This is the step of dissolving to produce polyglycerin, the primary reactant.
2차반응단계(S20)는 1차반응단계(S20)로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr 저진공 조건에서 3시간 반응시켜 2차반응물인 폴리글리세릴 스테아레이트(Polyglyceryl stearate)를 합성하는 단계이다. In the second reaction step (S20), stearic acid is added to the polyglycerin obtained from the first reaction step (S20) and reacted for 3 hours at a temperature of 180°C and a low vacuum of 1×10 -3 torr. This is the step of synthesizing the secondary reactant, polyglyceryl stearate.
보다 구체적으로, 2차반응단계(S20)는 1차반응단계(S20)로부터 수득된 폴리글리세린에 스테아르산(Searic acid) 1mol을 부가하여 180℃의 온도조건과 1×10-3 torr 저진공 조건에서 3시간 반응시켜 2차반응물인 폴리글리세릴 스테아레이트(Polyglyceryl stearate)를 합성하는 단계이다. More specifically, in the second reaction step (S20), 1 mol of stearic acid was added to the polyglycerin obtained from the first reaction step (S20) under a temperature condition of 180°C and a low vacuum of 1×10 -3 torr. This is the step of synthesizing polyglyceryl stearate, a secondary reactant, by reacting for 3 hours.
3차반응단계(S30)는 2차반응단계(S20)로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 2시간 동안 반응시켜 폴리글리세릴 카프릴로일스테아레이트(Polyglyceryl capryloyl stearate)를 합성하는 단계이다. The third reaction step (S30) is performed by adding caprylic acid to the polyglyceryl stearate obtained from the second reaction step (S20) at a temperature of 120°C and 1×10 -3 torr for 2 hours. This is the step of reacting to synthesize polyglyceryl capryloyl stearate.
보다 구체적으로, 3차반응단계(S30)는 2차반응단계(S20)로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid) 1mol을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 2시간 동안 반응시켜 폴리글리세릴 카프릴로일스테아레이트(Polyglyceryl capryloyl stearate)를 합성하는 단계이다. More specifically, in the third reaction step (S30), 1 mol of caprylic acid was added to the polyglyceryl stearate obtained in the second reaction step (S20) under a temperature condition of 120°C and 1×10 -3 . This is the step of synthesizing polyglyceryl capryloyl stearate by reacting at torr for 2 hours.
상기 2차반응단계(S20) 및 3차반응단계(S30)는 반응 중 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정을 더 포함한다. The second reaction step (S20) and the third reaction step (S30) further include dehydration and propylene glycol removal processes to condense and remove moisture and propylene glycol evaporated during the reaction.
구체적으로, 2차반응단계(S20)는 1차반응단계(S10)로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정을 더 포함한다. Specifically, in the second reaction step (S20), stearic acid is added to the polyglycerin obtained from the first reaction step (S10) and the reaction is performed under temperature conditions of 180°C and low vacuum conditions of 1×10 -3 torr. It further includes dehydration and propylene glycol removal processes to condense and remove moisture and propylene glycol evaporated in the initial reaction stage.
또한, 3차반응단계(S30)는 2차반응단계(S20)로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정을 더 포함한다. In addition, the third reaction step (S30) is performed by adding caprylic acid to the polyglyceryl stearate obtained in the second reaction step (S20) at a temperature of 120°C and 1×10 -3 torr. It further includes dehydration and propylene glycol removal processes to condense and remove moisture and propylene glycol evaporated in the initial reaction stage.
냉각단계(S40)는 3차반응단계(S30)를 거쳐 수득된 폴리글리세릴 카프릴로일스테아레이트를 냉각시키는 단계이다. The cooling step (S40) is a step of cooling the polyglyceryl capryloyl stearate obtained through the third reaction step (S30).
본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 지방산에스테르 기반 방부성 유화제 제조 방법은 수산화나트륨 0.2mol, 프로필렌글라이콜 2mol, 글리세린 2mol 내지 10mol을 110℃에서 1시간 동안 완전 용해시키고 이후 스테아르산 1mol을 부가하여 180℃, 저진공 조건(1×10-3 )torr에서 3시간 반응 시켜 폴리글리세릴-n 스테아레이트를 합성하고, 그 다음, 합성된 화합물에 카프릴산 1mol을 부가하여 120℃, 저진공 조건(1×10-3 )torr에서 2시간 동안 탈수 및 프로필렌글라이콜을 증발 및 응축 시켜 제거하여 폴리글리세릴-n 카프릴로일스테아레이트를 합성한다. The method for producing a polyglyceryl-n fatty acid ester-based preservative emulsifier according to a preferred embodiment of the present invention is to completely dissolve 0.2 mol of sodium hydroxide, 2 mol of propylene glycol, and 2 to 10 mol of glycerin at 110°C for 1 hour, and then add 1 mol of stearic acid. was added to synthesize polyglyceryl-n stearate by reacting at 180°C and low vacuum conditions (1×10 -3 )torr for 3 hours. Then, 1 mol of caprylic acid was added to the synthesized compound, and the mixture was reacted at 120°C. Polyglyceryl-n capryloyl stearate is synthesized by dehydrating and removing propylene glycol by evaporation and condensation under low vacuum conditions (1×10 -3 )torr for 2 hours.
상기 실시예의 방법과 동일하게 진행하되, 글리세린 및 지방산의 몰수는 하기의 표 1과 같이 조정하여 합성하면, 폴리글리세릴-2카프릴로일스테아레이트, 폴리글리세릴-4, 카프릴로일스테아레이트, 폴리글리세릴-6 카프릴로일스테아레이트, 폴리글리세릴-8 카프릴로일스테아레이트, 폴리글리세릴-10 카프릴로일스테아레이트를 각각 수득할 수 있다. Proceed in the same way as in the above example, but when synthesized by adjusting the moles of glycerin and fatty acid as shown in Table 1 below, polyglyceryl-2 capryloyl stearate, polyglyceryl-4, capryloyl stearate, Polyglyceryl-6 capryloyl stearate, polyglyceryl-8 capryloyl stearate, and polyglyceryl-10 capryloyl stearate can be obtained, respectively.
하기의 표 1은 폴리글리세릴-n 카프릴로일스테아레이트의 반응 몰수를 나타낸 표이다. Table 1 below is a table showing the number of reaction moles of polyglyceryl-n capryloyl stearate.
도 4는 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 카프릴로일스테아레이트의 구조분석 결과를 나타낸 도면으로, 구조분석을 위해 1H NMR 및 13C NMR을 수행하였다. Figure 4 is a diagram showing the results of structural analysis of polyglyceryl-n capryloylstearate according to a preferred embodiment of the present invention. 1 H NMR and 1 3C NMR were performed for structural analysis.
이하에서는, 본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 카프릴로일스테아레이트의 합성 전환율을 아래의 산출식을 이용하여 산출하고, 그 결과를 나타내었다. Below, the synthetic conversion rate of polyglyceryl-n capryloyl stearate according to a preferred embodiment of the present invention was calculated using the formula below, and the results are shown.
본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 카프릴로일스테아레이트의 합성전환율은 하기 산가 및 전환율 식을 이용하여 산출되었으며, 합성 전환율은 하기의 표 2와 같다. The synthetic conversion rate of polyglyceryl-n capryloyl stearate according to a preferred embodiment of the present invention was calculated using the acid value and conversion rate equations below, and the synthetic conversion rate is shown in Table 2 below.
<폴리글리세릴-n 카프릴로일스테아레이트의 유화테스트><Emulsification test of polyglyceryl-n capryloyl stearate>
본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 카프릴로일스테아레이트를 사용하여 에멀젼을 제조하고 유화입자 형태를 관찰하였다. 관찰 결과, 도 5를 참조하면, 대조군인 글리세릴스테아레이트에 의한 에멀젼의 유화입자에 비해 본 발명에 따라 제조된 결과물이 입자크기 및 분포가 작고 조밀하여 분산성이 우수한 유화 안정성을 나타내었다. An emulsion was prepared using polyglyceryl-n capryloyl stearate according to a preferred embodiment of the present invention, and the shape of the emulsified particles was observed. As a result of observation, referring to Figure 5, compared to the emulsion particles of the emulsion using glyceryl stearate, which is the control, the resultant product prepared according to the present invention had smaller and denser particle size and distribution, showing excellent emulsion stability with excellent dispersibility.
<폴리글리세릴-4 카프릴로일스테아레이트의 MIC 테스트> <MIC test of polyglyceryl-4 capryloylstearate>
본 발명의 바람직한 실시예에 따른 폴리글리세릴-n 카프릴로일스테아레이트중 하나인 폴리글리세릴-4 카프릴로일스테아레이트를 사용하여 화장품 방부력 테스트에 사용하는 미생물들에 대한 항균력에 대한 평가를 실시하였다. 실시 결과는 도 6에 나타내었다. Polyglyceryl-4 capryloyl stearate, one of the polyglyceryl-n capryloyl stearates according to a preferred embodiment of the present invention, was used to evaluate the antibacterial activity against microorganisms used in the cosmetic preservative power test. It was carried out. The implementation results are shown in Figure 6.
도 6을 참조하면, 폴리글리세릴-4 카프릴로일스테아레이트의 농도구간이 1~1.5%까지는 5종의 미생물에 대하여 생육억제를 나타내었으며, 2~3%까지의 농도구간에서는 생육하지 못하는 것으로 나타나 화장품의 방부력 효과가 있는 것으로 판단되었다. Referring to Figure 6, the concentration range of polyglyceryl-4 capryloylstearate was 1 to 1.5%, showing growth inhibition for 5 types of microorganisms, and growth was not possible in the concentration range of 2 to 3%. It was found to have a preservative effect on cosmetics.
< 폴리글리세릴-n 카프릴로일스테아레이트의 피부저자극 테스트> <Skin hypoallergenic test of polyglyceryl-n capryloylstearate>
본 발명의 바람직한 실시예에 따라 제조된 폴리그릴세릴-n 카프릴로일스테아레이트(폴리글리세릴-2 카프릴로일스테아레이트, 폴리그릴세릴-4 카프릴로일스테아레이트, 폴리글리세릴-6 카프릴로일스테아레이트, 폴리그릴세릴-8 카프릴로일스테아레이트, 폴리그릴세릴-10 카프릴로일스테아레이트)이 포함된 크림을 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되는지를 관찰하고, 평균 피부반응도를 판정기준에 따라 판단하였다. Polyglyceryl-n capryloyl stearate (polyglyceryl-2 capryloyl stearate, polyglyceryl-4 capryloyl stearate, polyglyceryl-6 capryloyl stearate) prepared according to a preferred embodiment of the present invention. After removing the patch, observe whether irritation is observed 30 minutes, 24 hours, and 48 hours after applying the cream containing (ylstearate, polygylseryl-8 capryloylstearate, polygylseryl-10 capryloylstearate) And the average skin reactivity was judged according to the judgment criteria.
하기의 표 3은 폴리글리세릴-n 카프릴로일스테아레이트의 피부저자극 테스트 결과를 나타낸 표이다. Table 3 below shows the results of a skin hypoallergenic test of polyglyceryl-n capryloyl stearate.
표 3을 살펴보면, 폴리글리세릴-2카프릴로일 스테아레이트 크림은 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되지 않았다. 평균 피부반응도는 0.00으로 판정기준에 따라 무자극으로 판정되었다.Looking at Table 3, no irritation was observed with the polyglyceryl-2capryloyl stearate cream 30 minutes, 24 hours, and 48 hours after the patch was removed. The average skin reactivity was 0.00, which was judged to be non-irritating according to the criteria.
또한, 폴리글리세릴-4카프릴로일 스테아레이트 크림은 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되지 않았다. 평균 피부반응도는 0.00으로 판정기준에 따라 무자극으로 판정되었다.Additionally, no irritation was observed with polyglyceryl-4capryloyl stearate cream 30 minutes, 24 hours, and 48 hours after the patch was removed. The average skin reactivity was 0.00, which was judged to be non-irritating according to the criteria.
또한, 폴리글리세릴-6카프릴로일 스테아레이트 크림은 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되지 않았다. 평균 피부반응도는 0.00으로 판정기준에 따라 무자극으로 판정되었다.Additionally, no irritation was observed with the polyglyceryl-6capryloyl stearate cream 30 minutes, 24 hours, and 48 hours after the patch was removed. The average skin reactivity was 0.00, which was judged to be non-irritating according to the criteria.
또한, 폴리글리세릴-8카프릴로일 스테아레이트 크림은 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되지 않았다. 평균 피부반응도는 0.00으로 판정기준에 따라 무자극으로 판정되었다.Additionally, no irritation was observed with polyglyceryl-8capryloyl stearate cream 30 minutes, 24 hours, and 48 hours after the patch was removed. The average skin reactivity was 0.00, which was judged to be non-irritating according to the judgment criteria.
또한, 폴리글리세릴-10카프릴로일 스테아레이트 크림은 첩포 제거 후 30분, 24시간, 48시간 경과 후에 자극이 관찰되지 않았다. 평균 피부반응도는 0.00으로 판정기준에 따라 무자극으로 판정되었다.Additionally, no irritation was observed with the polyglyceryl-10 capryloyl stearate cream 30 minutes, 24 hours, and 48 hours after the patch was removed. The average skin reactivity was 0.00, which was judged to be non-irritating according to the criteria.
하기의 표 4는 피시험자가 보고한 피부이상반응에 대한 결과를 나타낸 표이며, 본 발명의 바람직한 실시예에 따라 제조된 폴리글리세릴-n 카프릴로일 스테아레이트가 함유된 화장료를 도포한 후, 홍반(붉어짐), 부종(부어오름), 인설(각질), 가려움, 자통(통증), 작열감, 뻣뻣함, 따끔거림 총 8가지 피부이상반응에 대해 30분, 24분, 48시간 경과 후 반응정도에 따라 0(없음), 1(약한정도), 2(중간정도), 3(심한정도)으로 피부이상반응을 평가한 결과를 나타내었다 Table 4 below shows the results of adverse skin reactions reported by test subjects. After applying a cosmetic containing polyglyceryl-n capryloyl stearate prepared according to a preferred embodiment of the present invention, Erythema (redness), edema (swelling), scale (scaly), itching, stinging (pain), burning, stiffness, tingling. For a total of 8 types of skin adverse reactions, the degree of reaction is assessed after 30 minutes, 24 minutes, and 48 hours. The results of skin adverse reactions were evaluated as 0 (none), 1 (mild), 2 (moderate), and 3 (severe).
1) 시험담당자에 의한 피부이상반응 평가1) Evaluation of adverse skin reactions by test personnel
피시험자에게 시험물질을 사용한 후 알레르기성 접촉 피부염(allergic contact dermatitis)이나 자극성 접촉 피부염(irritant contact dermatitis)한 이상반응은 관찰되지 않았다.No adverse reactions such as allergic contact dermatitis or irritant contact dermatitis were observed in test subjects after using the test substance.
2) 피시험자 설문조사에 의한 피부이상반응 보고 2) Reporting of adverse skin reactions based on test subject survey
시험담당자에 의한 이상반응 평가와는 별도로, 피시험자를 대상으로 설문조사를 한 결과 피시험자가 보고한 피부이상반응은 표 4를 참조하면, 시험자를 대상으로 한 설문조사에서 특별한 피부이상반응은 관찰되지 않았다.Separately from the evaluation of adverse reactions by the test personnel, as a result of a survey of test subjects, see Table 4 for adverse skin reactions reported by test subjects. Special adverse skin reactions were observed in the survey of test subjects. It didn't work.
시험기간 중 시험담당자는 피시험자의 안전을 최우선으로 생각하며 시험을 진행하였다. 피시험자에게는 본 시험 또는 시험물질에 의해 피부이상반응이 발생하였을 경우, 필요한 검사 및 치료를 시험의뢰기관에 요구할 수 있음을 사전 고지하였다. During the test period, the test staff conducted the test with the safety of the test subjects as the top priority. The test subject was notified in advance that if an adverse skin reaction occurred due to this test or the test substance, the test requesting institution could be requested to provide necessary examination and treatment.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위 내에서 다양한 수정, 변경 및 치환이 가능할 것이다. 따라서, 본 발명에 개시된 실시예 및 첨부된 도면들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예 및 첨부된 도면에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely an illustrative explanation of the technical idea of the present invention, and various modifications, changes, and substitutions can be made by those skilled in the art without departing from the essential characteristics of the present invention. will be. Accordingly, the embodiments disclosed in the present invention and the attached drawings are not intended to limit the technical idea of the present invention, but are for illustrative purposes, and the scope of the technical idea of the present invention is not limited by these embodiments and the attached drawings. . The scope of protection of the present invention should be interpreted in accordance with the claims below, and all technical ideas within the equivalent scope should be construed as being included in the scope of rights of the present invention.
S10 : 1차반응
S20 : 2차반응
S30 : 3차반응
S40 : 냉각S10: First reaction
S20: Secondary reaction
S30: Third reaction
S40: Cooling
Claims (3)
1차반응단계로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 3시간 반응시켜 2차생성물인 폴리글리세릴 스테아레이트(Polyglyceryl stearate)를 합성하는 2차반응단계;
2차반응단계로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 2시간 동안 반응시켜 폴리글리세릴 카프릴로일스테아레이트(Polyglyceryl capryloyl stearate)를 합성하는 3차반응단계;
3차반응단계를 거쳐 수득된 폴리글리세릴 카프릴로일스테아레이트를 냉각시키는 냉각단계
를 포함하는 폴리글리세릴-n 지방산에스테르의 제조 방법. 0.2 mol of sodium hydroxide and 2 mol of propylene glycol as reaction solvents are added to the reactant glycerin in a vacuum reactor, and completely dissolved for 1 hour at a temperature of 110°C to produce polyglycerin, the primary product. Secondary reaction step;
Stearic acid was added to the polyglycerin obtained from the first reaction step and reacted for 3 hours at a temperature of 180°C and a low vacuum of 1×10 -3 torr to produce the secondary product, polyglyceryl stearate. secondary reaction step to synthesize stearate;
Caprylic acid was added to the polyglyceryl stearate obtained from the second reaction step and reacted at a temperature of 120°C and 1×10 -3 torr for 2 hours to produce polyglyceryl capryloylstearate ( Third reaction step to synthesize polyglyceryl capryloyl stearate;
Cooling step of cooling polyglyceryl capryloyl stearate obtained through the third reaction step
Method for producing polyglyceryl-n fatty acid ester comprising.
2차반응단계는
1차반응단계로부터 수득된 폴리글리세린에 스테아르산(Searic acid)을 부가하여 180℃의 온도조건과 1×10-3 torr저진공 조건에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정
을 더 포함하고,
3차반응단계는
2차반응단계로부터 수득된 폴리글리세릴 스테아레이트에 카프릴산(Caprylic acid)을 부가하여 120℃의 온도조건과 1×10-3 torr 에서 반응이 진행되는 초기반응단계에서 증발되는 수분과 프로필렌글라이콜을 응축시켜 제거하는 탈수 및 프로필렌글라이콜 제거과정
을 더 포함하며,
1차반응단계에서 이용되는 글리세린과 2차반응단계에서 이용되는 스테아르산 과 3차반응단계에서 이용되는 카프릴산의 반응몰비는 각 2mol~10mol : 1mol : 1mol 인 것
을 특징으로 하는 폴리글리세릴-n 지방산에스테르의 제조 방법.According to paragraph 1,
The second reaction step is
Stearic acid is added to the polyglycerin obtained from the first reaction step, and the moisture and propylene glycol evaporated in the initial reaction step where the reaction proceeds at a temperature of 180°C and a low vacuum of 1×10 -3 torr. Dehydration and propylene glycol removal process to remove cole by condensing it
It further includes,
The third reaction step is
Caprylic acid is added to the polyglyceryl stearate obtained from the second reaction step, and the moisture and propylene glycol evaporated in the initial reaction step where the reaction proceeds at a temperature of 120°C and 1×10 -3 torr. Dehydration and propylene glycol removal process to condense and remove Lycol
It further includes,
The reaction molar ratio of glycerin used in the first reaction step, stearic acid used in the second reaction step, and caprylic acid used in the third reaction step is 2 mol ~ 10 mol : 1 mol : 1 mol each.
A method for producing polyglyceryl-n fatty acid ester, characterized by:
A preservative emulsifier containing polyglyceryl-n fatty acid ester prepared according to the production method of claim 1 or 2.
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US5147644A (en) * | 1990-02-23 | 1992-09-15 | Basf Aktiengesellschaft | Use of mixtures of polyglycerol fatty esters as emulsifiers in cosmetic and pharmaceutical formulations |
KR20050084009A (en) * | 2002-11-28 | 2005-08-26 | 다이셀 가가꾸 고교 가부시끼가이샤 | Polyglycerols, polyglycerol/fatty acid ester, and processes for producing these |
KR20120042396A (en) * | 2010-10-25 | 2012-05-03 | (주)아모레퍼시픽 | Nanoemulsion cosmetic composition produced by using polyglyceryl ester alone as an emulsifier and the method for preparing thereof |
KR20170086126A (en) * | 2014-12-29 | 2017-07-25 | 킴벌리-클라크 월드와이드, 인크. | Cosmetic emulsions |
KR20170124320A (en) * | 2016-05-02 | 2017-11-10 | (주)아모레퍼시픽 | Nanoemulsion composition comprising polyglyceryl emulsifier |
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- 2023-05-02 KR KR1020230056819A patent/KR102633521B1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5147644A (en) * | 1990-02-23 | 1992-09-15 | Basf Aktiengesellschaft | Use of mixtures of polyglycerol fatty esters as emulsifiers in cosmetic and pharmaceutical formulations |
KR20050084009A (en) * | 2002-11-28 | 2005-08-26 | 다이셀 가가꾸 고교 가부시끼가이샤 | Polyglycerols, polyglycerol/fatty acid ester, and processes for producing these |
KR20120042396A (en) * | 2010-10-25 | 2012-05-03 | (주)아모레퍼시픽 | Nanoemulsion cosmetic composition produced by using polyglyceryl ester alone as an emulsifier and the method for preparing thereof |
KR20170086126A (en) * | 2014-12-29 | 2017-07-25 | 킴벌리-클라크 월드와이드, 인크. | Cosmetic emulsions |
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