WO2014003241A1 - Skin temperature sensitive hydrogel composition and preparation method thereof - Google Patents

Skin temperature sensitive hydrogel composition and preparation method thereof Download PDF

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Publication number
WO2014003241A1
WO2014003241A1 PCT/KR2012/007657 KR2012007657W WO2014003241A1 WO 2014003241 A1 WO2014003241 A1 WO 2014003241A1 KR 2012007657 W KR2012007657 W KR 2012007657W WO 2014003241 A1 WO2014003241 A1 WO 2014003241A1
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Prior art keywords
skin
hydrogel
skin temperature
cosmetic composition
polymer
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PCT/KR2012/007657
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French (fr)
Korean (ko)
Inventor
이준배
박천호
유희창
Original Assignee
코스맥스 주식회사
코스맥스 (중국)화장품 유한공사
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Publication of WO2014003241A1 publication Critical patent/WO2014003241A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90Block copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/81Preparation or application process involves irradiation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/95Involves in-situ formation or cross-linking of polymers

Definitions

  • the present invention relates to a cosmetic composition having a skin temperature sensitizing hydrogel to more quickly and uniformly deliver the water-soluble beauty agent contained in the hydrogel into the skin through shrinkage according to the temperature of the hydrogel in response to the skin temperature. This shrinkage can also help the hydrogel adhere to the skin more tightly.
  • Hydrogel is a material having a polymer network structure containing a large amount of water is made by a homopolymer or a copolymer.
  • the hydrogel becomes transparent as it swells through absorption of hydrophilic components, including water, in aqueous solution and also has adequate mechanical properties. Such swelling and mechanical properties of the polymer mainly depend on the properties of the polymer network structure.
  • As a material for making such a hydrogel a large number of polymers are mainly used. The polymer is divided into two kinds of natural polymer and synthetic polymer according to the origin of the material.
  • Hydrogels made of natural polymers are made of polymers derived from natural materials such as agar, carrageenan, cellulose, and xanthan gum, which may give consumers a good impression of the origin of nature, but they are weak in mechanical properties. It is characteristic. Since most of these natural polymers are made by physical gelation reaction, hydrogels are easily dissolved and changed to a sol state at high temperature conditions, and at low temperature or room temperature conditions, the mechanical strength is weak so that they are broken or torn even in a small impact. Great care must be taken in the use of the product. In contrast, hydrogels made of synthetic polymers have strong binding properties such as chemical covalent bonds between molecules through crosslinking, and thus, unlike natural polymers, hydrogels have strong mechanical properties.
  • Hydrogel-related patents made by such synthetic polymers include a temperature sensitive state change hydrogel composition patent (Korean Patent No. 506543). According to this patent, the hydrogel state is changed to a fluid state by the body temperature when it comes into contact with the skin, and it has flowability. Through this, the beauty agent or drug contained in the hydrogel is uniformly coated on the skin and quickly penetrates. In this case, only a part of the hydrogel is changed to a fluid state through the reaction with the skin and has a limit.
  • Pluronic polymer is a trione block copolymer composed of PE0-PP0-PE0 (polyethyl eneox i de-po 1 ypr opy 1 eneox i de-po 1 ye t hy 1 eneox i de) ⁇ - biocompatible and physiological conditions It is widely known as a biodegradable polymer that decomposes in, and is known to be safe in the human body.
  • Pluronic has a low critical solution temperature (LCST) characteristic of the hydrophobic group (PP0), which enables self-assembly above a certain temperature and thus temperature sensitivity.
  • LCST critical solution temperature
  • Most polymers, including the pluronic, are obtained through a polymerization process, the molecular weight of which is not always constant, but even distribution in various regions, Since it is obtained by averaging it, it is impossible to obtain a polymer of uniform quality. Therefore, hydrogels made with these polymers are not likely to have a constant sol-gel transition temperature obtained during the manufacturing process, and thus may not be uniform in the temperature conditions that change from the hydrogel to the flowable sol state. This is high.
  • the present invention after introducing a double bond at both ends of the pluronic polymer, and chemically cross-linked through ultraviolet (UV) irradiation to produce a hydrogel having the desired physical properties.
  • UV ultraviolet
  • some water-soluble natural polymers are included for the superior feeling.
  • the purpose of the present invention is to provide a cosmetic composition that gives the skin a refreshing and moisturizing feeling by using the hydrogel thus produced and the elasticity and adhesion to the skin by producing a hydrogel that shrinks in size by reacting to the skin temperature. .
  • the invention is reversible swelling in the skin temperature range, obtained by chemical crosslinking by ultraviolet (UV) in the presence or absence of a diacrylated pluronic polymer, a water soluble natural polymer, a photoinitiator or not. And it has a shrinking property, and provides a skin temperature-sensitive hydrogel cosmetic composition characterized in that it has a porous structure in its internal structure.
  • UV ultraviolet
  • a hydrogel without a porous structure only water-soluble agonists that are moistened on the surface can be delivered to the skin, but a pluronic hydrogel with a porous structure may contract the pluronic hydrogel in response to skin temperature.
  • the porous structure serves as a way to allow the release of various water-soluble substances inside the skin.
  • the pluronic polymer is PE0-PP0-PE0 (poly ethyl eneoxide- o 1 ypr opy 1 eneox i de-po 1 yet hy 1 eneox i de) ⁇ .
  • Any tri-block copolymer constructed may be used, but preferably has a molecular weight of about 8,700 Da's Pluronic F68 ((PE0) 75 (PP0) 30 (PE0) 75) or ⁇ Pluronic F127 ((PE0) 99 (PP0) 69 (PE0) 99) It provides a skin temperature sensitive hydrogel cosmetic composition.
  • Pluronic polymers include F38, F68, F77, F98, F108, F127 starting with F and L31, L42, L43, L44, L62, L72, Ll () l starting with L and P75, P103, starting with P, P104 and the like, the difference in brand name is due to the difference in composition ratio and form.
  • F127 ((PE0) 99 (PP0) 69 (PE0) with a molecular weight of about 12,600 Da are approved by the US Food and Drug Administration (FDA). 99) and the like are mainly used as biological materials.
  • the diacrylated pluronic polymer provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that the synthesis by adding a double bond acrylate at both ends of the pluronic polymer.
  • the present invention provides a skin temperature sensitive hydrogel cosmetic composition characterized in that the nucleic acid is used as the precipitation solvent during the synthesis process.
  • the nucleic acid is used as the precipitation solvent, the synthesis reaction time of the polymer is drastically shortened and the double bond introduction rate is equal to or higher than that of diethyl ether as the conventional precipitation solvent.
  • the water-soluble natural polymer may be used any water-soluble natural polymer capable of forming a hydrogel with the diacrylated pluronic polymer, preferably carrageenan, cellulose, agar, galactomannan, It provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that at least one water-soluble natural polymer selected from the group consisting of glucomannan, guar gum, locust bean gum, alginic acid, carrageenan, xanthan gum and gellan.
  • the additional use of the water-soluble natural polymer has a better feeling in ease of skin adhesion, degree of adhesion and moisturizing after use.
  • the skin temperature range is 0 ° C-50 ° C temperature range, preferably provides a skin temperature sensitivity hydrogel cosmetic composition, characterized in that 30 ° C-40 ° C.
  • a skin temperature sensitivity hydrogel cosmetic composition characterized in that 30 ° C-40 ° C.
  • the reversible swelling and shrinking properties in the skin degree range provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that it changes from the swollen gel state to the contracted gel state in response to skin temperature.
  • Conventional hydrogels have a reversible reaction from gel to sol in the skin temperature range, whereas the hydrogels of the present invention have a difference in reversible reaction from a swollen gel in the skin temperature range.
  • the present invention provides a skin sensitizing hydrogel cosmetic composition characterized by imparting a feeling of cooling and moisturizing to the skin as well as imparting elasticity and fit to the skin.
  • Hydrogel of the present invention by contracting by the skin temperature when attached to the skin to release the moisture and water-soluble potent substances can not only enjoy the refreshing and moisturizing feeling on the skin, but also gives the skin a feeling of elasticity and fit.
  • a hydrogel was prepared with or without a small amount of photoinitiator, and hydrogel production was possible regardless of the photoinitiator.
  • the photoinitiator functions to promote the polymerization reaction by forming radicals well when irradiated with UV rays.
  • photoinitiators may remain on the surface or inside of the hydrogel after UV irradiation ends, use a small amount as much as possible in consideration of skin safety. It is preferable not to.
  • the skin affinity enhancer is a skin temperature sensitive hydrogel cosmetic composition, characterized in that at least one polysaccharide or protein selected from the group consisting of chitosan, chitosan derivatives, elastin, collagen, hyaluronic acid to provide.
  • the natural biomaterial is aloe, green tea, It provides a skin temperature sensitivity hydrogel cosmetic composition characterized in that the natural extract of plants, animals or minerals extracted from the gimgle, ginkgo leaves and the like.
  • the polyhydric alcohol preferably provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that the water-soluble liquid butylene glycol, propylene glycol or glycerin.
  • the functional additive is methyl paraben, ethyl paraben, phenoxyethanol, alcohol, ⁇ -hydroxy as an additive that can impart cosmetic functionality through the addition of the stability and preservation of the hydrogel and the active ingredient.
  • a skin temperature sensitive hydrogel cosmetic composition characterized by an acid, clofenesin, or kojic acid, titanium dioxide, aluminum oxide and the like.
  • the present invention provides a skin external cosmetics or medicines comprising the skin temperature sensitive hydrogel composition according to the present invention.
  • the external skin cosmetics or medicines may be any external skin cosmetics or medicines that can use a conventional hydrogel as a medium.
  • the Pluronic F-127 polymer When the Pluronic F-127 polymer is at a suitable concentration, a transition occurs between a fluid-free gel and a fluid sol at temperatures near body temperature (33-37 ° C). At this time, the resulting gel is a physical gel that is weak in mechanical properties so that its shape can be collapsed by external temperature and force. Therefore, the inventors of the present invention by using the ultraviolet light (UV) to make a chemically cross-linked gel by using this simple transition phenomenon alone to make a hydrogel applicable to cosmetics.
  • UV ultraviolet light
  • the present inventors synthesized diacrylated pluronic by adding an acrylate having a double bond at both ends of the pluronic polymer.
  • nucleic acid is used instead of the diethyl ether used in the previous paper (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004) for the safety of the workers in the synthesis process. It was.
  • the vapor pressure of the nucleic acid (124 ⁇ Hg, 20 ° C) is lower than the diethyl ether vapor pressure (440 ⁇ 3 ⁇ 4, 20 ° C), thus reducing the risk of solvent inhalation during the operation.
  • the boiling point (about 69 ° C) is higher than the boiling point of diethyl ether (about 35 ° C), so it is much more efficient in terms of evaporation of solvents that can be produced by exothermic reactions during the synthesis process.
  • diethyl ether dispersion similar to emulsion occurs during the precipitation process, which takes a long time to settle, whereas nucleic acid can be precipitated immediately, which is much superior to diethyl ether in terms of safety and process efficiency.
  • the diacrylated pluronic acid made as described above alone and in combination with other water-soluble polymers to prepare a hydrogel through ultraviolet irradiation Although diacrylated pluronic alone can produce hydrogels through UV irradiation, the present inventors invented water-soluble natural polymers such as cellulose and carrageenan gum to produce hydrogels with excellent feeling. Hydrogels were prepared. Existing hydrogels made of only water-soluble natural polymers did not have any specificities in their internal structure, but a clear porous structure was observed in hydrogels made by UV irradiation alone or in combination with other water-soluble polymers. .
  • the present invention also prepared hydrogels with little or no initiator.
  • the hydrogel thus produced was swelled by the cosmetic composition in an aqueous solution at room temperature or refrigerated conditions and then reacted at 37 ° C, which is the skin temperature, to release the aqueous solution collected therein.
  • the temperature sensitive hydrogel made by the present invention reacts to the skin temperature and releases moisturizing ingredients and various active ingredients, including water that was swelling inside the hydrogel while simultaneously shrinking the hydrogel itself. This gives the skin a refreshing and moisturizing feeling, and can supply various effective ingredients to the skin.
  • the shrinking nature of the hydrogel gives a sense of elasticity to the skin, and also due to this shrinkage may help to attach the hydrogel more tightly to the skin.
  • FIG. 1 is a graph measuring the swelling ratio (Swelling ratio) of the Pluronic hydrogel prepared according to an embodiment of the present invention.
  • Figure 2 is a graph measuring the contraction ratio (Contract ion ratio) of the Pluronic hydrogel prepared according to the embodiment of the present invention.
  • Pluronic F-127 (PE0) 99 (PP0) 69 (PE0) 99) was purchased from BASF, Triethylamine was purchased from Sigma and Acryloyl chloride was purchased from Wako. In addition, methylene chloride, a solvent used in the synthesis reaction, was purchased from J & T Baker and nucleic acid (Hexane) used for precipitation was obtained from Daejeong (Korea).
  • Example 1 Synthesis of Acrylated Pluronic
  • This step is to introduce double bonds at both ends of the Pluronic F127 polymer and to dry the Pluronic polymer by vacuum or hot air conditions for at least one day before synthesis.
  • the dried fluorogenic F127 polymer 80 g, ca. 6.36 mmol
  • triarylamine 2 mL, 14.48 mmol
  • acryloyl chloride 1 mL, 25.44 mmol
  • the vapor pressure at 20 ° C. is 124 mmHg, which is relatively less volatile than diethyl ether.
  • nucleic acid as a precipitation solution in terms of yield, such as rapid precipitation, in the case of nucleic acid, whereas the dispersion turned cloudy similarly to an emulsion upon excessive precipitation. That is, in the case of dietel ether, the yield of the finally obtained diacrylated pluronic polymer was about 60 to 70% by weight, whereas in the case of nucleic acid, the yield was about 80 to 90% or more.
  • the polymer semi-aerated product (diacrylated pluronic) thus obtained was dried in a hood to the extent that the residual solvent was removed and then completely dried again in vacuo.
  • the synthesized polymer was dissolved in CDC13 solvent and the 400MHZ 1H NMR spectrum was measured to calculate the double bond incorporation rate.
  • the double bond incorporation rate of diacrylated pluronic F127 obtained by precipitation with nucleic acid after 3 hours reaction was about 74. It was about%.
  • the double bond introduction rate was about 72% when diethyl ether was used and the reaction time was increased to this level (Table 1). This was similar to about 72% of double bond incorporation of diacrylated Pluronic F127 obtained from a previous paper (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004).
  • Example 2 Preparation of Photopolymerized Polyuronic Hydrogel
  • the polymer obtained in Example 1 was dissolved in water to make an aqueous solution.
  • the diacrylated pluronic polymer dissolves well after being put in water or left at room temperature for one day at room temperature.
  • at least one of the water-soluble natural polymers composed of carrageenan and cellulose, agar, galactomannan, glucomannan, guar gum, locust bean gum, alginic acid, carrageenan, xanthan gum and gellan is dissolved together. This is to make the hydrogel with excellent usability.
  • natural biological substances such as natural extracts of plants, animals or minerals extracted from at least one skin affinity enhancer composed of chitosan, chitosan derivatives, elastin, collagen, hyaluronic acid, aloe, green tea, citrus, ginkgo biloba, etc.
  • skin affinity enhancer composed of chitosan, chitosan derivatives, elastin, collagen, hyaluronic acid, aloe, green tea, citrus, ginkgo biloba, etc.
  • polyhydric alcohols such as butylene glycol, propylene glycol, glycerin, methyl paraben, ethyl paraben, phenoxy ethane, alcohol, ⁇ -hydroxy acid, clophenesine, or kojic acid
  • titanium dioxide Use at least one of functional additives such as aluminum oxide.
  • a photoinitiator as needed to enhance the efficiency of photopolymerization.
  • a photoinitiator a product of (4-Benzoylbenzyl) trimethylammonium chloride or Irgacure 1 Lease is used, and a maximum weight of 0.5% (w / vv) is used.
  • Example 2 Since there is no significant difference in hydrogel manufacturing ability between the # 1 and # 2, Example 2 in the following experimental results will be described based on # 2 without the photoinitiator.
  • the concentration of the aqueous solution may be changed to a physical gel state first. The physical gel was confirmed by inverting the plastic container and judging whether the gel was kept. After the physical gel is confirmed, ultraviolet rays are irradiated to prepare a chemical gel. At this time, ultraviolet rays were irradiated for 5 minutes, 10 minutes and 20 minutes.
  • Di-acryloyl Pluronic F127 made by the reaction of acryloyl chloride and pluronic, introduces double bonds at both ends of the polymer, and the double bonds polymerize when irradiated with UV light. After UV irradiation, after washing with water in order to remove the unbanung polymer that may remain on the surface of the hydrogel, the hydrogel is removed using the desired shape.
  • Hydrogel prepared in the present invention was designed to be a disk shape diameter of about 1.7 cm, the thickness is about 2.2 kPa. According to the concentration of the polymer and the preparation of the chemically cross-linked hydrogel according to the UV irradiation time is shown in Table 3 below.
  • the degree of swelling is 5 minutes, 10 minutes, 30 minutes at 4 ° C, room temperature (23 ° C) and 37 ° C by adding a certain amount of water (10 mL) to the weight (Wo) of the hydrogel obtained immediately after the initial preparation. After 1 hour, the relative swelling degree was confirmed by changing the weight and diameter of the hydrogel. The degree of swelling was measured as a ratio of how much the weight of the hydrogel increased after a certain amount of time with respect to the weight of the hydrogel before adding water. ⁇ ⁇ ⁇ Essential weight of hydrogel (g) -initial hydro weight (g)
  • Example 4 Contraction Ratio of Pluronic Hydrogel 4 ° C. and room temperature for measuring the swelling degree of the hydrogel in Example 3
  • the shrinkage degree of the hydrogel may be measured by weight as shown in FIG. 2, but it is most effective to measure the change in the diameter of the hydrogel to enable consumers to know the immediate and visible effect.
  • the hydrogel used in Figures 1 and 2 is not easy to check the change in diameter since the initial diameter itself is small as about 1.7 cm. Therefore, in the present invention, a relatively large hydrogel having a diameter of 5 cm was prepared and shrinkage was measured.
  • the prepared hydrogel condition is that the content of the polymer
  • the sample was irradiated with UV at 25 weight ( ⁇ ⁇ )% for 20 minutes.
  • the initial thickness was designed to be 2 3 and 3 ⁇ , respectively.
  • Composition # 3 of Table 2 was used as Comparative Example 2, and Composition # 2 of Example 2 of Table 2 was used in order to measure the degree of improvement in feeling of use. 10 female consumers in their 50s and 50s Table 5 shows the consumer quality evaluation. Consumer quality evaluation was performed based on the items on the ease of attachment of hydrogel, degree of adhesion and moisturizing after use. Table 5
  • Example 2 1 point: very bad, 2 points: bad, 3 points: normal 4 points: good, 5 points: very good
  • Table 4 the quality satisfaction of Example 2 was found to be superior to Comparative Example 2. This suggests that the feeling of use of water-soluble natural polymer and that of diacrylated pluronic polymer showed synergistic effect. In addition, there was no significant difference between swelling and shrinkage between Example 2 and Comparative Example 2 to which the water-soluble natural polymer was added. This is a part of the diacrylated pluronic polymer, which mainly contributes to the swelling and shrinkage according to the temperature sensitization of the hydrogel, but it is judged to have a better feeling when additionally using a water-soluble natural polymer.
  • the water-soluble cosmetics contained in the hydrogel are more quickly and uniformly delivered into the skin through shrinkage according to the temperature of the hydrogel. It can be used as a skin temperature sensitive hydrogel cosmetic composition because it can be attached more tightly.

Abstract

The present invention relates to a preparation of a skin temperature sensitive hydrogel, and a hydrogel composition providing a cool feeling, moisture, and various active ingredients to the skin by using a contracting property which responds to skin temperature through a use thereof. The hydrogel of the present invention is obtained by adding a double bond to both ends of Pluronic, which is a temperature sensitive polymer, and chemically cross-linking the same through UV radiation. The hydrogel obtained thereby responds to skin temperature so as to show a contraction property, and thereby can provide water collected inside, a moisturizing ingredient, and various active ingredients to the skin. In addition, elasticity is provided to the skin and adhesion of the hydrogel to the skin is increased by the contracting property of the hydrogel.

Description

【명세서】  【Specification】
【발명의 명칭】 [Name of invention]
피부온도 감응성 하이드로겔 조성물 및 그 제조방법  Skin temperature sensitive hydrogel composition and preparation method thereof
【기술분야】 Technical Field
본 발명은 피부온도 감웅성 하이드로겔을 갖는 화장료 조성물에 관한 것으로 피부온도에 반응하여 하이드로겔의 온도에 따른 수축성을 통해 하이드로겔에 함유된 수용성 미용제를 피부속으로 보다 신속하고 균일하게 전달하도록 하였으며, 또한 이러한 수축성으로 인해 피부에 하이드로겔이 좀 더 밀착감있게 붙을 수 있도록 도움을 줄 수 있다. 【배경기술】  The present invention relates to a cosmetic composition having a skin temperature sensitizing hydrogel to more quickly and uniformly deliver the water-soluble beauty agent contained in the hydrogel into the skin through shrinkage according to the temperature of the hydrogel in response to the skin temperature. This shrinkage can also help the hydrogel adhere to the skin more tightly. Background Art
하이드로겔은 다량의 수분을 함유하는 고분자 네트워크 구조를 가진 물질로 단일중합체 또는 공중합체등에 의해 이루워진다. 하이드로겔은 수용액 상에서 물을 비롯한 친수성 성분들의 흡수를 통해 팽윤되면서 투명하게 되고, 또한 적당한 기계적 물성을 가진다. 이러한 팽윤도와 고분자의 기계적 물성은 주로 고분자 네트워크 구조의 물성에 의존한다. 이러한 하이드로겔을 만들 수 있는 소재로는 주로 고분자가 많이 사용되는데, 이 고분자는 그 소재의 기원에 따라 천연고분자와 합성고분자 2가지로 나뉜다. 천연고분자로 만든 하이드로겔은 한천, 카라기난, 셀롤로스 및 잔탄검등과 같은 천연소재에서 유래한 고분자를 가지고 만들기 때문에 소비자들에게는 천연 유래라는 의미의 좋은 인상올 줄 수는 있지만, 기계적 물성이 약한 것이 특징이다. 이러한 천연고분자는 대부분 물리적 겔화반응에 의해 만들어졌기 때문에 고온조건에서는 하이드로겔이 용해되어 졸 (Sol) 상태로 변하기 쉽고, 또한 저온이나 실온조건에서는 기계적 강도가 약하여 작은 충격에도 깨지거나 찢어지기 때문에 유통 및 제품사용 과정에서 상당한 주의가 필요하게 된다. 이에 비해 합성고분자로 만든 하이드로젤은 가교결합을 통해 분자들 사이에 화학적 공유결합과 같은 강한 결합력을 가지고 았기 때문에 천연고분자와 달리 강한 기계적 물성을 가지고 있어 온도와 외력 등 외부 자극에 대해 하이드로겔 형태가 손상되는 경우가 비교적 드물다. 또한, 최근 기술의 진보에 의해 생분해성, 생체적합성 특징을 가진 다양한 고분자들이 출시되었기 때문에 합성고분자에 대한 인식도 점점 좋아지고 있다. 이러한 합성고분자에 의해 만들어진 하이드로겔 관련 특허로는 온도 감웅성 상태변화 하이드로겔 조성물 특허 (대한민국 특허번호 제 506543호)가 있다. 이 특허에서는 피부와 접촉시 체온에 의해 하이드로겔 상태가 유동상태로 변화되어 흐름성을 갖으며, 이를 통해 하이드로겔 내에 함유되어 있는 미용제 또는 약물이 피부에 고르게 피복되고 신속하게 침투한다고 하였으나, 이 경우 실제 피부와의 반응을 통해 하이드로겔 중 일부만이 유동성이 있는 상태로 변화하는 등 한계를 갖고 있다. Hydrogel is a material having a polymer network structure containing a large amount of water is made by a homopolymer or a copolymer. The hydrogel becomes transparent as it swells through absorption of hydrophilic components, including water, in aqueous solution and also has adequate mechanical properties. Such swelling and mechanical properties of the polymer mainly depend on the properties of the polymer network structure. As a material for making such a hydrogel, a large number of polymers are mainly used. The polymer is divided into two kinds of natural polymer and synthetic polymer according to the origin of the material. Hydrogels made of natural polymers are made of polymers derived from natural materials such as agar, carrageenan, cellulose, and xanthan gum, which may give consumers a good impression of the origin of nature, but they are weak in mechanical properties. It is characteristic. Since most of these natural polymers are made by physical gelation reaction, hydrogels are easily dissolved and changed to a sol state at high temperature conditions, and at low temperature or room temperature conditions, the mechanical strength is weak so that they are broken or torn even in a small impact. Great care must be taken in the use of the product. In contrast, hydrogels made of synthetic polymers have strong binding properties such as chemical covalent bonds between molecules through crosslinking, and thus, unlike natural polymers, hydrogels have strong mechanical properties. Damaged Cases are relatively rare. In addition, due to the recent advances in technology, various polymers having biodegradable and biocompatible characteristics have been released, and thus, the recognition of synthetic polymers is also getting better. Hydrogel-related patents made by such synthetic polymers include a temperature sensitive state change hydrogel composition patent (Korean Patent No. 506543). According to this patent, the hydrogel state is changed to a fluid state by the body temperature when it comes into contact with the skin, and it has flowability. Through this, the beauty agent or drug contained in the hydrogel is uniformly coated on the skin and quickly penetrates. In this case, only a part of the hydrogel is changed to a fluid state through the reaction with the skin and has a limit.
또 다른 특허 (대한민국 특허번호 제 848712)에서는 플투로닉의 양 말단에 이중결합을 도입하고, 광개시제와 자외선을 사용하여 고분자 중합을 시킨 화학적 겔을 제조하였다. 그러나ᅳ 이 방법은 주로 주입형 겔을 주사를 통해 생체 내로 주입시 낮은 온도에서 겔화되는 플루로닉의 단점을 막기 위해 키토산과 흔용하여 졸 (Sol)-겔 (Gel) 전이온도를 올리는 데에 목적이 있다. 또한, 플루로닉 고분자의 양 말단에 이중결합을 도입하는 합성과정에서 침전현상을 위해 디에틸에테르를 사용하는데, 디에틸에테르는 휘발성이 강하고 끓는점이 낮기 때문에 양산을 위해 공장에서 사용시 적절하지 않은 용매로 알려져 있다.  In another patent (Korean Patent No. 848712), a double bond was introduced at both ends of the Pturonic and a polymer gel was prepared by polymerizing the polymer using a photoinitiator and ultraviolet light. However, this method is mainly aimed at raising the sol-gel transition temperature in combination with chitosan to avoid the drawback of Pluronic gelation at low temperatures when injecting gel into the body via injection. There is this. In addition, diethyl ether is used for precipitation during the synthesis of introducing double bonds at both ends of the pluronic polymer. Diethyl ether is not suitable for use in factories for mass production because of its high volatility and low boiling point. Known as
본 발명에서는 온도 및 외력에 대한 강한 저항성을 갖는 하이드로겔을 만들기 위해 물리적 겔화 작용이 아닌 화학적 가교결합에 의해 하이드로겔 제조방법을 제공하고자 한다. 이를 위해 본 발명에서는 플루로닉 고분자를 이용하였다. 플루로닉 고분자는 PE0-PP0-PE0 (polyethyl eneox i de-po 1 ypr opy 1 eneox i de-po 1 ye t hy 1 eneox i de )≤- 구성된 t r i一 block copolymer로서 생체적합성을 갖고 생리적인 조건에서 분해되는 생분해성 고분자로 널리 알려져 있어 인체 내에서도 안전하다고 알려져 있다. 플루로닉은 소수성 그룹인 (PP0)가 LCST(Low Critical Solution Temperature) 특징을 갖고 있어 특정 온도 이상에서 자가 조립 (Self- assembly)을 할 수 있으며, 이에 따라 온도 감응성을 갖게 된다. 상기 플루로닉을 포함한 대부분의 고분자들은 중합과정을 거쳐 얻어지는데, 그 분자량은 항상 일정한 것이 아니라 다양한 영역에서의 고른 분포를 갖고, 이것을 평균하여 얻어지기 때문에 균일한 품질의 고분자를 얻기란 불가능하다. 따라서, 이러한 고분자를 가지고 만든 하이드로겔은 제조과정에서 얻어지는 졸-겔 전이온도가 일정하지 않을 가능성이 높고 , 그에 따라서 피부에 반웅하여 하이드로겔로부터 유동성이 있는 졸 상태로 변하는 온도조건 또한 균일하지 못할 가능성이 높다. In the present invention, to provide a hydrogel production method by chemical crosslinking rather than physical gelling action to make a hydrogel having a strong resistance to temperature and external force. To this end, in the present invention, a pluronic polymer was used. Pluronic polymer is a trione block copolymer composed of PE0-PP0-PE0 (polyethyl eneox i de-po 1 ypr opy 1 eneox i de-po 1 ye t hy 1 eneox i de) ≤- biocompatible and physiological conditions It is widely known as a biodegradable polymer that decomposes in, and is known to be safe in the human body. Pluronic has a low critical solution temperature (LCST) characteristic of the hydrophobic group (PP0), which enables self-assembly above a certain temperature and thus temperature sensitivity. Most polymers, including the pluronic, are obtained through a polymerization process, the molecular weight of which is not always constant, but even distribution in various regions, Since it is obtained by averaging it, it is impossible to obtain a polymer of uniform quality. Therefore, hydrogels made with these polymers are not likely to have a constant sol-gel transition temperature obtained during the manufacturing process, and thus may not be uniform in the temperature conditions that change from the hydrogel to the flowable sol state. This is high.
【발명의 상세한 설명】 [Detailed Description of the Invention]
【기술적 과제】  [Technical problem]
본 발명은 플루로닉 고분자의 양 말단에 이중결합을 도입 후, 자외선 (UV) 조사를 통해 화학적으로 가교를 시켜 원하는 물성을 갖는 하이드로겔을 제조한다. 이 과정에서 사용감의 우수성을 위해 수용성 천연 고분자도 일부 포함한다. 또한, 이렇게 만들어진 하이드로젤을 이용하여 피부에 청량감과 보습감을 부여하고 피부온도에 반웅하여 크기가 수축되는 하이드로겔을 제조하여 피부에 탄력감과 밀착감을 부여하는 화장료 조성물을 제공하는 데에 그 목적이 있다.  The present invention, after introducing a double bond at both ends of the pluronic polymer, and chemically cross-linked through ultraviolet (UV) irradiation to produce a hydrogel having the desired physical properties. In this process, some water-soluble natural polymers are included for the superior feeling. In addition, the purpose of the present invention is to provide a cosmetic composition that gives the skin a refreshing and moisturizing feeling by using the hydrogel thus produced and the elasticity and adhesion to the skin by producing a hydrogel that shrinks in size by reacting to the skin temperature. .
【기술적 해결방법】 Technical Solution
본 발명의 한 양태에 따르면, 본 발명은 디아크릴레이티드 플루로닉 고분자, 수용성 천연 고분자, 광개시제 존재 또는 미존재하에서 자외선 (UV)에 의해 화학적으로 가교결합하여 얻어진, 피부 온도범위에서 가역적인 팽윤성 및 수축성 성질을 갖고, 그 내부 구조에 다공성 구조를 갖는 것올 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물를 제공한다.  According to one aspect of the invention, the invention is reversible swelling in the skin temperature range, obtained by chemical crosslinking by ultraviolet (UV) in the presence or absence of a diacrylated pluronic polymer, a water soluble natural polymer, a photoinitiator or not. And it has a shrinking property, and provides a skin temperature-sensitive hydrogel cosmetic composition characterized in that it has a porous structure in its internal structure.
다공성 구조가 없는 하이드로겔의 경우, 표면에 적셔져 있는 수용성 효능물질들만이 피부에 전달될 수 있으나, 다공성 구조를 가진 플루로닉 하이드로겔은 피부온도에 감응하여 플루로닉 하이드로겔이 수축하게 될 때, 다공성 구조를 통해 내부에 있는 각종 수용성 효능 물질들이 피부에 방출될 수 있도록 하는 길의 역할을 하게 된다.  In the case of a hydrogel without a porous structure, only water-soluble agonists that are moistened on the surface can be delivered to the skin, but a pluronic hydrogel with a porous structure may contract the pluronic hydrogel in response to skin temperature. At this time, the porous structure serves as a way to allow the release of various water-soluble substances inside the skin.
본 발명에 있어서, 상기 플루로닉 고분자는 PE0-PP0-PE0 (poly ethyl eneoxide- o 1 ypr opy 1 eneox i de-po 1 yet hy 1 eneox i de )≤. 구성된 어떤 tri— block copolymer도 사용될 수 있으나, 바람직하게는 분자량 약 8,700 Da의 플루로닉 F68 ((PE0)75(PP0)30(PE0)75) 또는 ^자량 약 12,600 Da의 플루로닉 F127((PE0)99(PP0)69(PE0)99) 인 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물올 제공한다. In the present invention, the pluronic polymer is PE0-PP0-PE0 (poly ethyl eneoxide- o 1 ypr opy 1 eneox i de-po 1 yet hy 1 eneox i de) ≤. Any tri-block copolymer constructed may be used, but preferably has a molecular weight of about 8,700 Da's Pluronic F68 ((PE0) 75 (PP0) 30 (PE0) 75) or ^ Pluronic F127 ((PE0) 99 (PP0) 69 (PE0) 99) It provides a skin temperature sensitive hydrogel cosmetic composition.
플루로닉 고분자는 F로 시작하는 F38, F68, F77, F98, F108, F127등과 L로 시작하는 L31, L42, L43, L44, L62, L72, Ll()l등과 P로 시작하는 P75, P103, P104 등이 있는데, 이러한 상품명의 차이는 조성비나 형태의 차이에 기인한다. 그 가운데 미국 식품의약청 (FDA)의 허가를 받은 분자량 약 8,700 Da의 F68((PE0)75(PP0)30(PE0)75)과 분자량 약 12,600 Da의 F127( (PE0)99(PP0)69(PE0)99) 등이 주로 생체 재료로서 사용되고 있다. 본 발명에 있어서, 상기 디아크릴레이티드 플루로닉 고분자는 플루로닉 고분자의 양 말단에 이중결합이 있는 아크릴레이트를 부가하여 합성되는 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다.  Pluronic polymers include F38, F68, F77, F98, F108, F127 starting with F and L31, L42, L43, L44, L62, L72, Ll () l starting with L and P75, P103, starting with P, P104 and the like, the difference in brand name is due to the difference in composition ratio and form. Among them, F68 ((PE0) 75 (PP0) 30 (PE0) 75) with a molecular weight of about 8,700 Da and F127 ((PE0) 99 (PP0) 69 (PE0) with a molecular weight of about 12,600 Da are approved by the US Food and Drug Administration (FDA). 99) and the like are mainly used as biological materials. In the present invention, the diacrylated pluronic polymer provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that the synthesis by adding a double bond acrylate at both ends of the pluronic polymer.
본 발명에 있어서, 상기 합성공정시 침전용매로서 핵산을 사용하는 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다. 본 발명의 실시예에서는 침전용매로서 핵산을 사용할 경우 종래 침전용매로서 디에틸에테르를 사용한 것에 비하여 고분자의 합성반웅시간이 획기적으로 단축되는 동시에 이중결합 도입율은 동등이상임을 확인하였다. 본 발명에 있어서, 상기 수용성 천연 고분자는 디아크릴레이티드 플루로닉 고분자와 함께 하이드로겔을 형성할 수 있는 어떤 수용성 천연 고분자도 사용될 수 있으나, 바람직하게는 카라기난, 셀를로스, 한천, 갈락토만난, 글루코만난, 구아검, 로카스트 빈 검, 알긴산, 카라기난, 잔탄검 및 겔란 으로 구성된 그룹으로부터 선택된 최소 1종의 수용성 천연 고분자인 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다. 본 발명의 실시예에서는 수용성 천연 고분자를 추가 사용시 피부 부착의 용이성, 밀착감 정도 및 사용 후 보습감 등에서 더 우수한 사용감을 갖는 것을 확인하였다.  In the present invention, it provides a skin temperature sensitive hydrogel cosmetic composition characterized in that the nucleic acid is used as the precipitation solvent during the synthesis process. In the embodiment of the present invention, when the nucleic acid is used as the precipitation solvent, the synthesis reaction time of the polymer is drastically shortened and the double bond introduction rate is equal to or higher than that of diethyl ether as the conventional precipitation solvent. In the present invention, the water-soluble natural polymer may be used any water-soluble natural polymer capable of forming a hydrogel with the diacrylated pluronic polymer, preferably carrageenan, cellulose, agar, galactomannan, It provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that at least one water-soluble natural polymer selected from the group consisting of glucomannan, guar gum, locust bean gum, alginic acid, carrageenan, xanthan gum and gellan. In the embodiment of the present invention it was confirmed that the additional use of the water-soluble natural polymer has a better feeling in ease of skin adhesion, degree of adhesion and moisturizing after use.
본 발명에 있어서, 상기 피부온도 범위는 0° C-50° C 온도범위, 바람직하게는 30° C— 40° C 인 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다. 본 발명의 실시예에서는 실제 피부에 도포한 경우 피부온도에 감웅하여 팽윤된 하이드로겔이 시간에 따라 수축된 하이드로겔로 변화하는 것을 확인하였다. In the present invention, the skin temperature range is 0 ° C-50 ° C temperature range, preferably provides a skin temperature sensitivity hydrogel cosmetic composition, characterized in that 30 ° C-40 ° C. In the embodiment of the present invention, when applied to the actual skin swelling hydrogel swells at skin temperature over time It was confirmed to change to the contracted hydrogel.
본 발명에 있어서, 상기 피부은도 범위에서 가역적인 팽윤성 및 수축성 성질은 피부온도에 반웅하여 팽윤된 겔 상태에서 수축된 겔 상태로 변화하는 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물올 제공한다. 종래 하이드로겔은 피부온도범위에서 겔에서 졸로 가역적인 반웅을 하는 반면, 본 발명의 하이드로겔은 피부온도 범위에서 팽윤된 겔에서 수축된 겔로 가역적인 반웅을 하는 점에 차이가 있다.  In the present invention, the reversible swelling and shrinking properties in the skin degree range provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that it changes from the swollen gel state to the contracted gel state in response to skin temperature. Conventional hydrogels have a reversible reaction from gel to sol in the skin temperature range, whereas the hydrogels of the present invention have a difference in reversible reaction from a swollen gel in the skin temperature range.
본 발명에 있어서, 피부에 청량감과 보습감을 부여할뿐만 아니라 피부에 탄력감과 밀착감을 부여하는 것을 특징으로 하는 피부은도감웅성 하이드로겔 화장료 조성물을 제공한다. 본 발명의 하이드로겔은 피부에 부착시 피부온도에 의해 수축함으로써 수분 및 수용성 효능물질들을 방출하여 피부에 청량감과 보습감을 즐뿐만 아니라 피부에 탄력감과 밀착감을 부여할 수 있다.  In the present invention, it provides a skin sensitizing hydrogel cosmetic composition characterized by imparting a feeling of cooling and moisturizing to the skin as well as imparting elasticity and fit to the skin. Hydrogel of the present invention by contracting by the skin temperature when attached to the skin to release the moisture and water-soluble potent substances can not only enjoy the refreshing and moisturizing feeling on the skin, but also gives the skin a feeling of elasticity and fit.
본 발명에 있어서, 바람직하게는 조성물의 총 중량을 기준으로 디아크릴레이티드 플루로닉 고분자 1-60%, 수용성 천연 고분자 0.1-30중량 ¾>, 피부친화성 증진제 1-20 중량 %, 천연생체물질 1-20 중량 %, 다가알코올 1-30 중량 %, 기능첨가제 0.01-10 중량 % 및 물 20-90 중량 %를 포함하여 구성되고, 여기에 광개시제를 첨가하지 않거나 또는 소량 첨가하여 자외선 (UV)에 의해 화학적으로 가교결합하여 얻어지는 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다.  In the present invention, preferably 1-60% of diacrylated pluronic polymer, 0.1-30% of water-soluble natural polymer, 1-20% by weight of skin affinity enhancer, and natural organisms, based on the total weight of the composition. 1-20% by weight of material, 1-30% by weight of polyhydric alcohol, 0.01-10% by weight of functional additives and 20-90% by weight of water, with no or no small amount of photoinitiator added thereto. It provides a skin temperature-sensitive hydrogel cosmetic composition, which is obtained by chemically crosslinking by.
본 발명에서는 광개시제를 소량사용하거나 또는 사용하지 않고 하이드로겔을 제조하였는데, 광개시제 여부와 상관없이 하이드로겔 생성이 가능하였다. 광개시제는 자외선 조사시 라디칼을 잘 형성하여 중합반응을 촉진시키는 기능을 수행하지만, 자외선 조사 종료 후 하이드로겔의 표면 또는 내부에 잔류할 수도 있기 때문에 피부 안전성을 고려하여 가급적 소량을 사용하거나 또는 전혀 사용하지 않는 것이 바람직하다.  In the present invention, a hydrogel was prepared with or without a small amount of photoinitiator, and hydrogel production was possible regardless of the photoinitiator. The photoinitiator functions to promote the polymerization reaction by forming radicals well when irradiated with UV rays. However, since photoinitiators may remain on the surface or inside of the hydrogel after UV irradiation ends, use a small amount as much as possible in consideration of skin safety. It is preferable not to.
본 발명에 있어서, 바람직하게는 상기 피부친화성 증진제는 키토산, 키토산유도체, 엘라스틴, 콜라겐, 히알루로닉산으로 구성된 그룹으로부터 선택된 최소 1종의 다당류 또는 단백질임을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물을 제공한다.  In the present invention, preferably the skin affinity enhancer is a skin temperature sensitive hydrogel cosmetic composition, characterized in that at least one polysaccharide or protein selected from the group consisting of chitosan, chitosan derivatives, elastin, collagen, hyaluronic acid to provide.
본 발명에 있어서, 바람직하게는 상기 천연생체물질은 알로에, 녹차, 감글, 은행잎등으로부터 추출된 식물, 동물 또는 광물의 천연추출물임을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물을 제공한다. In the present invention, preferably the natural biomaterial is aloe, green tea, It provides a skin temperature sensitivity hydrogel cosmetic composition characterized in that the natural extract of plants, animals or minerals extracted from the gimgle, ginkgo leaves and the like.
본 발명에 있어서, 바람직하게는 상기 다가알코올은 수용성 액상의 부틸렌글리콜, 프로필렌글리콜 또는 글리세린임을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물을 제공한다.  In the present invention, the polyhydric alcohol preferably provides a skin temperature sensitive hydrogel cosmetic composition, characterized in that the water-soluble liquid butylene glycol, propylene glycol or glycerin.
본 발명에 있어서, 바람직하게는 상기 기능첨가제는 하이드로겔의 안정성 및 방부성, 유효성분의 첨가를 통해 미용기능성을 부여할 수 있는 첨가제로서 메틸파라벤, 에틸파라벤, 페녹시에탄올, 알콜, α-히드록시산, 클로페네신, 또는 코직산, 이산화티탄, 알루미늄 옥사이드등을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물올 제공한다.  In the present invention, preferably, the functional additive is methyl paraben, ethyl paraben, phenoxyethanol, alcohol, α-hydroxy as an additive that can impart cosmetic functionality through the addition of the stability and preservation of the hydrogel and the active ingredient. Provided is a skin temperature sensitive hydrogel cosmetic composition characterized by an acid, clofenesin, or kojic acid, titanium dioxide, aluminum oxide and the like.
본 발명의 다른 양태에 따르면, 본 발명은 상기 본 발명에 따른 피부온도감웅성 하이드로겔 조성물을 포함하는 피부외용 화장품 또는 의약품을 제공한다. 상기 피부외용 화장품 또는 의약품은 종래 하이드로겔을 매체로 사용할 수 있는 어떤 피부외용 화장품 또는 의약품도 될 수 있다.  According to another aspect of the present invention, the present invention provides a skin external cosmetics or medicines comprising the skin temperature sensitive hydrogel composition according to the present invention. The external skin cosmetics or medicines may be any external skin cosmetics or medicines that can use a conventional hydrogel as a medium.
이하, 본 발명을 더욱 구체적으로 설명한다.  Hereinafter, the present invention will be described in more detail.
플루로닉 F-127 고분자는 적당한 농도일 때, 체온 근처의 온도 (33- 37° C)범위에서 유동성이 없는 겔 상태와 유동성이 있는 졸 상태 사이에 전이현상이 일어난다. 이 때, 만들어지는 겔은 물리적 겔로 외부의 온도와 힘에 의해 그 형태가 붕괴될 수 있을만큼 기계적 물성이 약하다. 그렇기 때문에 이러한 단순한 전이현상만으로는 화장품에 적합한 제형을 만들 수 없기 때문에 본 발명의 발명자들은 자외선 (UV)을 사용하여 화학적으로 가교결합된 겔을 만들고 이를 통해 화장품에 적용가능한 하이드로겔을 제조하였다. When the Pluronic F-127 polymer is at a suitable concentration, a transition occurs between a fluid-free gel and a fluid sol at temperatures near body temperature (33-37 ° C). At this time, the resulting gel is a physical gel that is weak in mechanical properties so that its shape can be collapsed by external temperature and force. Therefore, the inventors of the present invention by using the ultraviolet light (UV) to make a chemically cross-linked gel by using this simple transition phenomenon alone to make a hydrogel applicable to cosmetics.
본 발명자들은 이를 위하여 플루로닉 고분자의 양 말단에 이중결합이 있는 아크릴레이트를 부가하여 디아크릴레이티드 플루로닉을 합성하였다. 이 때, 합성공정시 작업자의 안전을 위해 침전용매로는 이전의 논문 (Lee 등, J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004)에서 사용한 디에틸에테르 대신 핵산을 사용하였다. 핵산의 증기압 (124 隱 Hg, 20° C)은 디에틸에테르의 증기압 (440 薩 ¾, 20° C)에 비해 낮기 때문에 작업시 작업자들의 용매흡입에 따른 위험성을 감소시켜줄 수 있고, 또한 핵산의 끓는점 (약 69° C)은 디에틸에테르의 끓는점 (약 35° C)보다 높기 때문에 합성공정시 발열반웅에 의해 생길 수 있는 용매의 증발면에 있어서도 훨씬 효율적이다. 뿐만 아니라, 디에틸에테르의 경우 침전 공정시 에멀젼과 유사한 분산현상이 발생하여 침전시간이 오래 걸리는 데 비하여 핵산의 경우는 그 즉시 침전이 가능하기 때문에 안전 및 공정의 효율성 측면에서 디에틸에테르보다 훨씬 우수한 용매이다. The present inventors synthesized diacrylated pluronic by adding an acrylate having a double bond at both ends of the pluronic polymer. At this time, nucleic acid is used instead of the diethyl ether used in the previous paper (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004) for the safety of the workers in the synthesis process. It was. The vapor pressure of the nucleic acid (124 隱 Hg, 20 ° C) is lower than the diethyl ether vapor pressure (440 薩 ¾, 20 ° C), thus reducing the risk of solvent inhalation during the operation. The boiling point (about 69 ° C) is higher than the boiling point of diethyl ether (about 35 ° C), so it is much more efficient in terms of evaporation of solvents that can be produced by exothermic reactions during the synthesis process. In addition, in the case of diethyl ether, dispersion similar to emulsion occurs during the precipitation process, which takes a long time to settle, whereas nucleic acid can be precipitated immediately, which is much superior to diethyl ether in terms of safety and process efficiency. Solvent.
본 발명에서는 상기와 같이 만들어진 디아크릴레이티드 플루로닉을 단독으로 또한 다른 수용성 고분자와 흔합을 하여 자외선 조사를 통해 하이드로겔을 제조하였다. 디아크릴레이티드 플루로닉 단독으로도 자외선 조사를 통하여 하이드로겔올 제조할 수 있지만, 우수한 사용감의 하이드로겔을 제조하기 위해 본 발명자들은 샐를로스, 카라기난검과 같은 수용성 천연 고분자를 흔입하여 우수한 사용감을 가진 하이드로겔을 제조하였다. 수용성 천연 고분자만으로 제조된 기존의 하이드로겔은 내부 구조에서 특이한 점이 없었지만, 디아크릴레이티드 플루로닉 고분자를 단독으로 또는 다른 수용성 고분자와 흔합올 하여 자외선 조사로 만든 하이드로겔에서는 명확한 다공성 구조가 관찰되었다.  In the present invention, the diacrylated pluronic acid made as described above alone and in combination with other water-soluble polymers to prepare a hydrogel through ultraviolet irradiation. Although diacrylated pluronic alone can produce hydrogels through UV irradiation, the present inventors invented water-soluble natural polymers such as cellulose and carrageenan gum to produce hydrogels with excellent feeling. Hydrogels were prepared. Existing hydrogels made of only water-soluble natural polymers did not have any specificities in their internal structure, but a clear porous structure was observed in hydrogels made by UV irradiation alone or in combination with other water-soluble polymers. .
또한, 본 발명에서는 또한 개시제를 소량하거나 또는 전혀 사용하지 않고 하이드로겔을 제조하였다. 이렇게 만들어진 하이드로겔은 상온 또는 냉장조건에서 수용액 상태의 화장료 조성물에 의해 팽윤된 후 피부 온도인 37° C에 반웅하여 내부에 포집된 수용액을 방출하면서 그 무게와 크기가 현저하게 수축됨을 확인하였다.  In addition, the present invention also prepared hydrogels with little or no initiator. The hydrogel thus produced was swelled by the cosmetic composition in an aqueous solution at room temperature or refrigerated conditions and then reacted at 37 ° C, which is the skin temperature, to release the aqueous solution collected therein.
【유리한 효과】 Advantageous Effects
본 발명으로 만들어진 온도 민감성 하이드로겔은 피부온도에 반웅하여 하이드로겔 자체가 수축하면서 동시에 하이드로겔 내부에 팽윤되어 있던 물을 비롯하여 보습성분 및 각종 유효성분을 피부에 방출한다 . 이를 통해 피부에 청량감과 보습감을 부여하고, 피부에 좋은 각종 유효성분을 공급할 수 있다. 또한, 하이드로겔의 수축하는 성질로 인하여 피부에 탄력감을 부여하고, 또한 이러한 수축성으로 인해 피부에 하이드로겔이 좀 더 밀착감있게 붙을 수 있도록 도움을 줄 수 있다. 【도면의 간단한 설명】 The temperature sensitive hydrogel made by the present invention reacts to the skin temperature and releases moisturizing ingredients and various active ingredients, including water that was swelling inside the hydrogel while simultaneously shrinking the hydrogel itself. This gives the skin a refreshing and moisturizing feeling, and can supply various effective ingredients to the skin. In addition, due to the shrinking nature of the hydrogel gives a sense of elasticity to the skin, and also due to this shrinkage may help to attach the hydrogel more tightly to the skin. [Brief Description of Drawings]
도 1은 본 발명의 실시예에 따라 제조된 플루로닉 하이드로겔의 팽윤도 (Swelling ratio)를 측정한 그래프이다.  1 is a graph measuring the swelling ratio (Swelling ratio) of the Pluronic hydrogel prepared according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따라 제조된 플루로닉 하이드로겔의 수축도 (Contract ion ratio)를 측정한 그래프이다.  Figure 2 is a graph measuring the contraction ratio (Contract ion ratio) of the Pluronic hydrogel prepared according to the embodiment of the present invention.
도 3은 본 발명의 실시예에 따라 제조된 플루로닉 하이드로겔의 내부구조 및 수용성 고분자 단독으로 만들어진 하이드로겔을 주사전자현미경 (SEM)으로 관찰한 결과이다. 【발명의 실시를 위한 형태】  3 is a result of observing the hydrogel made of the internal structure of the Pluronic hydrogel prepared according to the embodiment of the present invention and the water-soluble polymer alone with a scanning electron microscope (SEM). [Form for implementation of invention]
이하, 본 발명을 하기 실시 예에 의거하여 좀 더 상세하게 설명하고자 한다. 단, 하기 실시 예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 제한되는 것은 아니다. 시약 및 시료  Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto. Reagents and Samples
플루로닉 F-127 ((PE0)99(PP0)69(PE0)99)는 BASF에서 구입하였고, 트리에틸아민 (Triethylamine)은 Sigma에서 그리고 아크릴로일 클로라이드 (Acryloyl chloride)는 Wako로부터 구입하였다. 또한, 합성반웅에 사용된 용매인 메틸렌클로라이드 (Methylene chloride)는 J&T Baker에서 그리고 침전을 위해 사용된 핵산 (Hexane)은 대정 (한국)으로부터 구입하였다. 실시예 1 : 아크릴레이티드 플루로닉의 합성  Pluronic F-127 ((PE0) 99 (PP0) 69 (PE0) 99) was purchased from BASF, Triethylamine was purchased from Sigma and Acryloyl chloride was purchased from Wako. In addition, methylene chloride, a solvent used in the synthesis reaction, was purchased from J & T Baker and nucleic acid (Hexane) used for precipitation was obtained from Daejeong (Korea). Example 1 Synthesis of Acrylated Pluronic
이 단계는 플루로닉 F127 고분자의 양 말단에 이중결합을 도입시키는 과정으로 합성하기전 플루로닉 고분자를 진공조건 또는 열풍조건에 의해 하루이상 건조시킨다. 층분히 건조시킨 플로로닉 F127 고분자 (80 g, ca. 6.36 mmol)와 트리에될아민 (2 mL, 14.48 隱 ol)을 디클로로메탄 200 mL에 넣고 녹인다. 플루로닉 고분자가 모두 용해되어 투명하게 되면, 플루로닉 고분자의 양 말단에 이중결합을 도입하기 위하여 아크릴로일 클로라이드 (1 mL, 25.44 mmol)를 한 방울씩 천천히 투입하였다. 트리에틸아민의 특이취와 반응시 생성되는 염화수소 (HC1) 기체로 인하여 이 과정은 반드시 후드안에서 진행하였다. This step is to introduce double bonds at both ends of the Pluronic F127 polymer and to dry the Pluronic polymer by vacuum or hot air conditions for at least one day before synthesis. The dried fluorogenic F127 polymer (80 g, ca. 6.36 mmol) and triarylamine (2 mL, 14.48 mmol) are added to 200 mL of dichloromethane and dissolved. When all of the pluronic polymer was dissolved and transparent, acryloyl chloride (1 mL, 25.44 mmol) was slowly added dropwise to introduce double bonds at both ends of the pluronic polymer. This process is essential because of the specific odor of triethylamine and the hydrogen chloride (HC1) gas produced during the reaction. Proceed in the hood.
종래 논문 (Lee 등, J. Biomater. Sci. Polymer Edn, Vol. 15, 1571- 1583, 2004)과 특허 (특허번호 848712)에서는 이 합성반웅을 4° C에서 12시간 수행 후 24° C에서 12시간 수행하였지만, 본 발명에서는 상온에서 3시간만 수행하여도 유사한 결과가 얻을 수 있음을 확인하였다. Prior papers (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004) and patent (Patent No. 848712) performed this synthesis reaction at 12 ° C at 12 ° C after 12 hours at 4 ° C. Although performed for a time, in the present invention, it was confirmed that similar results can be obtained by performing only 3 hours at room temperature.
또한, 종래 논문 (Lee 등, J. Biomater. Sci . Polymer Edn, Vol. 15, In addition, conventional papers (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15,
1571-1583, 2004)과 특허 (특허번호 848712)에서는 반응 후 차갑게 해놓은 과량의 디에틸에테르로 반웅물을 침전시킨 후 여과하였지만, 본 발명에서는 디에틸에테르 대신 핵산을 사용하였다. 앞서 발명의 구성 및 작용에서 디에틸에테르의 경우, 끓는점이 약 35° C이고, 20° C에서 증기압도 440 mmHg 정도로 휘발성이 강한데 비하여 핵산은 끓는점이 약 69° C이고,1571-1583, 2004) and patent (Patent No. 848712) precipitated the semicolumn with an excess amount of cold diethyl ether after the reaction and filtered, but in the present invention, nucleic acid was used instead of diethyl ether. In the configuration and operation of the present invention, diethyl ether has a boiling point of about 35 ° C., a vapor pressure of 440 mmHg at 20 ° C., whereas a nucleic acid has a boiling point of about 69 ° C.,
20° C에서 증기압이 124 mmHg 정도로 상대적으로 디에틸에테르에 비하여 휘발성이 작다. 또한, 디에틸에테르의 경우 과량 침전시 에멀젼과 유사하게 분산액이 뿌옇게 변하는 데에 비하여 핵산의 경우에는 신속하게 침전이 얻어지는등 수율면에 있어서도 침전용액으로 핵산을 사용하는 것이 더 우수하였다. 즉, 디에텔에테르의 경우 최종적으로 얻어진 디아크릴레이티드 플루로닉 고분자의 수율이 중량대비 약 60~70% 정도인데 비하여 핵산의 경우는 약 80~90% 이상의 우수한 수율을 보여주었다. 이렇게 얻어진 고분자 반웅물 (디아크릴레이티드 플루로닉)은 잔류용매를 제거시키기 위해 이를 정도 후드에서 건조시킨 후 진공에서 다시 한 번 완전히 건조시켰다. 합성된 고분자는 CDC13 용매에 녹여 400MHZ 1H NMR 스펙트럼을 측정하여 이중결합의 도입율을 계산하였고, 3시간 반응 후 핵산으로 침전을 하여 얻은 디아크릴레이티드 플루로닉 F127의 이중결합 도입율은 약 74% 정도였다. 또한, 이전의 논문에서처럼 디에틸에테르를 사용하고 반웅시간을 이를정도로 진행한 경우에서의 이중결합 도입율은 약 72% 수준이었다 (표 1). 이것은 이전의 논문 (Lee 등, J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004)에서 얻은 디아크릴레이티드 플루로닉 F127의 이중결합 도입율 약 72%와 유사한 수치였다. 【표 1】 The vapor pressure at 20 ° C. is 124 mmHg, which is relatively less volatile than diethyl ether. In addition, in the case of diethyl ether, it was better to use nucleic acid as a precipitation solution in terms of yield, such as rapid precipitation, in the case of nucleic acid, whereas the dispersion turned cloudy similarly to an emulsion upon excessive precipitation. That is, in the case of dietel ether, the yield of the finally obtained diacrylated pluronic polymer was about 60 to 70% by weight, whereas in the case of nucleic acid, the yield was about 80 to 90% or more. The polymer semi-aerated product (diacrylated pluronic) thus obtained was dried in a hood to the extent that the residual solvent was removed and then completely dried again in vacuo. The synthesized polymer was dissolved in CDC13 solvent and the 400MHZ 1H NMR spectrum was measured to calculate the double bond incorporation rate. The double bond incorporation rate of diacrylated pluronic F127 obtained by precipitation with nucleic acid after 3 hours reaction was about 74. It was about%. Also, as in the previous paper, the double bond introduction rate was about 72% when diethyl ether was used and the reaction time was increased to this level (Table 1). This was similar to about 72% of double bond incorporation of diacrylated Pluronic F127 obtained from a previous paper (Lee et al., J. Biomater. Sci. Polymer Edn, Vol. 15, 1571-1583, 2004). Table 1
Figure imgf000011_0001
비톡 표 1의 비교예 1에서의 반응시간이 48시간으로 실시예 1에 비해 길었지만, 이중결합 도입율은 오히려 실시예 1에서의 경우가 다소 컸다. 이것은 초기 플루로닉 고분자를 건조하는 환경에서 기인한 차이와 침전과정에서 사용된 용매의 차이에 기인한 것으로 판단된다. 실시예 2 : 광중합된 폴루로닉 하이드로겔의 제조
Figure imgf000011_0001
Although the reaction time in Comparative Example 1 of Beating Table 1 was longer than that of Example 1 at 48 hours, the rate of double bond introduction was rather large in Example 1. This may be due to the difference in the environment of drying the initial Pluronic polymer and the solvent used in the precipitation process. Example 2 Preparation of Photopolymerized Polyuronic Hydrogel
플루로닉 하이드로겔을 만들기 위하여 앞의 실시예 1 에서 얻어진 고분자를 물에 녹여 수용액으로 만든다. 구체적으로는 디아크릴레이티드 플루로닉 고분자는 물에 투입 후, 넁장고 또는 상온에서 하루 정도 방치하면 잘 용해된다. 이 때, 카라기난과 셀를로스, 한천, 갈락토만난, 글루코만난, 구아검, 로카스트 빈 검, 알긴산, 카라기난, 잔탄검 및 겔란으로 구성된 수용성 천연 고분자 중 최소 1종이상을 같이 녹여준다. 이것은 우수한 사용감의 하이드로겔을 만들기 위함이다. 또한 키토산, 키토산유도체, 엘라스틴, 콜라겐, 히알루로닉산등으로 구성된 피부친화성 증진제 중 최소 1종 이상, 알로에, 녹차, 감귤, 은행잎등으로부터 추출된 식물, 동물 또는 광물의 천연추출물등 천연 생체물질 중 최소 1종 이상, 부틸렌글리콜, 프로필렌글리콜, 글리세린등 다가 알코올 중 최소 1종 이상, 메틸파라벤, 에틸파라벤, 페녹시에탄을, 알콜, α-히드록시산, 클로페네신, 또는 코직산, 이산화티탄, 알루미늄 옥사이드등 기능첨가제 중 최소 1종 이상을 사용한다. 본 발명에서는 또한 광중합의 효율을 증진시키기 위해 광개시제를 필요에 따라 사용할 수 있다. 광개시제로는 (4-Benzoylbenzyl) trimethylammonium chloride 또는 Irgacure 1리즈의 제품을 人]"용하고, 중량대비 최대 0.5%(w/vv)를 사용한다.  In order to make a pluronic hydrogel, the polymer obtained in Example 1 was dissolved in water to make an aqueous solution. Specifically, the diacrylated pluronic polymer dissolves well after being put in water or left at room temperature for one day at room temperature. At this time, at least one of the water-soluble natural polymers composed of carrageenan and cellulose, agar, galactomannan, glucomannan, guar gum, locust bean gum, alginic acid, carrageenan, xanthan gum and gellan is dissolved together. This is to make the hydrogel with excellent usability. Also, among natural biological substances such as natural extracts of plants, animals or minerals extracted from at least one skin affinity enhancer composed of chitosan, chitosan derivatives, elastin, collagen, hyaluronic acid, aloe, green tea, citrus, ginkgo biloba, etc. At least one or more of polyhydric alcohols such as butylene glycol, propylene glycol, glycerin, methyl paraben, ethyl paraben, phenoxy ethane, alcohol, α-hydroxy acid, clophenesine, or kojic acid, titanium dioxide Use at least one of functional additives such as aluminum oxide. In the present invention, it is also possible to use a photoinitiator as needed to enhance the efficiency of photopolymerization. As a photoinitiator, a product of (4-Benzoylbenzyl) trimethylammonium chloride or Irgacure 1 Lease is used, and a maximum weight of 0.5% (w / vv) is used.
하이드로겔을 제조하기 위한 구체적인 성분표는 다음 표 2와 같다. 【표 2] Specific ingredient table for preparing a hydrogel is shown in Table 2 below. [Table 2]
Figure imgf000012_0001
상기 #1, #2 사이에 하이드로겔 제조능에 큰 차이가 없으므로 이하 실험결과에서 실시예 2는 광개시제가 없는 #2를 기준으로 설명한다. 냉장상태에서 용해된 고분자 수용액을 상온에 방치하면 수용액의 농도가 고농도일수특 먼저 물리적인 겔 상태로 변화된다. 물리적 겔은 플라스틱 용기를 뒤집어 겔 상태의 유지여부를 판단하여 확인하였다. 물리적 겔이 확인된 후, 자외선을 조사하여 화학적 겔을 제조한다. 이 때, 자외선은 5분, 10분, 20분 동안 조사하였다. 아크릴로일 클로라이드와 플루로닉의 반응으로 만들어진 di-acryloyl Pluronic F127은 고분자의 양 말단에 이중결합이 도입되어 자외선을 조사할 경우, 이중결합들이 서로 중합하게 된다. 자외선 조사 후, 하이드로겔 표면에 잔류할 수 있는 미반웅 고분자를 제거하기 위해 물로 층분히 세척한 후, 원하는 모양의 를을 사용하여 하이드로겔을 떼어낸다. 본 발명에서 제조된 하이드로겔은 디스크 모양으로 직경은 약 1.7 cm이고, 두께는 약 2.2 隱가 되도톡 설계하였다. 고분자의 농도와 자외선 조사 시간에 따라 화학적으로 가교결합된 하이드로겔의 제조여부는 다음의 표 3에서와 같다.
Figure imgf000012_0001
Since there is no significant difference in hydrogel manufacturing ability between the # 1 and # 2, Example 2 in the following experimental results will be described based on # 2 without the photoinitiator. When the polymer solution dissolved in the cold state is left at room temperature, the concentration of the aqueous solution may be changed to a physical gel state first. The physical gel was confirmed by inverting the plastic container and judging whether the gel was kept. After the physical gel is confirmed, ultraviolet rays are irradiated to prepare a chemical gel. At this time, ultraviolet rays were irradiated for 5 minutes, 10 minutes and 20 minutes. Di-acryloyl Pluronic F127, made by the reaction of acryloyl chloride and pluronic, introduces double bonds at both ends of the polymer, and the double bonds polymerize when irradiated with UV light. After UV irradiation, after washing with water in order to remove the unbanung polymer that may remain on the surface of the hydrogel, the hydrogel is removed using the desired shape. Hydrogel prepared in the present invention was designed to be a disk shape diameter of about 1.7 cm, the thickness is about 2.2 kPa. According to the concentration of the polymer and the preparation of the chemically cross-linked hydrogel according to the UV irradiation time is shown in Table 3 below.
【표 31 Table 31
Figure imgf000013_0001
Figure imgf000013_0001
0: 화학적으로 가교된 하이드로겔 형성  0: Form chemically crosslinked hydrogel
X: 화학적으로 가교된 하이드로겔 미형성 실시예 3 : 플루로닉 하이드로겔의 팽윤도 (Swelling ratio)  X: Chemically Crosslinked Hydrogel Not Forming Example 3 Swelling Ratio of Pluronic Hydrogel
상기 실시예 2 에서 얻어진 하이드로겔에 대한 팽윤성질을 측정하였다. 팽윤도는 초기 제조된 직후 얻어진 하이드로겔의 무게 (Wo)에 대하여 일정량의 물 (10 mL)을 투입하여 4° C, 상온 (23° C) 및 37° C에서 5분, 10분, 30분 및 1시간 경과 후 하이드로겔의 무게와 직경의 변화를 통해 상대적인 팽윤도를 확인하였다. 팽윤도는 물을 투입하기 전 하이드로겔 무게에 대하여 물 투입 후 하이드로겔의 무게가 일정 시간에 따라 얼마나 증가했는지에 대한 비율로 측정하씼다. 。 ^。八一 시간/에서의하이드로질무게 (g)-초기하이드로질무게 (g) Swelling properties of the hydrogel obtained in Example 2 were measured. The degree of swelling is 5 minutes, 10 minutes, 30 minutes at 4 ° C, room temperature (23 ° C) and 37 ° C by adding a certain amount of water (10 mL) to the weight (Wo) of the hydrogel obtained immediately after the initial preparation. After 1 hour, the relative swelling degree was confirmed by changing the weight and diameter of the hydrogel. The degree of swelling was measured as a ratio of how much the weight of the hydrogel increased after a certain amount of time with respect to the weight of the hydrogel before adding water. 。 ^ 。Essential weight of hydrogel (g) -initial hydro weight (g)
¾ ^ ( /0) 초기하이드로겔무게 (g) s ιυυ 팽윤도 실험에 사용된 샘플은 25 및 30 중량^ w/w)에서 20분간 자외선 조사에 의해 중합된 하이드로겔로 제조직후 초기직경은 약 1.7 cm 정도이었다. (도 1) ¾ ^ (/ 0) Initial Hydrogel Weight (g) s ιυυ The samples used in the swelling experiments were hydrogels polymerized by UV irradiation for 20 minutes at 25 and 30 weight ^ w / w). It was about cm. (Figure 1)
도 1에서 보이는 것처럼 고분자 함량이 적을수록 팽윤도가 증가하고, 또한 보관되는 온도가 낮을수록 팽윤도가 커짐을 알 수 있다. 실시예 4 : 플루로닉 하이드로겔의 수축도 (Contraction ratio) 상기 실시예 3 에서 하이드로겔의 팽윤도 측정을 위해 4° C 및 상온 As shown in FIG. 1, the swelling degree increases as the polymer content decreases, and the swelling degree increases as the storage temperature is lowered. Example 4 Contraction Ratio of Pluronic Hydrogel 4 ° C. and room temperature for measuring the swelling degree of the hydrogel in Example 3
(23° C)에서 보관중인 시료를 각각의 조건에서 하루동안 방치하여 하이드로겔이 물에 완전히 팽윤되었다고 가정한다. 그 후, 시료를 꺼내어 피부에 도포한 다음 일정 시간 간격 (5분, 10분 및 30분)마다 하이드로겔의 무게를 측정하여 하이드로겔의 수축도를 측정하였고, 이를 도 2에 나타내었다. Samples stored at (23 ° C.) are allowed to stand for one day at each condition and the hydrogel is fully swollen in water. Thereafter, the sample was taken out and applied to the skin, and then the hydrogel shrinkage was measured by measuring the weight of the hydrogel every predetermined time interval (5 minutes, 10 minutes and 30 minutes), which is shown in FIG. 2.
^츠 。八- 초기하이드로겔무게 (g)-시간/에서의하이드로겔무게 (g) , Ί Λ ᅮ^노( /0) 초기하이드로겔무게 (g) s ιυυ 하이드로겔 무게 측정시에는 표면에 물어있는 물방울에 의해 측정오차가 생길 수 있기 때문에 가능한 한 하이드로젤 표면에 있는 물기를 제거한 후 무게를 측정하였다. 도 2에서처럼 고분자 함량이 적을수록, 그리고 초기온도가 낮을수록 수축도가 더 커짐을 알 수 있다. 츠 八。- Initial hydrogel weight (g) -hour / hydrogel weight (g), Ί Λ TT ^ no ( / 0 ) Initial hydrogel weight (g) s ιυυ Ask the surface to measure the hydrogel weight Since the measurement error may occur due to the water droplets present, the weight was measured after removing water on the surface of the hydrogel as much as possible. As shown in FIG. 2, the smaller the polymer content and the lower the initial temperature, the greater the shrinkage.
하이드로겔의 수축정도는 도 2와 같이 무게 기준으로 측정할 수도 있지만, 소비자들로 하여금 즉각적이고 가시적인 효과를 알 수 있게 하려면 하이드로겔의 직경의 변화를 측정하는 것이 가장 효과적이다. 하지만, 도 1과 도 2에서 사용된 하이드로겔은 초기직경 자체가 약 1.7 cm로 작기 때문에 직경의 변화를 가시작으로 확인하기가 용이하지 않다. 그래서, 본 발명에서는 직경 5 cm의 비교적 큰 하이드로겔을 제조하여 수축도를 측정하였다. 이 때, 제조된 하이드로겔 조건은 고분자의 함량이 25중량 (\¥ )%로 UV를 20분간 조사한 샘플이었다. 또한, 초기두께가 각각 2 隱와 3 隱가 되도록 설계하였다. 하이드로겔은 제조 후 최대의 수축효과를 측정하기 위해 냉장조건 (4° C)에서 하루 동안 팽윤시킨 후, 37° C 조건에서 수축실험을 진행하였다. 초기직경 5 cm로 만들어진 하이드로겔은 하루 동안 냉장조건에서 팽윤된 후에 직경이 7.9 cm 정도로 증가하였다. 또한, 하이드로겔의 초기 두께에 따른 수축도를 고려하여 실험하였다. 실험결과, 표 4에서와 같이 하이드로겔의 초기 두께가 얇을수록 직경에 의한 수축효과가 크게 나타남을 알 수 있었다. 이것은 두께가 두꺼울수록 하이드로겔 내에 좀 더 많은 가교결합이 존재하기 때문에 수축과 팽윤이 상대적으로 용이하게 일어나지 않기 때문으로 생각된다. The shrinkage degree of the hydrogel may be measured by weight as shown in FIG. 2, but it is most effective to measure the change in the diameter of the hydrogel to enable consumers to know the immediate and visible effect. However, the hydrogel used in Figures 1 and 2 is not easy to check the change in diameter since the initial diameter itself is small as about 1.7 cm. Therefore, in the present invention, a relatively large hydrogel having a diameter of 5 cm was prepared and shrinkage was measured. At this time, the prepared hydrogel condition is that the content of the polymer The sample was irradiated with UV at 25 weight (\ ¥)% for 20 minutes. In addition, the initial thickness was designed to be 2 3 and 3 隱, respectively. Hydrogel swelled for one day in refrigerated conditions (4 ° C) in order to measure the maximum shrinkage effect after the manufacture, the shrinkage experiment was carried out at 37 ° C conditions. Hydrogels made up to an initial diameter of 5 cm increased in diameter to about 7.9 cm after swelling in refrigerated conditions for one day. In addition, the experiment was considered considering the shrinkage according to the initial thickness of the hydrogel. As a result, as shown in Table 4, the smaller the initial thickness of the hydrogel, the larger the shrinkage effect by the diameter. This is thought to be because shrinkage and swelling do not occur relatively easily because the thicker the thickness, the more crosslinks are present in the hydrogel.
【표 4】 Table 4
Figure imgf000015_0001
실시예 5 : 하이드로겔의 내부 구조 확인
Figure imgf000015_0001
Example 5 Confirmation of Internal Structure of Hydrogel
상기 실시예 2 의 15%(wAv) 고분자로만 만든 플루로닉 하이드로겔과 한천과 같은 수용성 고분자를 자외선 조사없이 가온 후 넁각하여 만들어진 하이드로겔을 대상으로 주사전자현미경 (SEM)을 관찰하였다. 관찰결과, 플루로닉 하이드로겔에서는 도 3과 같이 2으30 um 크기의 다공성 구조가 관찰된 반면, 수용성 고분자만으로 만들어진 하이드로겔에서는 다공성 구조가 관찰되지 않았다. 이러한 하이드로겔내의 다공성 구조는 하이드로겔의 가교 정도에 따라 영향을 받을 수 있다. 실시예 6 : 수용성 천연 고분자유무에 따른사용감 개선  Scanning electron microscopy (SEM) was observed for hydrogels prepared by heating water-soluble polymers such as Pluronic hydrogels made of only 15% (wAv) polymers of Example 2 and agar without UV irradiation. As a result, in the pluronic hydrogel, a porous structure having a size of 30 μm was observed as shown in FIG. 3, while the porous structure was not observed in a hydrogel made of only a water-soluble polymer. The porous structure in the hydrogel may be affected by the degree of crosslinking of the hydrogel. Example 6 improvement of feeling according to the presence or absence of water-soluble natural polymer
상기 표 2 의 조성 #3을 비교예 2로 하고, 표 2 의 조성 #2번 실시예 2로 하여 사용감상의 개선정도를 측정하기 위해 이를 품질 만족도의 기준인 5점 척도로 비교하기 위해 30대 내지 50대에 분포한 여성 소비자 10명을 대상으로 표 5에 소비자 품질평가로 나타내었다. 소비자 품질평가는 하이드로겔의 부착의 용이성, 밀착감 정도 및 사용 후 보습감에 대한 항목을 기준으로 수행하였다. 【표 5】 Composition # 3 of Table 2 was used as Comparative Example 2, and Composition # 2 of Example 2 of Table 2 was used in order to measure the degree of improvement in feeling of use. 10 female consumers in their 50s and 50s Table 5 shows the consumer quality evaluation. Consumer quality evaluation was performed based on the items on the ease of attachment of hydrogel, degree of adhesion and moisturizing after use. Table 5
Figure imgf000016_0001
Figure imgf000016_0001
- 품질만족도 평가기준 - -Quality Satisfaction Evaluation Criteria-
1점: 매우 나쁘다, 2점 : 나쁘다, 3점 : 보통 4점 : 좋다, 5점: 매우 좋다 상기 표 4에서 보인 바와 같이 실시예 2의 품질만족도는 비교예 2에 비하여 매우 우수한 것으로 나타났으며, 이것은 수용성 천연 고분자의 사용감과 디아크릴레이티드 플루로닉 고분자의 사용감이 시너지 효과를 보인 것으로 판단된다. 또한, 수용성 천연 고분자가 첨가된 실시예 2와 비교예 2 사이에는 팽윤도와 수축성 사이에 유의적인 차이가 발생하지 않았다. 이것은 하이드로겔의 온도감웅에 따른 팽윤도와 수축성에 주로 기여하는 것은 디아크릴레이티드 플루로닉 고분자 부분이지만, 수용성 천연 고분자를 추가사용시 좀 더 우수한사용감을 갖는 것으로 판단된다. 1 point: very bad, 2 points: bad, 3 points: normal 4 points: good, 5 points: very good As shown in Table 4, the quality satisfaction of Example 2 was found to be superior to Comparative Example 2. This suggests that the feeling of use of water-soluble natural polymer and that of diacrylated pluronic polymer showed synergistic effect. In addition, there was no significant difference between swelling and shrinkage between Example 2 and Comparative Example 2 to which the water-soluble natural polymer was added. This is a part of the diacrylated pluronic polymer, which mainly contributes to the swelling and shrinkage according to the temperature sensitization of the hydrogel, but it is judged to have a better feeling when additionally using a water-soluble natural polymer.
【산업상 이용가능성】 Industrial Applicability
이상 설명한 바와 같이, 본 발명에 따르면 하이드로겔의 온도에 따른 수축성을 통해 하이드로겔에 함유된 수용성 미용제를 피부속으로 보다 신속하고 균일하게 전달하도록 하였으며, 또한 이러한 수축성으로 인해 피부에 하이드로겔이 좀 더 밀착감있게 붙을 수 있도록 하므로 피부온도감응성 하이드로겔 화장료 조성물로 이용할 수 있다.  As described above, according to the present invention, the water-soluble cosmetics contained in the hydrogel are more quickly and uniformly delivered into the skin through shrinkage according to the temperature of the hydrogel. It can be used as a skin temperature sensitive hydrogel cosmetic composition because it can be attached more tightly.

Claims

【청구의 범위】 [Range of request]
【청구항 1】 [Claim 1]
디아크릴레이티드 플루로닉 고분자 및 수용성 천연 고분자가 광개시제 존재 또는 미존재하에서 자외선 (UV)에 의해 화학적으로 가교결합하여 얻어진, 피부 온도범위에서 가역적인 팽윤성 및 수축성 성질을 갖고, 그 내부 구조에 다공성 구조를 갖는 것을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물.  Diacrylated pluronic polymers and water-soluble natural polymers have reversible swelling and shrinking properties over the skin temperature range, obtained by chemical crosslinking by ultraviolet (UV) with or without a photoinitiator and porous to its internal structure. Skin temperature sensitive hydrogel cosmetic composition characterized in that it has a structure.
【청구항 2】 [Claim 2]
제 1항에 있어서, 상기 플루로닉 고분자는 분자량 약 8,700 Da의 플루로닉 F68 ((PEO)75(PPO)30(PEO)75) 또는 분자량 약 12,600 Da의 플로로닉 F127((PE0)99(PP0)69(PE0)99) 인 것을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물.  The method of claim 1, wherein the pluronic polymer is Pluronic F68 ((PEO) 75 (PPO) 30 (PEO) 75) having a molecular weight of about 8,700 Da or Floronic F127 ((PE0) having a molecular weight of about 12,600 Da. ) 99 (PP0) 69 (PE0) 99) skin temperature sensitive hydrogel cosmetic composition, characterized in that.
【청구항 3】 [Claim 3]
제 1항에 있어서, 상기 디아크릴레이티드 플루로닉 고분자는 플루로닉 고분자의 양 말단에 이중결합이 있는 아크릴레이트를 부가하여 합성되는 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물.  The skin temperature sensitive hydrogel cosmetic composition according to claim 1, wherein the diacrylated pluronic polymer is synthesized by adding acrylates having double bonds to both ends of the pluronic polymer.
【청구항 4】 [Claim 4]
제 3항에 있어서, 상기 합성공정시 침전용매로서 핵산을 사용하는 것올 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물.  The skin temperature sensitive hydrogel cosmetic composition according to claim 3, wherein a nucleic acid is used as a precipitation solvent in the synthesis process.
【청구항 5】 [Claim 5]
제 1항에 있어서, 상기 수용성 천연 고분자는 카라기난, 샐를로스, 한천, 갈락토만난, 글루코만난, 구아검, 로카스트 빈 검, 알긴산, 카라기난, 잔탄검 및 겔란 으로 구성된 그룹으로부터 선택된 최소 1종의 수용성 천연 고분자인 것을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물. The method of claim 1, wherein the water-soluble natural polymer is at least one water-soluble selected from the group consisting of carrageenan, salulose, agar, galactomannan, glucomannan, guar gum, locust bean gum, alginic acid, carrageenan, xanthan gum and gellan Skin temperature-sensitive hydrogel cosmetic composition, characterized in that the natural polymer.
【청구항 6】 [Claim 6]
제 1항에 있어서, 상기 피부온도 범위는 0° C-50° C 온도범위인 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물. According to claim 1, wherein the skin temperature range is a skin temperature sensitivity hydrogel cosmetic composition, characterized in that 0 ° C-50 ° C temperature range.
【청구항 7】 [Claim 7]
제 1항에 있어서, 상기 피부온도 범위에서 가역적인 팽윤성 및 수축성 성질은 피부온도에 반웅하여 팽윤된 겔 상태에서 수축된 겔 상태로 변화하는 것을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물.  The skin temperature sensitive hydrogel cosmetic composition according to claim 1, wherein the reversible swelling and shrinking properties in the skin temperature range change from the swollen gel state to the shrunken gel state in response to the skin temperature.
【청구항 8】 [Claim 8]
제 1항에 있어서, 피부에 청량감과 보습감을 부여할뿐만 아니라 피부에 탄력감과 밀착감을 부여하는 것을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물.  The skin temperature-sensitive hydrogel cosmetic composition according to claim 1, which not only imparts a refreshing and moisturizing feeling to the skin but also imparts elasticity and adhesion to the skin.
【청구항 9】 [Claim 9]
제 1항에 있어서, 조성물의 총 중량을 기준으로 디아크릴레이티드 폴루로닉 고분자 1-60%, 수용성 천연 고분자 0.1-30 중량 %, 피부친화성 증진제 1-20 중량 %, 천연생체물질 1-20 중량 ¾>, 다가알코올 1-30 증량 %, 기능첨가제 0.01-10 중량 ¾ 및 물 20—90 중량 %를 포함하여 구성되고, 여기에 광개시제를 첨가하지 않거나 또는 소량 첨가하여 자외선 (UV)에 의해 화학적으로 가교결합하여 얻어지는 것을 특징으로 하는 피부온도감웅성 하아드로겔 화장료 조성물.  The method of claim 1, based on the total weight of the composition 1-60% diacrylated polyuronic polymer, 0.1-30% by weight of water-soluble natural polymer, 1-20% by weight of skin affinity enhancer, natural biomaterial 1- 20 weight ¾>, 1-30 weight percent polyhydric alcohol, 0.01-10 weight ¾ weight functional additive, and 20-90 weight% water, which is added by ultraviolet (UV) with or without a small amount of photoinitiator. Skin temperature sensitive hadrogel cosmetic composition, characterized in that obtained by chemically crosslinking.
【청구항 10】 [Claim 10]
제 9항에 있어서, 상기 피부친화성 증진제는 키토산, 키토산유도처 1, 엘라스틴, 콜라겐, 히알루로닉산으로 구성된 그룹으로부터 선택된 최소 1종의 다당류 또는 단백질임을 특징으로 하는 피부온도감응성 하이드로겔 화장료 조성물.  The skin temperature sensitive hydrogel cosmetic composition according to claim 9, wherein the skin affinity enhancer is at least one polysaccharide or protein selected from the group consisting of chitosan, chitosan derivative 1, elastin, collagen, hyaluronic acid.
【청구항 11】 [Claim 11]
제 9항에 있어서, 상기 천연생체물잘은 알로에, 녹차, 감귤, 은행잎등으로부터 추출된 식물, 동물 또는 광물의 천연추출물임을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물. 10. The method of claim 9, wherein the natural biomass is aloe, green tea, citrus, Skin thermosensitizing hydrogel cosmetic composition, characterized in that the natural extract of plants, animals or minerals extracted from ginkgo leaves and the like.
【청구항 12】 [Claim 12]
제 9항에 있어서, 상기 다가알코을은 수용성 액상의 부틸렌글리콜, 프로필렌글리콜 또는 글리세린임을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물.  The skin temperature-sensitive hydrogel cosmetic composition according to claim 9, wherein the polyhydric alcohol is a water-soluble liquid butylene glycol, propylene glycol or glycerin.
【청구항 13] [Claim 13]
제 9항에 있어서, 상기 기능첨가제는 하이드로겔의 안정성 및 방부성, 유효성분의 첨가를 통해 미용기능성올 부여할 수 있는 첨가제로서 메틸파라벤, 에틸파라벤, 페녹시에탄올, 알콜, α-히드록시산, 클로페네신, 또는 코직산, 이산화티탄, 알루미늄 옥사이드등을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물.  10. The method of claim 9, wherein the functional additive is a hydrogel stability and preservatives, through the addition of an active ingredient as a cosmetic functional additives that can be given to methyl parabens, ethyl parabens, phenoxyethanol, alcohols, α-hydroxy acids, A skin temperature sensitive hydrogel cosmetic composition characterized by clofenesin, kojic acid, titanium dioxide, aluminum oxide and the like.
【청구항 14】 [Claim 14]
제 9항에 있어서, 상기 광개시제는 trimethylamonium chloride (4- benzoyl benzyl) 또는 Irgacure 시리즈인 것을 특징으로 하는 피부온도감웅성 하이드로겔 화장료 조성물.  The skin temperature-sensitive hydrogel cosmetic composition according to claim 9, wherein the photoinitiator is trimethylamonium chloride (4-benzoyl benzyl) or Irgacure series.
【청구항 15] [Claim 15]
제 1항 내지 제 14항 중 어느 한 항에 기재된 피부온도감웅성 하이드로겔 조성물을 포함하는 피부외용 화장품 또는 의약품.  An external skin cosmetic or pharmaceutical product comprising the skin thermosensitizing hydrogel composition according to any one of claims 1 to 14.
PCT/KR2012/007657 2012-06-27 2012-09-24 Skin temperature sensitive hydrogel composition and preparation method thereof WO2014003241A1 (en)

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