TWI759283B - Composition containing biocellulose microfibril network water dispersions, compositions, and uses thereof - Google Patents
Composition containing biocellulose microfibril network water dispersions, compositions, and uses thereof Download PDFInfo
- Publication number
- TWI759283B TWI759283B TW106107124A TW106107124A TWI759283B TW I759283 B TWI759283 B TW I759283B TW 106107124 A TW106107124 A TW 106107124A TW 106107124 A TW106107124 A TW 106107124A TW I759283 B TWI759283 B TW I759283B
- Authority
- TW
- Taiwan
- Prior art keywords
- water
- biocellulose
- composition
- dispersed
- dispersion
- Prior art date
Links
Images
Landscapes
- Cosmetics (AREA)
Abstract
一種水分散生物纖維素微纖維網路分散體，生物纖維素的醇基被羧基取代，數均直徑為30~60nm、最大直徑為60~100nm，在水相中形成網路並分散到水相中。水分散生物纖維素微纖維網路分散體具有優異的皮膚安放性、增強水分吸收和彈性的效果，能夠廣泛用作化妝材料和類藥品。生物纖維素微纖維水分散體網路組合物具有的負電荷排斥微塵的負電荷來減少微塵附著，能夠廣泛應用於具有微塵隔絕效率的多種組合物的開發。含有生物纖維素微纖維網路水分散體的保護角蛋白結構體用組合物在毛髮或手腳趾甲等角蛋白結構體的表面牢固地形成網路，具有保護角蛋白結構的效果。 A water-dispersed bio-cellulose microfiber network dispersion, the alcohol group of bio-cellulose is substituted by carboxyl groups, the number-average diameter is 30-60 nm, the maximum diameter is 60-100 nm, and a network is formed in the water phase and dispersed in the water phase middle. The water-dispersed bio-cellulose microfiber network dispersion has excellent skin placement, enhanced moisture absorption and elasticity, and can be widely used as cosmetic materials and quasi-drugs. The negative charge of the biocellulose microfiber aqueous dispersion network composition repels the negative charge of the fine dust to reduce the attachment of the fine dust, and can be widely used in the development of various compositions with dust isolation efficiency. The composition for protecting a keratin structure containing a biocellulose microfiber network aqueous dispersion strongly forms a network on the surface of a keratin structure such as hair and fingernails, and has an effect of protecting the keratin structure.
Description
本發明涉及纖維素水分散體及其製備方法以及包含其的組合物。 The present invention relates to aqueous cellulose dispersions and methods for their preparation and compositions comprising the same.
皮膚起到隔絕來自外部環境的有害物質並防止水分損失的作用。施用於皮膚的包括天然高分子、合成高分子及有機高分子等的高分子起到從外部保護皮膚、將有效成分傳遞到皮膚並用於防止水分損失的屏障作用。這些高分子中的纖維素、酮酸及多糖類等天然高分子的生物相容性、生物降解性優異，對皮膚起到保濕、賦予彈性、保護皮膚等作用。 The skin functions to insulate harmful substances from the external environment and prevent moisture loss. Polymers including natural polymers, synthetic polymers, and organic polymers, etc., applied to the skin function as a barrier to protect the skin from the outside, deliver active ingredients to the skin, and prevent moisture loss. Among these polymers, natural polymers such as cellulose, ketoacids, and polysaccharides are excellent in biocompatibility and biodegradability, and have the functions of moisturizing, imparting elasticity, and protecting the skin.
目前用於人體的纖維素有自然纖維素、纖維素衍生物、生物纖維素等。其中，自然(天然)纖維素為幾十微米大小的粉末形態，其不溶於水，主要用於磨砂劑、去角質凝膠等中。纖維素衍生物可通過將纖維素的醇羥基取代而得到，由於纖維素自身不溶於水，因此包括進行取代以使該纖維素能夠溶解於水的羥乙基纖維素、羧甲基纖維素等。這種水溶性纖維素為高分子形態，主要用作增稠劑。生物纖維素作為由細菌纖維素合成的纖維素微纖維，與來自植物的纖維素相比，雖然纖維的厚度薄且具有高結晶度、高物理強度，但由於被合成為凝膠或片材的形態，因此主要用於面膜片材，存在難以適用於化妝品劑型的缺點。 The cellulose currently used in the human body includes natural cellulose, cellulose derivatives, biological cellulose, etc. Among them, natural (natural) cellulose is in the form of a powder with a size of several tens of microns, which is insoluble in water, and is mainly used in scrubs, exfoliating gels, and the like. Cellulose derivatives can be obtained by substituting alcoholic hydroxyl groups of cellulose. Since cellulose itself is insoluble in water, it includes hydroxyethyl cellulose, carboxymethyl cellulose, etc., which are substituted so that the cellulose can be dissolved in water. . This water-soluble cellulose is in the form of a polymer and is mainly used as a thickener. Biocellulose is a cellulose microfiber synthesized from bacterial cellulose. Compared with plant-derived cellulose, although the thickness of the fiber is thinner, the fiber has high crystallinity, and high physical strength, it is synthesized into a gel or sheet. Therefore, it is mainly used for mask sheets, and it has the disadvantage that it is difficult to apply to cosmetic formulations.
為了將纖維素系原料施用於人體進行了多種嘗試，作為其中的一個環節，韓國特許申請公開10-2012-0123371號(專利文獻1)和日本特許申請公開2010-037199號(專利文獻2)中記載了一種纖維素，其是最大纖維直徑為1000nm以下且數均纖維直徑為2~150nm的纖維素纖維，該纖維素具有纖維素I型晶體結構，而且纖維素分子中的葡萄糖單位(Glucose Unit)的C6位的羥基選擇性地被氧化而改性為醛基和羧基，並記載了該纖維素能夠用作化妝材料用、增稠劑/膠凝劑用、噴霧劑用組合物。但是，專利文獻1和專利文獻2中記載的纖維素雖然用作增稠劑/膠凝劑的用途而能夠在組合物中提高保型性、分散穩定性、耐鹽性，但不適合在皮膚上體現基於纖維素的優點。專利文獻1([0082])中記載了：優選使用針葉樹系紙漿、闊葉樹系紙漿、棉短絨、皮棉等棉系紙漿、麥秸紙漿、蔗渣紙漿等非木材系纖維素，且在實施例中使用了紙漿。另外，專利文獻2的實施例中使用了針葉樹紙漿。為了使纖維素能夠用作化妝材料組合物，需要使長度維持為微米以上且在被分散在水中之後也需要纖維間維持網路，但是為了這種非木材系纖維素或木材系纖維素的細化，自頂向下(top-own)方式的預處理過程是必不可少的，在此過程中，纖維素長度被任意地切斷，因此在纖維素纖維最終進入化妝品時，存在滲透皮膚的風險。另外，由於難以形成網路，因此雖然能夠用作增稠劑或劑型穩定劑，但作為化妝材料組合物使用是受限的。 Various attempts have been made to administer cellulose-based raw materials to the human body, and as one of the links, Korean Patent Application Laid-Open No. 10-2012-0123371 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2010-037199 (Patent Document 2) A cellulose is described, which is a cellulose fiber with a maximum fiber diameter of 1000 nm or less and a number-average fiber diameter of 2 to 150 nm, the cellulose having a cellulose I-type crystal structure, and the glucose unit (Glucose Unit) in the cellulose molecule. The hydroxyl group at the C6 position of ) is selectively oxidized to be modified into an aldehyde group and a carboxyl group, and it is described that the cellulose can be used as a composition for cosmetic materials, thickeners/gelling agents, and sprays. However, although the cellulose described in Patent Document 1 and Patent Document 2 is used as a thickener/gelling agent to improve shape retention, dispersion stability, and salt resistance in the composition, it is not suitable for use on the skin Embody the advantages of cellulose-based. Patent Document 1 ([0082]) describes that non-wood celluloses such as conifer-based pulp, broad-leaved tree pulp, cotton-based pulp such as cotton linters, and lint, wheat straw pulp, bagasse pulp, and the like are preferably used, and are used in Examples pulp. Moreover, in the Example of patent document 2, conifer pulp was used. In order for cellulose to be used as a cosmetic composition, it is necessary to maintain a length of micrometers or more and to maintain a network between fibers even after being dispersed in water. A pretreatment process in a top-down fashion is essential, in which the cellulose lengths are arbitrarily cut, so that when the cellulose fibers finally enter the cosmetic, there is a risk of penetrating the skin. risk. In addition, since it is difficult to form a network, it can be used as a thickener or a dosage form stabilizer, but its use as a cosmetic composition is limited.
另外，微塵根據顆粒的大小分為直徑10μm以下的微塵(PM10)、直徑2.5μm以下的超微塵(PM2.5)。微塵由通過燃燒作用而產生的硝酸鹽、銨、硫酸鹽等離子成分以及碳化合物、金屬化合物等構成。若反復長期地暴露於空氣中的微塵中，則會引發心力衰竭、哮喘、支氣管炎、肺炎、 肺癌等嚴重疾病。另外，皮膚暴露於微塵導致皮膚乾燥症、特異反應性、皮膚炎等嚴重問題。尤其已查明，微塵不僅損傷表皮屏障功能並惡化特異反應性皮膚炎，而且與皺紋和色斑增加的皮膚老化直接有關。 In addition, fine dust is classified into fine dust (PM10) with a diameter of 10 μm or less and ultrafine dust (PM2.5) with a diameter of 2.5 μm or less according to the size of the particles. The fine dust is composed of ionic components such as nitrates, ammonium, and sulfates, carbon compounds, metal compounds, and the like, which are generated by combustion. Repeated long-term exposure to fine dust in the air can cause serious diseases such as heart failure, asthma, bronchitis, pneumonia, and lung cancer. In addition, exposure of the skin to fine dust leads to serious problems such as dry skin, atopic reactions, and dermatitis. In particular, it has been found that fine dust not only damages the epidermal barrier function and worsens atopic dermatitis, but is also directly related to skin aging with increased wrinkles and pigmentation.
因此，為保護皮膚免受微塵的影響，進行了多種嘗試。為去除微塵而最常使用的方法為通過清潔霜而進行的去除，微塵通過清潔霜在一定程度上能夠被去除，但由於越微細，吸附力越強，因此事實上通常用清潔霜難以完全去除深入毛孔的微塵。 Therefore, various attempts have been made to protect the skin from fine dust. The most commonly used method for removing fine dust is the removal by cleansing cream. The fine dust can be removed to a certain extent by cleansing cream. However, since the finer particles are, the stronger the adsorption force is, so in fact, it is usually difficult to completely remove them with cleansing cream. Motes that penetrate deep into pores.
因此，需要在微塵直接吸附到皮膚之前隔絕微塵，使之不附著於皮膚的化妝材料組合物。 Therefore, there is a need for cosmetic compositions that block the fine dust and prevent it from adhering to the skin before the fine dust is directly adsorbed to the skin.
另外，體毛、手腳趾甲、皮膚等是由被稱為角蛋白(keratin)的結構蛋白構成的，將這些組織也稱為角蛋白結構體。以往，為保護這些組織的角蛋白，一直以來多數使用如下的方法：利用有機矽等原料覆蓋表面或者利用如指甲油等揮發性有機溶劑等塗抹表面。但是，這種方法作為不考慮如鱗片般形成於角蛋白結構體的最外側表面的角質層的特性的措施，由於角質層非常柔軟，因此用於保護角蛋白而使用的原料在從角蛋白表面分離時，反而多數情況下損傷角質層。因此，需要在角蛋白結構的表面保護角蛋白且不損傷角質層的角蛋白結構體護理組合物。 In addition, body hair, hand toenails, skin, etc. are composed of a structural protein called keratin, and these tissues are also called keratin structures. In the past, in order to protect the keratin of these tissues, the following methods have been used: covering the surface with a raw material such as silicone or coating the surface with a volatile organic solvent such as nail polish. However, this method is a measure that does not take into account the characteristics of the stratum corneum formed on the outermost surface of the keratin structure like scales. Since the stratum corneum is very soft, the raw material used for protecting the keratin is from the surface of the keratin. During separation, the stratum corneum is damaged in most cases. Therefore, there is a need for a keratin structure care composition that protects keratin on the surface of the keratin structure without damaging the stratum corneum.
鑒於上述情形，本發明要解決的課題在於，提供一種纖維素微纖維分散體，其具有無滲透皮膚風險的纖維素微纖維的長度和直徑，即使被劑型 化為水分散型組合物也能夠維持網路結構，且吸收水分的能力和增強彈性的能力優異。 In view of the above-mentioned circumstances, the problem to be solved by the present invention is to provide a cellulose microfiber dispersion having a length and diameter of cellulose microfibrils without risk of penetrating the skin, even if the dosage form is Even in the form of a water-dispersible composition, the network structure can be maintained, and the ability to absorb moisture and enhance elasticity is excellent.
另外，本發明要解決的課題在於，提供一種纖維素微纖維分散體，其具有無滲透皮膚風險的纖維素微纖維的長度和直徑，即使被劑型化為水分散型組合物也能夠維持網路結構，不僅能夠隔絕微塵還能夠隔絕超微塵的效果優異。 In addition, the problem to be solved by the present invention is to provide a cellulose microfiber dispersion having a length and diameter of cellulose microfibrils without risk of skin penetration, and which can maintain a network even when formulated into a water-dispersible composition. The structure is excellent in being able to isolate not only fine dust but also ultra-fine dust.
另外，本發明要解決的課題在於，提供一種保護角蛋白結構體用生物纖維素微纖維水分散體網路組合物及其製備方法，其施用於角蛋白結構體而保護它們的角蛋白又不損傷角質層。 In addition, the subject to be solved by the present invention is to provide a biocellulose microfiber aqueous dispersion network composition for protecting keratin structures, and a method for producing the same, which are applied to keratin structures without protecting their keratin. damage the stratum corneum.
另外，本發明要解決的課題在於，提供上述纖維素微纖維分散體的增強水分吸收和彈性的用途、隔絕微塵的用途或保護角蛋白結構體的用途。 Another object to be solved by the present invention is to provide the above-mentioned cellulose microfiber dispersion for enhancing water absorption and elasticity, for blocking fine dust, or for protecting keratin structures.
另外，本發明要解決的課題在於，提供將上述纖維素微纖維分散體施用於人體來增強水分吸收和彈性的方法、隔絕微塵的方法或保護角蛋白結構體的方法。 Another object to be solved by the present invention is to provide a method for enhancing moisture absorption and elasticity by applying the above-mentioned cellulose microfibril dispersion to a human body, a method for blocking fine dust, or a method for protecting a keratin structure.
為解決上述課題，本發明提供一種水分散生物纖維素微纖維網路分散體、其製備方法、其組合物、分散體和組合物的用途以及將分散體和組合物施用於人體的方法，所述水分散生物纖維素微纖維網路分散體的特徵在於，生物纖維素的醇基被羧基取代，優選地，上述分散體中的個別微纖維的最大直徑為60~100nm且數均直徑為30~60nm，能夠維持用作原料的生物纖維素的長度，在水相中形成網路並分散到水相中。 In order to solve the above-mentioned problems, the present invention provides a water-dispersed biocellulose microfiber network dispersion, its preparation method, its composition, the use of the dispersion and the composition, and the method of applying the dispersion and the composition to the human body. The water-dispersed biocellulose microfiber network dispersion is characterized in that the alcohol group of the biocellulose is substituted by a carboxyl group, preferably, the maximum diameter of the individual microfibers in the above-mentioned dispersion is 60-100 nm and the number average diameter is 30 nm. ~60nm, able to maintain the length of the biocellulose used as a raw material, form a network in the aqueous phase and disperse into the aqueous phase.
本發明人等選擇生物纖維素作為纖維素原料，氧化上述生物纖維素而將生物纖維素的醇基取代為羧基，並限制生物纖維素的直徑和長度來獲得生物纖維素微纖維網路分散體。發現，獲得的生物纖維素微纖維網路分散體在 氧化前維持與生物纖維素相似的長度和網路結構，分散到水相中，具有對人體有利的特徵例如皮膚安放性、高水分保持能力、彈性增加、皮膚摩擦力減少及增稠力。接著，根據生物纖維素微纖維網路分散體對人體的施用用途、例如根據作為化妝材料或類藥品(quasi drugs)的有用性而完成了本發明。 The inventors selected biocellulose as a cellulose raw material, oxidized the above-mentioned biocellulose to replace the alcohol group of the biocellulose with a carboxyl group, and limited the diameter and length of the biocellulose to obtain a biocellulose microfiber network dispersion . It was found that the obtained biocellulose microfibril network dispersion was in It maintains a similar length and network structure as biocellulose before oxidation, disperses in the aqueous phase, and possesses beneficial characteristics for the human body such as skin placement, high water retention capacity, increased elasticity, reduced skin friction and thickening power. Next, the present invention was completed according to the application of the biocellulose microfibril network dispersion to the human body, for example, according to the usefulness as a cosmetic material or quasi drugs.
另外，本發明人等通過選擇生物纖維素作為纖維素原料，將上述生物纖維素氧化而將生物纖維素的醇基取代為羧基，並限制生物纖維素的直徑和長度，從而獲得了生物纖維素微纖維網路分散體。確認所獲得的生物纖維素微纖維網路分散體保持與氧化前生物纖維素相似的長度和細密的網狀結構並分散到水相中，具有不滲透到皮膚的同時能夠防止微塵和超微塵滲透的效果，且分散到水相中而能夠被劑型化為多種劑型的組合物，從而完成了本發明。 In addition, the present inventors obtained biocellulose by selecting biocellulose as a cellulose raw material, oxidizing the above-mentioned biocellulose to replace the alcohol group of the biocellulose with a carboxyl group, and limiting the diameter and length of the biocellulose. Microfiber network dispersion. It was confirmed that the obtained biocellulose microfibril network dispersion maintained a similar length and fine network structure as the pre-oxidized biocellulose and dispersed into the aqueous phase, with impermeability to the skin while being able to prevent the penetration of fine dust and ultrafine dust The present invention is completed by dispersing in the water phase and being able to be formulated into a composition of various dosage forms.
本發明人等確認到：當選擇生物纖維素作為纖維素原料，使上述生物纖維素氧化而將生物纖維素的醇基取代為羧基並限制生物纖維素的直徑和長度時，在水相中保持與氧化前生物纖維素相似的長度和細密的網路結構、具有不滲透到皮膚的同時保護角蛋白結構的效果以及具有在被去除的過程中不損傷角質層的效果，且分散到水相中而能夠被劑型化為多種劑型的組合物，從而完成了本發明。 The present inventors have confirmed that when biocellulose is selected as a cellulose raw material, the biocellulose is oxidized to replace the alcohol group of the biocellulose with a carboxyl group, and the diameter and length of the biocellulose are restricted, the biocellulose is retained in the aqueous phase. Similar in length and fine network structure as pre-oxidized biocellulose, has the effect of not penetrating into the skin while protecting the keratin structure, and has the effect of not damaging the stratum corneum in the process of being removed, and is dispersed in the aqueous phase The present invention has been completed as a composition that can be formulated into a plurality of dosage forms.
本申請發明的水分散生物纖維素微纖維網路分散體以及包含上述水分散纖維素微纖維網路分散體的組合物具有如下的特徵：在水相中形成網路。上述“網路”是指，纖維素微纖維間的三維網狀結構。上述“水相”是指，溶劑中包含水的相(phase)，只要溶劑中包含水，就不限制除水以外還包含其它溶劑。例如還包括水溶液。 The water-dispersed biocellulose microfibril network dispersion of the present invention and the composition comprising the above-mentioned water-dispersed cellulose microfiber network dispersion are characterized in that a network is formed in an aqueous phase. The above-mentioned "network" refers to a three-dimensional network structure between cellulose microfibrils. The above-mentioned "aqueous phase" refers to a phase (phase) containing water in a solvent, and as long as water is contained in the solvent, it is not limited to contain other solvents other than water. For example, aqueous solutions are also included.
顯示出優異的皮膚安放性。上述“皮膚安放性”是指，水分散生物纖維素微纖維網路分散體在維持微纖維的結構性、物理化學特徵和/或水分散性的同時施用於皮膚表面。 Shows excellent skin placement. The above-mentioned "skin placement" means that the water-dispersible biocellulose microfibril network dispersion is applied to the skin surface while maintaining the structural, physicochemical characteristics and/or water dispersibility of the microfibers.
顯示出高水分保持能力。上述“水分保持能力”表示，吸引水分散生物纖維素微纖維網路分散體周圍水分的力或能力和/或保持周圍水分的力或能力。水分保持能力與吸收水分的能力或保濕能力相互成比例。由此，顯示出高吸收水分的能力或保濕能力。 Shows high moisture retention capacity. The above-mentioned "moisture retention capability" means the force or capability of attracting and/or the force or capability of retaining the surrounding moisture of the water-dispersed biocellulose microfiber network dispersion. The moisture retention capacity and the moisture absorption capacity or the moisturizing capacity are proportional to each other. Thereby, high water absorption ability or moisturizing ability is exhibited.
顯示出彈性增強效果。上述“彈性”表示對所施加的外力的阻力，與“恢復力”為相同的含義，反應出表面結構的緻密性。表示水分散生物纖維素微纖維網路分散體的成膜能力以及水分散生物纖維素微纖維網路分散體所施用的物件對外力的阻力增加、提高或改善。 Shows elasticity enhancement effect. The above-mentioned "elasticity" means resistance to an applied external force, has the same meaning as "restoring force", and reflects the compactness of the surface structure. Indicates that the film-forming ability of the water-dispersed bio-cellulose microfiber network dispersion and the resistance to external forces of the object to which the water-dispersed bio-cellulose microfiber network dispersion is applied are increased, improved or improved.
顯示出增稠力。上述“增稠力”表示粘度提高能力。表示水分散生物纖維素微纖維網路分散體在維持微纖維的結構性、物理化學特徵的同時具有提高粘度的能力。 Shows thickening power. The above-mentioned "thickening power" means viscosity increasing ability. It indicates that the water-dispersed biocellulose microfiber network dispersion has the ability to increase the viscosity while maintaining the structural and physicochemical characteristics of the microfibers.
顯示出摩擦力減少。上述“摩擦力”作為阻礙與接觸面接觸的物件的運動的力，皮膚摩擦力反映為皮膚粗糙度。是指阻礙與水分散生物纖維素微纖維網路分散體所施用的接觸面接觸的物件的運動程度減少，表示柔軟性增加、改善或提高，或者表示粗糙度減少。 Shows a reduction in friction. The above-mentioned "frictional force" is a force that hinders the movement of the object in contact with the contact surface, and the skin frictional force is reflected as skin roughness. Refers to a decrease in the degree of motion of objects that impede contact with the contact surface to which the water-dispersed biocellulose microfibrous network dispersion is applied, indicating an increase, improvement, or increase in softness, or a decrease in roughness.
具有隔絕微塵效果。上述“微塵”表示直徑為10μm以下的顆粒狀物質，包括直徑為2.5μm以下的超微塵。上述“隔絕微塵”表示，防止或抑制微塵直接附著或吸附於皮膚，或者防止微塵滲透到皮膚內，由此能夠容易地去除微塵。 It has the effect of isolating fine dust. The above-mentioned "fine dust" refers to particulate matter with a diameter of 10 μm or less, including ultrafine dust with a diameter of 2.5 μm or less. The above-mentioned "isolation of fine dust" means that the fine dust can be easily removed by preventing or suppressing the direct attachment or adsorption of fine dust to the skin, or preventing the fine dust from penetrating into the skin.
具有保護角蛋白結構體的效果。上述“角蛋白結構體”作為由被稱為角蛋白(keratin)的結構蛋白構成的人體器官或組織，例如包括手指甲、腳趾甲、體毛等。上述“保護角蛋白結構體”表示：使角蛋白結構體免受因角蛋白結構體外部的任意的原因導致的物理、化學性損傷或脫落；在受損的角蛋白結構體再生、恢復、被治療期間免受外部的物理、化學的不利影響；在從角蛋 白結構體去除本申請發明的分散體或包含其的組合物的過程中，不使包含角蛋白結構體的人體組織、尤其角質層受損而被保護等。水分散生物纖維素微纖維尤其起到在角蛋白結構體表面形成網路來阻擋表面角蛋白層脫落的作用，穩定地結合在角蛋白表面，在被去除時也不損傷角蛋白表面而脫落。 Has the effect of protecting the keratin structure. The above-mentioned "keratin structure" includes, for example, fingernails, toenails, body hair, and the like as human organs or tissues composed of a structural protein called keratin. The above-mentioned "protection of the keratin structure" means: to protect the keratin structure from physical and chemical damage or fall off due to any external cause of the keratin structure; Protection from external physical and chemical adverse effects during treatment; In the process of removing the white structure from the dispersion of the present invention or the composition containing the same, the human tissue containing the keratin structure, especially the stratum corneum, is protected from damage and the like. The water-dispersed biocellulose microfibrils especially play the role of forming a network on the surface of the keratin structure to prevent the surface keratin layer from falling off, and are stably bound to the keratin surface, and will not damage the keratin surface and fall off when removed.
上述水分散生物纖維素微纖維網路分散體的特徵，在包含水分散生物纖維素微纖維網路分散體的組合物中能夠得到保持或提高。 The characteristics of the water-dispersible biocellulose microfibrous network dispersion described above can be maintained or enhanced in compositions comprising the water-dispersible biocellulose microfibrous network dispersion.
本發明的水分散生物纖維素微纖維網路分散體使用生物纖維素作為纖維素原料。 The water-dispersed biocellulose microfibrous network dispersion of the present invention uses biocellulose as a cellulose raw material.
本發明中使用的“生物纖維素”表示通過細菌培養直接合成纖維素微纖維的細菌纖維素。其區別於：來自各種木材的牛皮(craft)紙或亞硫酸紙漿、將它們用高壓均質機(homogenizer)或粉碎機(mill)等粉碎的粉末纖維素、或者通過酸水解等化學處理對它們進行純化的微晶纖維素粉末，此外，區別於來自洋麻(kenaf)、***(hemp)、水稻、甘蔗渣(bagasse)、竹子等植物的纖維素。可利用的細菌，例如包括醋桿菌屬(Acetobacter)、根瘤菌屬(Rhizibium)及農桿菌屬(Agrobacterium)，若在包含用於細菌培養的營養源的培養基中進行培養，則在培養液的介面形成細菌纖維素。培養方法有靜置培養法(Static cultivation)和振盪培養法(Agitated cultivation)。靜置培養方法是先將細菌移植到培養基中後，直接放置在車床等上並在燒瓶中培養約10天的方法。作為另一方法的振盪培養法是，通過液體培養基在振盪培養箱中一邊持續地以恒定的速度攪拌一邊培養的方法。也可以不通過上述細菌培養而購買使用市面上流通的生物纖維素。生物纖維素具有三維網狀結構，具有高結晶度(84~89%)，且具有足夠的空隙。生物纖維素的長度為幾微米~幾十微米，具有一定長度分佈度的直徑，即具有均勻長度分佈度的直徑。 The "biocellulose" used in the present invention means bacterial cellulose in which cellulose microfibrils are directly synthesized by bacterial culture. It is distinguished from: craft paper or sulfite pulp from various woods, powdered cellulose pulverized by a homogenizer or mill, etc., or by chemical treatment such as acid hydrolysis. Purified microcrystalline cellulose powder, moreover, is distinguished from cellulose from plants such as kenaf, hemp, rice, bagasse, bamboo, etc. Available bacteria, for example, include Acetobacter, Rhizibium and Agrobacterium, if cultured in a medium containing a nutrient source for bacterial culture, at the interface of the culture medium Bacterial cellulose is formed. Cultivation methods include static cultivation and Agitated cultivation. The static culture method is a method in which bacteria are first transplanted into a medium, and then placed directly on a lathe or the like and cultured in a flask for about 10 days. As another method, the shaking culture method is a method in which a liquid medium is cultured in a shaking incubator while continuously stirring at a constant speed. Commercially available biocellulose can also be purchased and used without culturing the bacteria described above. Biocellulose has a three-dimensional network structure with high crystallinity (84~89%) and sufficient voids. The length of biocellulose is several micrometers to several tens of micrometers, and has a diameter with a certain length distribution, that is, a diameter with a uniform length distribution.
對於本發明的水分散生物纖維素微纖維網路分散體而言，本發明的生物纖維素的醇基被羧基取代。 For the water-dispersed biocellulose microfibril network dispersion of the present invention, the alcohol group of the biocellulose of the present invention is substituted with a carboxyl group.
生物纖維素所包含的纖維素中0.8mmol/g以上的總醇基、優選1.0mmol/g以上的總醇基被羧基取代。 In the cellulose contained in the biocellulose, 0.8 mmol/g or more of total alcohol groups, preferably 1.0 mmol/g or more of total alcohol groups are substituted with carboxyl groups.
可利用本領域的多種方法，將生物纖維素的醇基取代為羧基，例如可通過在溶解有N-氧化合物的蒸餾水中一起添加氧化劑和生物纖維素而進行攪拌的過程來實現。 Substituting the alcohol group of the biocellulose with the carboxyl group can be achieved by various methods in the art, for example, by adding an oxidant and biocellulose in distilled water in which the N-oxygen compound is dissolved and stirring.
本發明的水分散生物纖維素微纖維網路分散體中，生物纖維素的醇基被羧基取代，由此因羧基而顯示出負電荷。例如，顯示出-30mV以下的負電荷，優選顯示出-50mV以下、更優選顯示出-60mV以下的負電荷。最優選為顯示出-60mV~-90mV的負電荷。 In the water-dispersed biocellulose microfiber network dispersion of the present invention, the alcohol group of the biocellulose is substituted with a carboxyl group, thereby exhibiting a negative charge due to the carboxyl group. For example, it exhibits a negative charge of -30 mV or less, preferably -50 mV or less, and more preferably -60 mV or less. Most preferably, it exhibits a negative charge of -60mV to -90mV.
本發明的水分散生物纖維素微纖維網路分散體的負電荷排斥微塵的負電荷，以減少微塵附著。 The negative charge of the water-dispersed biocellulose microfiber network dispersion of the present invention repels the negative charge of the fine dust to reduce the attachment of the fine dust.
本發明的水分散生物纖維素微纖維網路分散體中的個別微纖維的數均直徑為0.1~200nm，優選為1~150nm，更優選為20~100nm，最優選為30~60nm。在上述範圍內時，有利於施用到人體，有利於應用到例如化妝材料組合物和類藥品組合物，尤其為30~60nm時，具有既形成網狀結構又在塗抹時不堆積而能夠顯示出固有功能的優點，具有不滲透到皮膚的同時有效地隔絕微塵的效果。 The number average diameter of the individual microfibers in the water-dispersed biocellulose microfibril network dispersion of the present invention is 0.1 to 200 nm, preferably 1 to 150 nm, more preferably 20 to 100 nm, and most preferably 30 to 60 nm. When it is within the above range, it is favorable for application to the human body, such as cosmetic material compositions and drug-like compositions, and especially when it is 30 to 60 nm, it has a network structure and does not accumulate during application and can be displayed. The advantage of the inherent function has the effect of effectively blocking fine dust without penetrating into the skin.
而且，本發明的水分散生物纖維素微纖維網路分散體中的個別微纖維的最大直徑為0.1~200nm，優選為1~150nm，更優選為20~100nm，最優選為60~100nm。此時，具有既形成網狀結構又在塗抹時不堆積而能夠顯示出固有功能的優點，並具有不滲透到皮膚的同時有效地隔絕微塵的效果。在上述範圍內 時，有利於施用到人體，有利於應用到例如化妝材料組合物和類藥品組合物中，若大於200nm，塗抹時會堆積。 Furthermore, the maximum diameter of the individual microfibers in the water-dispersed biocellulose microfibril network dispersion of the present invention is 0.1 to 200 nm, preferably 1 to 150 nm, more preferably 20 to 100 nm, and most preferably 60 to 100 nm. In this case, there is an advantage that a network structure is formed, an inherent function can be exhibited without accumulation during application, and it has the effect of effectively blocking fine dust without penetrating into the skin. within the above range When it is larger than 200 nm, it is beneficial to be applied to the human body, such as cosmetic material compositions and drug-like compositions. If it is larger than 200 nm, it will accumulate when smeared.
另外，本發明的水分散生物纖維素微纖維網路分散體中的個別微纖維的長度與被用作原料的生物纖維素的長度相似。換言之，本發明的微纖維保持被用作原料的生物纖維素的長度。上述“長度與…的長度…相似”或者“保持(維持)長度”，表示與被用作原料的生物纖維素的長度實質上不存在差異，實質上不存在差異表示長度間差異為±10%以下、±5%以下、±1%以下、±0.1%以下、最優選為±0.01%以下。本發明的分散體製備過程中，不包括切斷微纖維的工序，因此基本上保持作為原料的生物纖維素的長度。 In addition, the length of the individual microfibers in the water-dispersed biocellulose microfibril network dispersion of the present invention is similar to the length of the biocellulose used as a raw material. In other words, the microfibers of the present invention maintain the length of the biocellulose used as a raw material. The above "the length is similar to the length of ..." or "maintaining (maintaining) the length" means that there is no substantial difference from the length of the biocellulose used as a raw material, and that there is no substantial difference means that the difference between the lengths is ±10% or less, ±5% or less, ±1% or less, ±0.1% or less, and most preferably ±0.01% or less. In the preparation process of the dispersion of the present invention, the step of cutting the microfibers is not included, so the length of the biocellulose as the raw material is substantially maintained.
本發明的水分散生物纖維素微纖維網路分散體在被添加到水溶液中時，保持作為微纖維的結構性、物理化學性特徵和/或水分散性，尤其具有維持生物纖維素原有的網狀並穩定地分散的特徵。 When the water-dispersed biocellulose microfiber network dispersion of the present invention is added to an aqueous solution, the structure, physicochemical characteristics and/or water dispersibility of microfibers are maintained, and in particular, it has the property of maintaining the original biocellulose. Network-like and stably dispersed features.
本發明的水分散生物纖維素微纖維網路分散體可被劑型化為水分散型組合物。 The water-dispersible biocellulose microfiber network dispersion of the present invention can be formulated into a water-dispersible composition.
上述“水分散型組合物”是作為溶劑包含水的組合物，是指水分散生物纖維素微纖維網路分散體分散在水相中的組合物。組合物可以是單獨的水相，可以是油包水型、水包油型或多重乳液，不限於此。 The above-mentioned "water-dispersed composition" is a composition containing water as a solvent, and refers to a composition in which a water-dispersed biocellulose microfiber network dispersion is dispersed in an aqueous phase. The composition may be a separate aqueous phase, may be a water-in-oil type, an oil-in-water type, or a multiple emulsion, but is not limited thereto.
本發明的水分散生物纖維素微纖維網路分散體，可用本領域中公知的多種方法製備，不限於特定的方法。只是將生物纖維素用作原料，不需要用於細化的自頂向下(top-down)方式的預處理過程。例如，不包括切斷微纖維的工序。 The water-dispersed biocellulose microfiber network dispersion of the present invention can be prepared by various methods known in the art, and is not limited to a specific method. Only biocellulose is used as a raw material, and a top-down pretreatment process for refinement is not required. For example, the process of cutting the microfibers is not included.
優選地，可包括下面的步驟來進行製備：在水中溶解N-氧化合物的步驟；在溶解物中添加生物纖維素和氧化劑並進行攪拌的步驟；以及 通過清洗過程來去除反應物的步驟。 Preferably, the preparation may include the following steps: a step of dissolving an N-oxygen compound in water; a step of adding biocellulose and an oxidizing agent to the dissolved substance and stirring; and The step of removing reactants through a cleaning process.
本發明中可使用的“N-氧化合物”是催化劑，在本申請發明中為了促進氧化反應而使用。作為N-氧化合物，例如可選擇下述化合物中的1種以上：2,2,6,6-四甲基-1-呱啶-氧自由基(TEMPO)；將4-羥基-2,2,6,6-四甲基-1-呱啶-氧自由基(4-羥基TEMPO)的羥基用醇進行醚化或者用羧酸或磺酸進行酯化從而賦予合適的疏水性的4-羥基TEMPO衍生物；或者氮雜金剛烷型氮氧自由基，最優選可使用2,2,6,6-四甲基-1-呱啶-氧自由基(TEMPO)。對於N-氧化合物的使用量，只要是能夠將生物纖維素微纖維化的催化劑量即可，沒有特別限制。例如，相對於1g纖維素系乾燥原料，可使用0.01~100mmol，優選使用0.01~50mmol，特別優選使用0.05~30mmol左右。 The "N-oxygen compound" that can be used in the present invention is a catalyst, and is used in the present invention to promote the oxidation reaction. As the N-oxygen compound, one or more of the following compounds can be selected, for example: 2,2,6,6-tetramethyl-1-oxidine-oxyl radical (TEMPO); 4-hydroxy-2,2 ,6,6-Tetramethyl-1-oxidine-oxyl (4-hydroxy TEMPO) hydroxyl groups are etherified with alcohols or esterified with carboxylic acids or sulfonic acids to impart suitable hydrophobicity to the 4-hydroxy groups TEMPO derivatives; or azaadamantane-type nitroxyl radicals, most preferably, 2,2,6,6-tetramethyl-1-pyridine-oxyl radical (TEMPO) can be used. The amount of the N-oxygen compound used is not particularly limited as long as it is a catalyst amount capable of microfibrillating biocellulose. For example, 0.01 to 100 mmol can be used with respect to 1 g of the cellulose-based dry raw material, preferably 0.01 to 50 mmol, and particularly preferably about 0.05 to 30 mmol.
作為本發明中可使用的“氧化劑”，優選包括鹵素、次鹵酸、亞鹵酸、過鹵酸或其鹽等；鹵素氧化物；鹵素過氧化物等，優選使用鹵素中的氯，例如，優選氯、次氯酸、亞氯酸、高氯酸或其鹽等；氯氧化物；氯過氧化物，最優選地可以使用次氯酸鈉。次氯酸鈉在微纖維生產費用方面羥濟，在現代工業過程中最廣泛使用、廉價且環境負荷小，故特別優選。氧化劑的使用量可選自能夠促進氧化反應的範圍。例如，相對於1g纖維素系乾燥原料，可使用0.5~500mmol，優選使用0.5~50mmol，特別優選使用2.5~25mmol左右。 As the "oxidizing agent" that can be used in the present invention, it preferably includes halogens, hypohalous acids, halous acids, perhalic acids or salts thereof, etc.; halogen oxides; halogen peroxides, etc., preferably chlorine among halogens, for example, Preferably chlorine, hypochlorous acid, chlorous acid, perchloric acid or its salts, etc.; oxychloride; chlorine peroxide, most preferably sodium hypochlorite can be used. Sodium hypochlorite is economical in terms of microfiber production cost, and is the most widely used in modern industrial processes, is inexpensive and has a small environmental load, so it is particularly preferred. The amount of the oxidizing agent to be used can be selected from a range capable of promoting the oxidation reaction. For example, 0.5 to 500 mmol can be used with respect to 1 g of the cellulose-based dry raw material, preferably 0.5 to 50 mmol, and particularly preferably about 2.5 to 25 mmol.
根據本申請發明的生物纖維素微纖維網路分散體的製備方法中，實質上不使用溴化物。 In the preparation method of the biocellulose microfiber network dispersion according to the present invention, substantially no bromide is used.
上述“實質上不使用”表示相對於1g生物纖維素乾燥原料使用0.1mmol以下，優選使用0.01mmol以下，更優選使用0.001mmol以下。溴化物、例如氯化溴有可能對支氣管或肺部誘發毒性，存在操作時的安全性問題以及廢棄時的重金屬導致的環境污染的可能性，因此本發明中實質上不使用。即使不 使用溴化物，根據本發明也能夠製備優異功效的水分散生物纖維素微纖維網路分散體。 The above-mentioned "substantially not used" means to use 0.1 mmol or less, preferably 0.01 mmol or less, and more preferably 0.001 mmol or less with respect to 1 g of the dry raw material of biocellulose. Bromides such as bromine chloride may induce toxicity to the bronchi and lungs, and may cause safety problems during handling and environmental pollution due to heavy metals during disposal, so they are not substantially used in the present invention. even if not Using bromide, excellent efficacy water-dispersed biocellulose microfiber network dispersions can also be prepared according to the present invention.
根據本申請發明的水分散生物纖維素分散體的製備方法，即使在15~30℃左右室溫的溫和的條件下，也能夠順暢地進行氧化反應。 According to the preparation method of the water-dispersed biocellulose dispersion of the present invention, the oxidation reaction can proceed smoothly even under mild conditions at room temperature of about 15 to 30°C.
隨著氧化反應的進行，在生物纖維素結構中生成羧基，因此反應液的pH降低。由此，為進行有效的氧化反應，需要通過持續地添加鹼性溶液將反應液的pH維持為8~12，更優選維持為10~11左右。氧化反應的反應時間可適當地設定，不特別限制，例如為0.5~60小時，優選為1~50小時，特別優選為24~48小時左右。 As the oxidation reaction proceeds, carboxyl groups are formed in the biocellulose structure, so the pH of the reaction solution decreases. Therefore, in order to carry out an efficient oxidation reaction, it is necessary to maintain the pH of the reaction liquid at 8 to 12, more preferably at about 10 to 11, by continuously adding an alkaline solution. The reaction time of the oxidation reaction can be appropriately set and is not particularly limited, but is, for example, 0.5 to 60 hours, preferably 1 to 50 hours, and particularly preferably about 24 to 48 hours.
本發明的水分散生物纖維素微纖維網路分散體，能夠用作多種用途的組合物，尤其能夠用作化妝材料組合物和類藥品組合物。另外，本發明的水分散生物纖維素微纖維網路分散體不僅皮膚附著性優異，而且不滲透到皮膚內，能夠用作施用於人體、優選施用於皮膚的化妝材料組合物和類藥品組合物。 The water-dispersed biocellulose microfiber network dispersion of the present invention can be used as a composition for various purposes, especially as a cosmetic material composition and a drug-like composition. In addition, the water-dispersed biocellulose microfiber network dispersion of the present invention not only has excellent skin adhesion, but also does not penetrate into the skin, and can be used as a cosmetic composition and a drug-like composition to be applied to the human body, preferably to the skin .
本發明的水分散生物纖維素微纖維網路分散體具有在水相中形成網路並分散到水相中的特徵，在包含水相的組合物中尤其有用。 The water-dispersible biocellulose microfibrous network dispersions of the present invention have the characteristics of forming a network in and dispersing into an aqueous phase, and are particularly useful in compositions comprising an aqueous phase.
更具體而言，本發明的水分散生物纖維素微纖維網路分散體具有皮膚安放性、水分保持能力、彈性增加以及改善增稠力、柔軟性的能力，因此可用作基於它們的用途。本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物可用作增強水分或增強彈性的用途。 More specifically, the water-dispersible biocellulose microfiber network dispersions of the present invention have skin-embedding properties, moisture-retaining ability, increased elasticity, and ability to improve thickening power and softness, and thus can be used for applications based on them. The water-dispersed biocellulose microfiber network dispersion of the present invention or a composition comprising the same can be used for the purpose of enhancing moisture or enhancing elasticity.
更具體而言，本發明的水分散生物纖維素微纖維網路分散體不僅皮膚附著性優異，而且不滲透到皮膚內，對隔絕微塵具有優異的效果，因此可用作基於它們的用途。本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物可用作隔絕微塵的用途。 More specifically, the water-dispersed biocellulose microfiber network dispersion of the present invention is not only excellent in skin adhesion, but also does not penetrate into the skin and has an excellent effect on sequestering fine dust, and thus can be used for applications based on them. The water-dispersed biocellulose microfibril network dispersion of the present invention or a composition comprising the same can be used for the purpose of sequestering fine dust.
更具體而言，本發明的水分散生物纖維素微纖維網路分散體不僅皮膚附著性優異，而且不滲透到皮膚內，並對保護角蛋白結構體具有優異的效果，因此可用作基於它們的用途。本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物可用作保護角蛋白結構體的用途。 More specifically, the water-dispersed biocellulose microfiber network dispersion of the present invention is not only excellent in skin adhesion, but also does not penetrate into the skin, and has an excellent effect on protecting keratin structures, and thus can be used as products based on them. the use of. The water-dispersed biocellulose microfibril network dispersion of the present invention or a composition comprising the same can be used for the protection of keratin structures.
本發明提供一種包含水分散生物纖維素微纖維網路分散體的化妝材料組合物，其特徵在於，所述水分散生物纖維素微纖維網路分散體為生物纖維素微纖維網路分散體，優選最大直徑為60~100nm，數均直徑為30~60nm，在水相中形成網路並分散到水相中。 The present invention provides a cosmetic material composition comprising a water-dispersed bio-cellulose microfiber network dispersion, characterized in that the water-dispersed bio-cellulose microfiber network dispersion is a bio-cellulose microfiber network dispersion, Preferably, the maximum diameter is 60 to 100 nm, the number average diameter is 30 to 60 nm, and a network is formed in the aqueous phase and dispersed in the aqueous phase.
本發明的化妝材料組合物還可用作功能性化妝品。 The cosmetic material composition of the present invention can also be used as a functional cosmetic.
本發明中，“功能性化妝品(cosmedical，cosmeceutical)”是指，對化妝品導入醫藥品的專門治療功能而與普通化妝品有所不同地強化了生理活性功效、效果的具有專門功能性的產品，例如，是指有助於皮膚美白的產品、有助於改善皮膚皺紋的產品、有助於美膚或使皮膚免受紫外線損害的產品等衛生福利部(Ministry of Health & Welfare)令所指定的化妝品。 In the present invention, "functional cosmetics (cosmedical, cosmeceutical)" refers to products with specialized functionalities which are introduced into cosmetics with specialized therapeutic functions of pharmaceuticals, and which enhance physiologically active effects and effects differently from ordinary cosmetics. For example, , refers to cosmetics designated by the Ministry of Health & Welfare (Ministry of Health & Welfare), such as products that help skin whitening, products that help improve skin wrinkles, products that help skin beautification or protect skin from ultraviolet rays, etc. .
本發明的化妝材料組合物可與化妝領域中的通常的佐劑，例如與脂肪物質、有機溶劑、溶解劑、濃縮劑、膠凝劑、軟化劑、抗氧劑、懸浮劑、穩定劑、發泡劑(foamingagent)、芳香劑、表面活性劑、水、離子型或非離子型乳化劑、填充劑、多價螯合劑(sequestering agent)、螯合劑、防腐劑、維生素、阻滯劑、濕潤劑、精油、染料、顏料、親水性或親油性活性劑、脂質小囊以及如通常用於化妝品的任意的其它成分的、在化妝品學或皮膚科學領域中通常所使用的佐劑一起，作為普通化妝品或功能性化妝品的構成要素使用。 The cosmetic material composition of the present invention can be mixed with common adjuvants in the cosmetic field, such as fatty substances, organic solvents, dissolving agents, concentrating agents, gelling agents, softening agents, antioxidants, suspending agents, stabilizers, hair Foaming agents, fragrances, surfactants, water, ionic or nonionic emulsifiers, fillers, sequestering agents, chelating agents, preservatives, vitamins, retarders, wetting agents , essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles, and adjuvants commonly used in the field of cosmetic or dermatology, such as any other ingredients commonly used in cosmetics, as general cosmetic products Or use as a component of functional cosmetics.
包含本發明的化妝材料組合物的化妝品，可製備成本領域中通常所製備的任何劑型，例如能夠被劑型化為溶液、懸浮液、乳液、膏劑、凝膠、霜劑、潤膚乳、粉末、肥皂、含表面活性劑的清潔霜、油、粉末粉底霜、乳液 粉底霜、蠟粉底霜及噴霧液等，但不限於此。更詳細而言，可製備成柔軟化妝水、收斂化妝水、營養化妝水、營養霜、按摩霜、保濕霜、水分啫喱霜、潤膚乳、凝膠、精華液、眼霜、撕拉型面膜、清潔霜、清潔泡沫、卸妝水、面膜、軟膏、粉底、貼片、噴霧液或粉末的劑型。 Cosmetics comprising the cosmetic material composition of the present invention can be prepared in any dosage form usually prepared in the field, for example, can be formulated into solutions, suspensions, emulsions, ointments, gels, creams, lotions, powders, Soaps, surfactant-based cleansing creams, oils, powder foundations, lotions Cream foundation, wax foundation cream, spray liquid, etc., but not limited thereto. More specifically, it can be prepared into soft lotion, astringent lotion, nutritional lotion, nourishing cream, massage cream, moisturizing cream, moisture gel cream, body lotion, gel, essence, eye cream, peel-off mask, Dosage form of cleansing cream, cleansing foam, makeup remover, mask, ointment, foundation, patch, spray or powder.
本發明的水分散纖維素微纖維網路分散體的含量相對於化妝材料組合物的總重量可為0.0001~10乾燥重量%，優選為0.0001~5乾燥重量%，更優選為0.0005~5乾燥重量%。 The content of the water-dispersed cellulose microfiber network dispersion of the present invention may be 0.0001 to 10% by dry weight, preferably 0.0001 to 5% by dry weight, and more preferably 0.0005 to 5% by dry weight relative to the total weight of the cosmetic composition. %.
本發明提供一種包含水分散生物纖維素微纖維網路分散體的類藥品組合物，所述水分散生物纖維素微纖維網路分散體為生物纖維素微纖維網路分散體，優選最大直徑為60~100nm，數均直徑為30~60nm，在水相中形成網路並分散到水相中。 The present invention provides a drug-like composition comprising a water-dispersed bio-cellulose microfiber network dispersion, wherein the water-dispersed bio-cellulose microfiber network dispersion is a bio-cellulose microfiber network dispersion, and the preferred maximum diameter is 60~100nm, the number average diameter is 30~60nm, form a network in the water phase and disperse into the water phase.
本發明中，“類藥品”表示除如下物品以外的物品：以治療、減輕、處置或預防危害人或動物的症狀為目的而使用的物品；對人體的作用微弱或不直接作用於人體且不為機構或機器的物品及與之類似的物品；作為與為了預防而被用作殺菌、殺蟲及與之類似用途的製劑中的一種相當的物品，以診斷、治療、減輕、處置或預防為目的而使用的物品中不為機構、機器或裝置的物品；以及以對人或動物的結構和功能產生藥理學影響為目的而使用的物品中不為機構、機械或裝置的物品，所述類藥品還包括皮膚外用劑和個人衛生用品。 In the present invention, "quasi-drug" refers to items other than the following items: items used for the purpose of treating, alleviating, disposing or preventing symptoms that endanger humans or animals; Articles of establishment or machinery and the like; as an equivalent of one of preparations used for prophylactic, sterilizing, insecticidal and similar purposes for the purpose of diagnosis, treatment, mitigation, treatment or prophylaxis Articles used for purposes other than mechanisms, machines or devices; and articles used for the purpose of having a pharmacological effect on the structure and function of humans or animals that are not mechanisms, machines or devices, said categories Medicines also include topical skin preparations and personal hygiene products.
本發明中，“皮膚外用劑”表示，在油脂類、凡士林、羊毛脂、甘油等多種基質中混合藥品使得容易塗抹在皮膚上的固態、半固態或液態的外用藥。對外用劑型沒有特別限制，例如可包括粉末、凝膠、軟膏、霜劑、液體或氣溶膠的劑型。 In the present invention, "external preparation for skin" means a solid, semi-solid or liquid external medicine that is easily applied to the skin by mixing drugs in various bases such as oils, petrolatum, lanolin, and glycerin. The dosage form for external use is not particularly limited, and may include, for example, powder, gel, ointment, cream, liquid, or aerosol dosage forms.
本發明的水分散纖維素微纖維網路分散體的含量相對於類藥品組合物的總重量可為0.0001~10乾燥重量%，優選為0.0001~5乾燥重量%，更優選為0.0005~5乾燥重量%。 The content of the water-dispersible cellulose microfiber network dispersion of the present invention can be 0.0001-10% by dry weight relative to the total weight of the drug-like composition, preferably 0.0001-5% by dry weight, more preferably 0.0005-5% by dry weight %.
本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物具有皮膚安放性、水分保持能力、彈性增加以及改善增稠力、柔軟性的能力，因此可用作基於它們的有效方法。 The water-dispersed biocellulose microfiber network dispersion of the present invention or a composition comprising the same has skin-embedding properties, moisture-retaining ability, increased elasticity, and ability to improve thickening power and softness, and thus can be used as effective agents based on them. method.
更具體而言，本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物施用於人體而能夠用作增強水分或增加彈性的方法。 More specifically, the water-dispersible biocellulose microfiber network dispersion of the present invention or a composition comprising the same can be used as a method for enhancing moisture or increasing elasticity when applied to the human body.
上述人體優選包含皮膚。 The above-mentioned human body preferably includes skin.
上述施用(應用、適用)只要是對人體直接、間接產生影響的方式即可，並不受限制，例如可包括塗抹於人體的方式。 The above-mentioned administration (application, application) is not limited as long as it directly or indirectly affects the human body, and for example, it may include the method of applying to the human body.
本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物具有隔絕微塵的能力，因此可用作基於它們的有效方法。 The water-dispersed biocellulose microfiber network dispersion of the present invention or a composition comprising the same has the ability to isolate fine dust, and thus can be used as an effective method based on them.
更具體而言，能夠用作將本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物施用於人體來隔絕微塵的方法。 More specifically, it can be used as a method for sequestering fine dust by applying the water-dispersed biocellulose microfiber network dispersion of the present invention or a composition containing the same to a human body.
上述人體優選包含皮膚。 The above-mentioned human body preferably includes skin.
上述施用(應用、適用)只要是對人體直接、間接產生影響的方式即可，並不受限制，例如可包括塗抹於人體的方式。 The above-mentioned administration (application, application) is not limited as long as it directly or indirectly affects the human body, and for example, it may include the method of applying to the human body.
本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物具有保護角蛋白結構體的能力，因此可用作基於它們的有效方法。 The water-dispersed biocellulose microfibril network dispersion of the present invention or a composition comprising the same has the ability to protect keratin structures, and thus can be used as an effective method based on them.
更具體而言，能夠用作將本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物施用於人體來保護角蛋白結構體的方法。 More specifically, it can be used as a method for protecting a keratin structure by applying the water-dispersed biocellulose microfibril network dispersion of the present invention or a composition comprising the same to a human body.
上述人體優選包括皮膚。 The above-mentioned human body preferably includes skin.
上述施用(應用、適用)只要是對人體直接、間接產生影響的方式即可，並不受限制，例如可包括塗抹於人體的方式。 The above-mentioned administration (application, application) is not limited as long as it directly or indirectly affects the human body, and for example, it may include the method of applying to the human body.
本發明的水分散生物纖維素微纖維網路分散體或包含其的組合物可用於保護多種角蛋白結構體，例如在施用於毛髮的情況下，能夠被劑型化為選自由預洗髮(pre-shampoo)組合物、香波、護髮素、鋦油膏、蠟、凝膠、噴霧液、摩絲、潤髮露、髮膜、護髮精油、髮乳、永久染髮劑、臨時染髮劑、冷燙液、無紡布及片材所組成的組中的1種以上。另外，例如，在施用於手指甲或腳趾甲的情況下，能夠劑型化為選自由整理或保護手腳趾甲用基底、指甲油、面漆、營養素、增強劑及凝膠所組成的組中的1種以上。 The water-dispersed biocellulose microfibril network dispersion of the present invention or a composition comprising the same can be used to protect a variety of keratin structures, for example in the case of application to hair, can be formulated to be selected from pre-shampoo (pre-shampoo) -shampoo) composition, shampoo, conditioner, ointment, wax, gel, spray, mousse, conditioner, hair mask, hair oil, hair cream, permanent hair color, temporary hair color, cold perm One or more of the group consisting of a liquid, a nonwoven fabric, and a sheet. In addition, for example, in the case of applying to fingernails or toenails, it can be formulated into 1 selected from the group consisting of bases for finishing or protecting fingernails, nail polishes, top coats, nutrients, enhancers, and gels more than one species.
本發明的水分散生物纖維素微纖維網路分散體維持生物纖維素原料的長度，在被劑型化為組合物之後也維持纖維網路，在皮膚形成的微纖維具有優異的皮膚安放性、增強水分吸收和彈性的效果，並具有改善柔軟性的效果，因此能夠非常有效地用作類藥品和化妝材料。 The water-dispersed biocellulose microfiber network dispersion of the present invention maintains the length of the biocellulose raw material, maintains the fiber network even after being formulated into a composition, and the microfibers formed on the skin have excellent skin placement, reinforcement It has the effect of moisture absorption and elasticity, and has the effect of improving softness, so it can be used as a quasi-drug and cosmetic material very effectively.
本說明書中所附的以下附圖用於例示本發明的優選實施例，起到與前述發明內容一起進一步理解本發明的技術思想的作用，因此不應將本發明限定於這些附圖中記載的事項來進行解釋。 The following drawings attached to this specification are used to illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the foregoing summary of the invention. Therefore, the present invention should not be limited to those described in these drawings. matter to explain.
圖1(a)是比較例1的纖維素微纖維照片；圖1(b)是實施例1的化學處理後的水分散纖維素微纖維網路分散體的照片；圖2(a、b)是0.05%、0.015%濃度的比較例2的木質系纖維素分散體的照片； 圖2(c、d)是0.05%、0.015%濃度的實施例1的水分散生物纖維素微纖維網路分散體的照片；圖3是塗抹實施例1前後的豬皮膚的SEM照片；圖4的(a)是表示塗抹實施例和比較例的纖維素的豬皮膚上的水的接觸角隨時間變化的圖表；圖4(b)是初始接觸角的顯微鏡照片；圖5是表示將實施例1塗抹在皮膚上之後測定的摩擦力資料的圖表；圖6是表示精華液劑型(比較例5、實施例2和3)的粘度數據的圖表；圖7是表示塗抹比較例5和實施例2的豬皮膚上的水的接觸角隨時間變化的圖表；圖8(a)是塗抹比較例6的豬皮膚的SEM照片；圖8(b)是塗抹0.01乾燥重量%的實施例1的豬皮膚的SEM照片；圖8(c、d)是塗抹0.05乾燥重量%的實施例1的豬皮膚的SEM照片；圖9(a)是將0.05乾燥重量%的實施例1塗抹在豬皮膚上之後在其上塗抹微塵的SEM照片；圖9(b)是將比較例6塗抹在豬皮膚上之後在其上塗抹微塵的SEM照片；圖10(a)是將比較例6塗抹在豬皮膚上之後在其上塗抹微塵替代物的SEM照片(上)和螢光顯微鏡照片(下)；圖10(b)是將0.05乾燥重量%的比較例7塗抹在豬皮膚上之後在其上塗抹微塵替代物的SEM照片(上)和螢光顯微鏡照片(下)； 圖10(c)是將0.05乾燥重量%的實施例1塗抹在豬皮膚上之後在其上塗抹微塵替代物的SEM照片(上)和螢光顯微鏡照片(下)；圖11是用根據實施例6製備的含有生物纖維素微纖維網路水分散體的O/W乳化劑型的精華液對人的毛髮表面處理之後進行乾燥並用掃描電子顯微鏡(SEM)測定的照片；及圖12是用根據實施例6製備的含有生物纖維素微纖維網路水分散體的O/W乳化劑型的精華液對人的手指甲表面處理之後進行乾燥並用掃描電子顯微鏡(SEM)測定的照片。 Figure 1(a) is a photograph of the cellulose microfibrils of Comparative Example 1; Figure 1(b) is a photograph of the chemically treated water-dispersed cellulose microfibril network dispersion of Example 1; Figures 2(a, b) It is a photograph of the lignocellulose dispersion of Comparative Example 2 at a concentration of 0.05% and 0.015%; Figure 2 (c, d) are photographs of the water-dispersed biocellulose microfiber network dispersion of Example 1 at concentrations of 0.05% and 0.015%; Figure 3 is a SEM photograph of pig skin before and after application of Example 1; Figure 4 (a) is a graph showing the time-dependent change in the contact angle of water on pig skins coated with the cellulose of Examples and Comparative Examples; FIG. 4(b) is a micrograph of the initial contact angle; 1 is a graph of friction data measured after application to the skin; Figure 6 is a graph showing viscosity data for serum formulations (Comparative Example 5, Examples 2 and 3); Figure 7 is a graph showing application of Comparative Example 5 and Example 2 Figure 8(a) is a SEM photograph of the pig skin of Comparative Example 6 applied with time; Figure 8(b) is the pig skin of Example 1 applied at 0.01 dry weight % Figure 8(c, d) is the SEM photo of the pig skin of Example 1 applied with 0.05 dry weight %; The SEM photo of the fine dust smeared thereon; Fig. 9(b) is the SEM photograph of the fine dust smeared on the pig skin after the comparative example 6 is applied; SEM photo (top) and fluorescence microscope photo (bottom) of dust substitute applied thereon; Fig. 10(b) is the application of dust substitute on pig skin after 0.05 dry weight % of Comparative Example 7 was applied on it SEM photo (top) and fluorescence microscope photo (bottom); Fig. 10(c) is a SEM photograph (top) and a fluorescence microscope photograph (bottom) of a dust substitute applied on pig skin after 0.05 dry weight % of Example 1 was applied to pig skin; 6. The prepared essence of the O/W emulsification formulation containing the biocellulose microfiber network aqueous dispersion is dried and measured with a scanning electron microscope (SEM) after the surface treatment of human hair; Example 6 A photograph of a human fingernail surface treated with an O/W emulsion formulation containing an aqueous biocellulose microfiber network dispersion, dried and measured with a scanning electron microscope (SEM).
本申請要求基於2016年3月3日申請的韓國特許申請第10-2016-0025765號、2017年1月6日申請的韓國特許申請第10-2017-0002301號、2017年3月3日申請的韓國特許申請第10-2017-0027863號、2016年8月8日申請的韓國特許申請第10-2016-0100599號、2017年3月3日申請的韓國特許申請第10-2017-0027902號、2016年8月8日申請的韓國特許申請第10-2016-0100603號以及2017年3月3日申請的韓國特許申請第10-2017-0027721號的優先權，本申請援引相關申請的說明書以及附圖中公開的所有內容。 This application claims based on Korean Patent Application No. 10-2016-0025765 filed on March 3, 2016, Korean Patent Application No. 10-2017-0002301 filed on January 6, 2017, and Korean Patent Application No. 10-2017-0002301 filed on March 3, 2017 Korean Patent Application No. 10-2017-0027863, Korean Patent Application No. 10-2016-0100599 filed on August 8, 2016, Korean Patent Application No. 10-2017-0027902 filed on March 3, 2017, 2016 The priority of Korean Patent Application No. 10-2016-0100603 filed on August 8, 2017 and Korean Patent Application No. 10-2017-0027721 filed on March 3, 2017, the specification and drawings of the related applications are cited in this application All content disclosed in .
下面，為有助於理解本發明，舉出實施例等詳細地說明。但是，本發明的實施例可變形為多種其它形態，不應解釋為本發明的範圍限定於下述實施例。本發明的實施例用於向本領域的技術人員更完整地說明本發明而提供。 Hereinafter, in order to facilitate understanding of the present invention, examples and the like will be given and described in detail. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
製造例1：生物纖維素的化學處理 Production Example 1: Chemical Treatment of Biocellulose
為進行生物纖維素的化學處理，使用了生物纖維素(EZ Costec Co.,Ltd，無孔布料(unperforated fabric))、次氯酸鈉和2,2,6,6-四甲基-1-呱啶-N- 氧自由基(以下稱為TEMPO)催化劑。在100g蒸餾水中溶解10mgTEMPO催化劑之後，放入5g生物纖維素片，再放入8g次氯酸鈉之後，常溫下將pH維持在10以上，並攪拌12~24小時，從而製備成水中分散有生物纖維素片的微纖維形態(圖1的b、圖8的b)。將製備的水分散生物纖維素微纖維網路分散體通過純化和洗滌過程而進行調製之後，保存在常溫下。如此獲得的生物纖維素微纖維網路分散體(實施例1)中的微纖維的最大直徑為60~100nm，數均直徑為30~60nm，並且長度保持了生物纖維素(EZ Costec Co.,Ltd，無孔布料(unperforated fabric))的長度。 For chemical treatment of biocellulose, biocellulose (EZ Costec Co., Ltd, unperforated fabric), sodium hypochlorite and 2,2,6,6-tetramethyl-1-quadidine- N- Oxygen radical (hereinafter referred to as TEMPO) catalyst. After dissolving 10 mg of TEMPO catalyst in 100 g of distilled water, put 5 g of biocellulose sheets, and then put in 8 g of sodium hypochlorite, maintain the pH above 10 at room temperature, and stir for 12 to 24 hours to prepare bio-cellulose sheets dispersed in water The microfibril morphology (Figure 1b, Figure 8b). After the prepared water-dispersed biocellulose microfiber network dispersion was prepared through purification and washing processes, it was stored at normal temperature. The maximum diameter of the microfibrils in the thus obtained biocellulose microfibril network dispersion (Example 1) was 60 to 100 nm, the number average diameter was 30 to 60 nm, and the length of the biocellulose (EZ Costec Co., Ltd, unperforated fabric).
為確認合成的實施例1是否具有微纖維網路結構，使用掃描型電子顯微鏡(SEM)進行確認。其結果，確認到水分散生物纖維素具有微纖維網路形態(圖1的b、圖8的b、圖8的c、d)。 In order to confirm whether or not the synthesized Example 1 has a microfiber network structure, it was confirmed using a scanning electron microscope (SEM). As a result, it was confirmed that the water-dispersed biocellulose had a microfiber network morphology (b in FIG. 1 , b in FIG. 8 , and c and d in FIG. 8 ).
-實驗例1~實驗例7中所使用的實施例和比較例如下。 - Examples and comparative examples used in Experimental Example 1 to Experimental Example 7 are as follows.
實施例1是根據上述製備例1制得的生物纖維素微纖維網路分散體。 Example 1 is a biocellulose microfiber network dispersion prepared according to Preparation Example 1 above.
比較例1是在蒸餾水中放入生物纖維素片進行攪拌而製備的。 Comparative Example 1 was prepared by placing a biocellulose sheet in distilled water and stirring.
比較例2是將木質系纖維素通過與實施例1相同的方法合成的。在圖1的a、圖2的a、b中公開了SEM照片。 In Comparative Example 2, lignocellulose was synthesized by the same method as in Example 1. SEM photographs are disclosed in a of FIG. 1 and a and b of FIG. 2 .
比較例3是將通常被用作化妝材料的水溶性纖維素、即羧甲基纖維素放入蒸餾水中攪拌而製備的。 Comparative Example 3 was prepared by stirring water-soluble cellulose, ie, carboxymethyl cellulose, which is generally used as a cosmetic material in distilled water.
比較例4是將通常被用作化妝材料的水溶性纖維素、即羥乙基纖維素放入蒸餾水中攪拌而製備的。 Comparative Example 4 was prepared by stirring water-soluble cellulose, ie, hydroxyethyl cellulose, which is generally used as a cosmetic material in distilled water.
比較例5是不包含實施例1的精華液劑型。 Comparative Example 5 is a serum formulation that does not contain Example 1.
實施例2是包含0.015乾燥重量%的實施例1的水分散生物纖維素微纖維網路分散體的精華液劑型。 Example 2 is a serum dosage form comprising 0.015 dry weight percent of the water-dispersed biocellulose microfiber network dispersion of Example 1.
實施例3是包含0.03乾燥重量%的實施例1的水分散生物纖維素微纖維網路分散體的精華液劑型。 Example 3 is a serum dosage form comprising 0.03 dry weight percent of the water-dispersed biocellulose microfiber network dispersion of Example 1.
實驗例1：水分散生物纖維素微纖維網路分散體與木質系纖維素分散體的對比 Experimental Example 1: Comparison of water-dispersed biocellulose microfiber network dispersion and lignocellulose dispersion
實施了用於對比將水分散生物纖維素微纖維網路分散體和木質系纖維素氧化之後的分散體結構的實驗。將木質系纖維素原料(Whatman，濾紙，1005~110)通過與上述製備例1相同的方法合成的產物、即將比較例2，用SEM進行了確認。 Experiments were performed to compare the structure of the dispersion after oxidizing the water-dispersed biocellulose microfibrous network dispersion and the lignocellulose. A lignocellulosic raw material (Whatman, filter paper, 1005 to 110) synthesized by the same method as in the above-mentioned Preparation Example 1, that is, Comparative Example 2, was confirmed by SEM.
將比較例2稀釋為0.05乾燥重量%的示於圖2的a，將稀釋為0.015乾燥重量%的示於圖2的b。由圖2的a和b可知，顯示出針狀結構，且不形成網路。 The comparative example 2 was diluted to 0.05 dry weight % as shown in a of FIG. 2 , and diluted to 0.015 dry weight % as shown in FIG. 2 b . As can be seen from a and b of Fig. 2, a needle-like structure is shown, and no network is formed.
另外，將相同濃度的實施例1稀釋為0.05乾燥重量%的示於圖2的c，將稀釋為0.015乾燥重量%的示於圖2的d。由圖2的c和d可確認，實施例1的數均直徑為30~60nm，長度保持幾微米~幾十微米，從而顯示出在低濃度下也形成纖維間網路的結構。由此能夠確認，木質系纖維素和生物纖維素在形成網路方面，其結構不同，由此帶來的功能也顯示出差異。 In addition, Example 1 of the same concentration was diluted to 0.05 dry weight % as shown in c in FIG. 2 , and diluted to 0.015 dry weight % as shown in FIG. 2 d. From c and d of FIG. 2 , it was confirmed that Example 1 had a number-average diameter of 30 to 60 nm and a length of several to tens of microns, showing a structure in which an interfiber network was formed even at a low concentration. From this, it was confirmed that lignocellulose and biocellulose have different structures in forming a network, and thus also have different functions.
實驗例2：水分散生物纖維素微纖維網路分散體的皮膚安放確認 Experimental example 2: Confirmation of skin placement of water-dispersed biocellulose microfiber network dispersion
為確認將0.03乾燥重量%的實施例1塗抹在皮膚時是否安放於皮膚上，塗抹在豬皮膚(2cm×2cm)上之後進行乾燥，並用SEM進行確認。由圖3可確認，纖維素微纖維網路分散體穩定地塗抹在豬皮膚表面，由此證明了皮膚表面形成並安放有微纖維。 In order to confirm whether or not 0.03% by dry weight of Example 1 was applied to the skin or not, it was applied to pig skin (2 cm×2 cm), dried, and confirmed by SEM. From FIG. 3 , it was confirmed that the cellulose microfiber network dispersion was stably applied to the surface of the pig skin, thereby confirming that the microfibers were formed and settled on the skin surface.
實驗例3：水分散纖維素微纖維網路分散體的水分保持能力確認 Experimental Example 3: Confirmation of Water Retention Capability of Water-dispersed Cellulose Microfiber Network Dispersion
為確認水分保持能力，將比較例2、3、4以及實施例1以0.5乾燥重量%塗抹在豬皮膚上之後，進行乾燥，然後滴加水，測定接觸角，將測定的結果示於表1。初始接觸角顯示出比較例4>比較例2>比較例3>實施例1的順序，接觸角越小，表示越具有親水性質。 In order to confirm the water retention ability, Comparative Examples 2, 3, 4 and Example 1 were applied to pig skin at 0.5 dry weight %, dried, and then water was added dropwise to measure the contact angle. Table 1 shows the measurement results. The initial contact angle shows the order of Comparative Example 4>Comparative Example 2>Comparative Example 3>Example 1, and the smaller the contact angle, the more hydrophilic it is.
並且，將接觸角隨時間的變化示於圖4。在實施例1的情況下，接觸角急劇地減小，這表示水分散纖維素微纖維快速吸收水分，由此能夠確認可通過增加水分散纖維素微纖維的水分保持力而得到優異的保濕能力。 In addition, the change with time of the contact angle is shown in FIG. 4 . In the case of Example 1, the contact angle was sharply decreased, indicating that the water-dispersed cellulose microfibers rapidly absorbed water, and it was confirmed that excellent moisturizing ability could be obtained by increasing the water-retaining power of the water-dispersed cellulose microfibers .
實驗例4：水分散纖維素微纖維網路分散體的皮膚摩擦力確認 Experimental Example 4: Confirmation of skin friction force of water-dispersed cellulose microfiber network dispersion
將0.015乾燥重量%的水分散纖維素分散體塗抹在皮膚上，30分鐘之後，利用摩擦力儀(fractionmeter)測定皮膚摩擦力。其結果確認到，與塗抹前相比，皮膚摩擦力減少了10%(圖5)，並證明了殘留在皮膚上的纖維素微纖維網路分散體使皮膚變得柔軟。 0.015 % by dry weight of the water-dispersible cellulose dispersion was applied to the skin, and after 30 minutes, the skin friction was measured using a fractionmeter. As a result, it was confirmed that the skin friction force was reduced by 10% compared to before application ( FIG. 5 ), and it was confirmed that the cellulose microfibril network dispersion remaining on the skin softened the skin.
實驗例5：含有水分散纖維素微纖維網路分散體的劑型的增稠力確認 Experimental Example 5: Confirmation of Thickening Power of a Dosage Form Containing a Water-dispersed Cellulose Microfiber Network Dispersion
用表2示出的配方製造精華液劑型來進行評價(單位：重量%)。對製造後獲得的皮膚化妝材料的粘度進行測定，結果顯示出實施例1的比率越高，粘度越高的現象(圖6)。由此確認，不僅保持微纖維的結構，同時還顯示出現有纖維素所具有的增稠力。 The formulations shown in Table 2 were used to manufacture an essence formulation for evaluation (unit: % by weight). The viscosity of the skin cosmetic material obtained after production was measured, and as a result, the higher the ratio of Example 1, the higher the viscosity was shown ( FIG. 6 ). From this, it was confirmed that not only the structure of the microfibers was maintained, but also the thickening power possessed by existing cellulose was exhibited.
實驗例6：含有水分散纖維素微纖維網路分散體的劑型的水分保持力確認 Experimental Example 6: Confirmation of Water Retention of Dosage Forms Containing Water-dispersed Cellulose Microfiber Network Dispersion
為確認水分散纖維素微纖維網路分散體劑型的水分保持力，根據纖維素微纖維分散液的有/無而製備精華液劑型(比較例5、實施例2)之後，(重量%與表2相同)，塗抹在豬皮膚上，乾燥之後，滴加水來測定接觸角。其結果 能夠確認，隨著時間的推移，含有實施例1的劑型中的接觸角減少幅度大(圖7)。分析這是因為，即使纖維素微纖維包含在劑型中，也保持著吸引水而吸收的特性。 In order to confirm the water retention power of the water-dispersed cellulose microfiber network dispersion formulation, after preparing the essence formulation (Comparative Example 5, Example 2) according to the presence/absence of the cellulose microfiber dispersion, (weight % and Table 2) 2), smeared on pig skin, and after drying, water was added dropwise to measure the contact angle. as a result It was confirmed that the contact angle in the dosage form containing Example 1 decreased greatly over time ( FIG. 7 ). This is analyzed because, even if the cellulose microfibrils are contained in the dosage form, the property of attracting water and being absorbed is maintained.
實驗例7：水分散纖維素微纖維網路分散體的彈性增加功效評價 Experimental Example 7: Evaluation of Elasticity-Increasing Efficacy of Water-dispersed Cellulose Microfiber Network Dispersion
為確認上述合成的實施例1的功效，進行彈性測定實驗。在孔板上融化一定濃度的明膠之後，使之變硬而製成凝膠，在塗抹水分散纖維素微纖維網路分散體之後，使用質構分析儀(Texture Analyser)來測定彈性。彈性測定使用了如下方法：在質構分析儀上安裝尺寸小於明膠凝膠的面積的試樣，以恒定速度下落來按壓明膠凝膠來測定其壓力。此時，利用了如下原理：彈性增加時，表面的結構變得緻密，因此以恒定的力按壓時，阻力變強。通過下面的體外彈性評價方法，測定比較例2和0.03乾燥重量%的實施例1時，確認到與用比較例2處理的情況相比，用實施例1處理的情況下增加了約20%的彈性。這被解釋為，塗抹的纖維素微纖維在形成膜的同時，增加了彈性效果。另外，以10名普通人為物件對彈性改善度進行確認，結果確認到有顯著的增加。 To confirm the efficacy of Example 1 synthesized above, elasticity assay experiments were performed. After melting a certain concentration of gelatin on the orifice plate, it was hardened to form a gel, and after applying the water-dispersed cellulose microfiber network dispersion, the elasticity was measured using a texture analyzer (Texture Analyser). For the elasticity measurement, a sample having a size smaller than the area of the gelatin gel is mounted on a texture analyzer, and the pressure of the gelatin gel is measured by dropping at a constant speed to press the gelatin gel. At this time, the following principle is utilized: when the elasticity increases, the structure of the surface becomes dense, and therefore when pressed with a constant force, the resistance becomes stronger. When Comparative Example 2 and 0.03 dry weight % of Example 1 were measured by the following in vitro elasticity evaluation method, it was confirmed that the treatment with Example 1 increased by about 20% compared to the case treated with Comparative Example 2. elasticity. This is explained by the fact that the coated cellulose microfibrils, while forming the film, increase the elastic effect. In addition, the degree of elasticity improvement was confirmed with 10 ordinary people, and as a result, it was confirmed that there was a significant increase.
-實驗例8~實驗例12中所使用的實施例和比較例如下。 - Examples and comparative examples used in Experimental Example 8 to Experimental Example 12 are as follows.
實施例1是根據上述製備例1制得的生物纖維素微纖維網路分散體。 Example 1 is a biocellulose microfiber network dispersion prepared according to Preparation Example 1 above.
比較例6是蒸餾水。 Comparative Example 6 is distilled water.
比較例7是作為水溶性高分子的黃原膠。 Comparative Example 7 is xanthan gum which is a water-soluble polymer.
比較例8是不包含實施例1的精華液劑型。 Comparative Example 8 is a serum formulation that does not contain Example 1.
比較例9是不包含實施例1的護膚水劑型。 Comparative Example 9 is a skin lotion formulation that does not contain Example 1.
實施例4是包含0.05乾燥重量%的實施例1的精華液劑型。 Example 4 is a serum dosage form comprising 0.05 dry weight percent of Example 1.
實施例5是包含0.05乾燥重量%的實施例1的護膚水劑型。 Example 5 is a skin lotion formulation comprising 0.05 dry weight percent of Example 1.
實驗例8：生物纖維素微纖維水分散體網路組合物的皮膚安放確認 Experimental Example 8: Confirmation of skin placement of biocellulose microfiber aqueous dispersion network composition
為確認合成的實施例1是否保持原來的微纖維結構，使用掃描型電子顯微鏡(SEM)來進行確認。其結果，確認到纖維素保持微纖維形態(圖8的b、圖8的c、d及圖9的a)。 In order to confirm whether or not the synthesized Example 1 maintained the original microfiber structure, a scanning electron microscope (SEM) was used for confirmation. As a result, it was confirmed that the cellulose maintained the microfibril form (b in FIG. 8 , c and d in FIG. 8 , and a in FIG. 9 ).
為確認將0.01、0.05乾燥重量%的實施例1塗抹在皮膚時是否安放於皮膚上，塗抹在豬皮膚(2cm×2cm)上之後，進行乾燥並用SEM進行確認。由圖1可知，確認到豬皮膚表面也塗抹有生物纖維素微纖維水分散體網路組合物，由此證明了皮膚表面形成並安放有微纖維。另外，為確認0.05乾燥重量%的實施例1有多少塗抹在皮膚上，對塗抹的部分和未塗抹的部分的介面進行了測定，結果確認到塗抹的部分均被生物纖維素微纖維水分散體網路組合物覆蓋。由此確認到，將生物纖維素微纖維水分散體網路組合物塗抹在皮膚時，能夠覆蓋大部分的皮膚而不使微塵附著於皮膚。 In order to confirm whether or not Example 1 was applied to the skin at 0.01 or 0.05% by dry weight, it was applied to the skin of pigs (2 cm×2 cm), dried and confirmed by SEM. As can be seen from FIG. 1 , it was confirmed that the biocellulose microfiber aqueous dispersion network composition was also applied to the surface of the pig skin, thereby confirming that the microfibers were formed and settled on the skin surface. In addition, in order to confirm how much 0.05% by dry weight of Example 1 was applied to the skin, the interface between the applied part and the unapplied part was measured. As a result, it was confirmed that the applied part was all covered by the biocellulose microfiber aqueous dispersion. Net composition overlay. From this, it was confirmed that when the biocellulose microfiber aqueous dispersion network composition was applied to the skin, it was possible to cover most of the skin without causing fine dust to adhere to the skin.
實驗例9：生物纖維素微纖維水分散體網路組合物的電荷確認 Experimental Example 9: Charge Confirmation of Biocellulose Microfiber Aqueous Dispersion Network Composition
為確認上述實施例1的電荷，製備表3所示的精華液劑型，並測定比較例8以及實施例1、實施例4的Zeta電位。將實施例1、4、比較例8的表面電荷值示於表4。在實施例1的情況下，表面電荷值顯示出-77.5mV的負電荷，在實施例2的情況下，也顯示出-70.7mV的穩定的負電荷。但是，在比較例8的情況下，顯示出-7.1mV。對測定Zeta電位而言，-20mV~+20mV之間的值不能視為顯示出穩定的電荷，因此不能視為比較例8顯示出負電荷。由此能夠確認，由於生物纖 維素微纖維水分散體網路組合物的羧基具有負電荷，在應用於劑型上時也具有穩定的負電荷。 In order to confirm the electric charge of the above-mentioned Example 1, the serum formulations shown in Table 3 were prepared, and the Zeta potentials of Comparative Example 8, Example 1, and Example 4 were measured. Table 4 shows the surface charge values of Examples 1, 4, and Comparative Example 8. In the case of Example 1, the surface charge value showed a negative charge of -77.5 mV, and in the case of Example 2, it also showed a stable negative charge of -70.7 mV. However, in the case of Comparative Example 8, -7.1 mV was shown. For the measurement of the zeta potential, a value between -20mV and +20mV cannot be regarded as showing a stable electric charge, so Comparative Example 8 cannot be regarded as showing a negative electric charge. From this, it can be confirmed that due to the biological fiber The carboxyl group of the vitamin microfiber aqueous dispersion network composition has a negative charge, and also has a stable negative charge when applied to a dosage form.
實驗例10：生物纖維素微纖維水分散體網路組合物的微塵附著確認 Experimental example 10: Confirmation of dust adhesion of biocellulose microfiber aqueous dispersion network composition
在豬皮膚上塗抹0.05乾燥重量%的實施例1、比較例6，0.05乾燥重量%的比較例7之後，與未經處理的對照組一起塗抹1~5um的微塵替代物而進行乾燥，然後用SEM和螢光顯微鏡確認微塵替代物是否直接接觸皮膚表面。在螢光顯微鏡的情況下，對微塵替代物用紅色螢光進行處理，對皮膚用綠色螢光進行處理，對塗抹的水溶性高分子和生物纖維素微纖維水分散體不進行螢光處理，從而根據塗抹的物質來確認紅色顆粒是否直接接觸綠色皮膚。 After smearing 0.05 dry weight % of Example 1, Comparative Example 6, and 0.05 dry weight % of Comparative Example 7 on pig skin, 1~5um of fine dust substitute was applied together with the untreated control group for drying, and then used SEM and fluorescence microscopy confirm whether the dust substitute directly contacts the skin surface. In the case of fluorescence microscopy, the dust substitute is treated with red fluorescence, the skin is treated with green fluorescence, and the water-soluble polymer and biocellulose microfiber aqueous dispersion applied are not subjected to fluorescence treatment, Thereby, it can be confirmed whether the red particles are in direct contact with the green skin according to the substance applied.
由圖9、10可知，在用蒸餾水處理的情況下，確認到微塵與皮膚直接接觸(圖9的b和圖10的a)，在塗抹水溶性高分子的情況下，也確認到微塵滲透水溶性高分子而與皮膚直接接觸(圖10的b)。與此相對，在生物纖維素微纖維水分散體的情況下，細密的網路結構(微纖維間間距為10nm以下)隔絕微塵使之不直接接觸皮膚(圖9的a、圖10的c)。 As can be seen from Figures 9 and 10, in the case of treating with distilled water, it was confirmed that the fine dust was in direct contact with the skin (b in Figure 9 and a in Figure 10), and in the case of applying a water-soluble polymer, it was also confirmed that the fine dust penetrated and dissolved in water. direct contact with the skin (Fig. 10b). On the other hand, in the case of the biocellulose microfiber aqueous dispersion, the fine network structure (the distance between the microfibers is 10 nm or less) isolates the fine dust from direct contact with the skin (Fig. 9a, Fig. 10c) .
實驗例11：生物纖維素微纖維水分散體網路組合物的微塵附著率確認 Experimental Example 11: Confirmation of dust adhesion rate of biocellulose microfiber aqueous dispersion network composition
用表4表示的配方，製備包含生物纖維素微纖維水分散體網路組合物的護膚水劑型，對微塵附著程度進行確認。在聚甲基丙烯酸甲酯板(PMMA plate)上以1.3mg/cm2的量塗抹人工皮脂之後，進行乾燥，然後將實驗產品等量地塗抹在乾燥後的人工皮脂上後，進行乾燥。其後，將1~5um的微塵替代物暴露5分鐘之後，確認附著在聚甲基丙烯酸甲酯板上的微塵圖像以進行評價。 Using the formulation shown in Table 4, a skin lotion formulation containing the biocellulose microfiber aqueous dispersion network composition was prepared, and the degree of adhesion of fine dust was confirmed. After applying artificial sebum in an amount of 1.3 mg/cm 2 on a polymethyl methacrylate plate (PMMA plate), it was dried, and then an equal amount of the experimental product was applied on the dried artificial sebum, followed by drying. After that, after exposing the fine dust substitute of 1 to 5 um for 5 minutes, the image of the fine dust attached to the polymethyl methacrylate plate was confirmed for evaluation.
其結果，當將附著在未塗抹實驗產品的比較例6上的微塵附著率設為100%時，在比較例9的情況下微塵附著率為94%，在實施例5的情況下微塵 附著率為70%，確認微塵附著率減少。可認為，生物纖維素微纖維水分散體網路組合物自身所包含的負電荷排斥微塵的負電荷，從而防止微塵附著於包含生物纖維素微纖維水分散體網路組合物的劑型上。 As a result, when the adhesion rate of fine dust adhering to Comparative Example 6, which was not coated with the test product, was 100%, the adhesion rate of fine dust was 94% in the case of Comparative Example 9 and 94% in the case of Example 5. The adhesion rate was 70%, and it was confirmed that the fine dust adhesion rate decreased. It is believed that the negative charge contained in the biocellulose microfiber aqueous dispersion network composition itself repels the negative charge of the dust particles, thereby preventing the dust particles from adhering to the dosage form containing the biocellulose microfibril dispersion network composition.
實驗例12：生物纖維素微纖維水分散體網路組合物劑型的微塵清洗效果 Experimental example 12: Dust cleaning effect of biocellulose microfiber aqueous dispersion network composition dosage form
用表3所示的配方製備精華液劑型來進行評價(單位：重量%)。 Essence formulations were prepared with the formulations shown in Table 3 for evaluation (unit: % by weight).
若微塵直接附著於皮膚，則進入毛孔或皺紋之間，難以清洗且清洗效率也降低。因此，將規定量的生物纖維素微纖維網路水分散體以及包含生物纖維素微纖維網路水分散體的組合物的劑型塗抹於皮膚，並將1~5μm的微塵替代物塗抹在其上，用微溫水清洗之後，測定微塵替代物塗抹前、塗抹後、清洗後的圖像，從而評價微塵清洗率。 When the fine dust directly adheres to the skin, it enters between pores and wrinkles, making it difficult to clean and reducing the cleaning efficiency. Therefore, a prescribed amount of the aqueous dispersion of biocellulose microfibril network and the dosage form of the composition comprising the aqueous dispersion of biocellulose microfiber network are applied to the skin, and 1 to 5 μm of the dust substitute is applied thereon , after washing with lukewarm water, the images of the dust substitutes before, after application and after cleaning were measured to evaluate the dust removal rate.
其結果確認到，在未塗抹實驗產品的比較例6的情況下，微塵清洗率為58%，對於劑型評價而言，比較例9的微塵清洗率為85%，實施例5的微塵清洗率為99%，微塵清洗率得到提高。可認為，由於生物纖維素微纖維水分散體網路組合物在皮膚上形成微網而減少微塵直接吸附在皮膚，從而在清洗時容易去除微塵。 As a result, it was confirmed that in the case of Comparative Example 6 in which the test product was not applied, the dust removal rate was 58%. For the formulation evaluation, the dust removal rate of Comparative Example 9 was 85%, and the dust removal rate of Example 5 was 85%. 99%, the dust cleaning rate is improved. It is considered that since the biocellulose microfiber aqueous dispersion network composition forms a micronetwork on the skin, the direct adsorption of the fine dust on the skin is reduced, and the fine dust is easily removed during washing.
製備例2：含有生物纖維素微纖維網路水分散體的O/W乳化劑型精華液(100g)的製備 Preparation Example 2: Preparation of O/W Emulsion Essence (100g) Containing Biocellulose Microfiber Network Water Dispersion
根據下述表7的成分和含量，製備含有製備例1中製備的生物纖維素微纖維網路水分散體的O/W乳化劑型的精華液。 According to the ingredients and contents of Table 7 below, an O/W emulsion formulation containing the biocellulose microfiber network aqueous dispersion prepared in Preparation Example 1 was prepared.
量取生物纖維素微纖維網路水分散體至純化水，充分浸濕之後，利用分散機以1500rpm使之均勻地分散30分鐘以上。其後，添加原料2~5，加熱至60℃，與預先稱量並加熱至60℃的原料7~8混合，用均勻混合器以4500rpm混合10分鐘。其後，進行消泡、過濾、冷卻而完成劑型。 The biocellulose microfiber network aqueous dispersion was weighed into purified water, and after being sufficiently wetted, it was uniformly dispersed for 30 minutes or more at 1500 rpm using a disperser. Then, the raw materials 2 to 5 were added, heated to 60° C., mixed with the raw materials 7 to 8 weighed in advance and heated to 60° C., and mixed with a homomixer at 4500 rpm for 10 minutes. Thereafter, defoaming, filtration, and cooling are performed to complete the dosage form.
表7
實驗例13：生物纖維素微纖維水分散體網路組合物的角蛋白表面處理 Experimental Example 13: Keratin Surface Treatment of Biocellulose Microfiber Aqueous Dispersion Network Composition
用根據上述實施例6製備的含有生物纖維素微纖維水分散體網路的O/W乳化劑型的精華液，對人的毛髮和手指甲表面處理之後，進行乾燥，然後使用掃描電子顯微鏡(SEM)對毛髮和手指甲表面進行觀察。如圖11和圖12所示，能夠確認在毛髮和手指甲表面，生物纖維素微纖維網路水分散體形成如網的網路而覆蓋表面。 Human hair and fingernails were surface-treated with the serum in O/W emulsified formulation containing the biocellulose microfibril aqueous dispersion network prepared according to Example 6 above, dried, and then subjected to scanning electron microscopy (SEM). ) on the surface of hair and fingernails. As shown in FIGS. 11 and 12 , it was confirmed that on the surfaces of hair and fingernails, the biocellulose microfiber network aqueous dispersion formed a network like a network and covered the surfaces.
實驗例14：生物纖維素微纖維水分散體網路組合物處理前後的毛髮截面積對比 Experimental Example 14: Comparison of hair cross-sectional area before and after treatment with biocellulose microfiber aqueous dispersion network composition
以上述實驗例1的毛髮試樣為物件，對根據實施例6製備的含有生物纖維素微纖維網路水分散體的O/W乳化劑型的精華液處理前/後的毛髮截面積進行測定，將測定結果示於表8。10個毛髮試樣的平均截面積從精華液處理前的約4012
實驗例15：生物纖維素微纖維水分散體網路組合物處理前後的手指甲評價 Experimental Example 15: Evaluation of fingernails before and after treatment with biocellulose microfiber aqueous dispersion network composition
通過用於去除凝膠指甲(gel nail)的丙酮，對2名測驗物件的手指甲1天1次進行處理共5天而使手指甲受損後，使用根據上述實施例6製備的含有生物纖維素微纖維網路水分散體的O/W乳化劑型的精華液，對該2名測驗物件的手指甲進行處理，1天2次共處理2周。然後，使用SkiN-glossymetergL200®(Courage+Khazaka ElectronicgmbH)對手指甲的光澤程度進行測定，將其結果示於表9。在使用含有生物纖維素微纖維網路水分散體的精華液的情況下，與未 經任何處理的對照組相比，指甲的光澤得到了顯著提高。由於使用了丙酮等有機溶劑，指甲變得乾燥，表面角質層浮起而受損，生物纖維素微纖維網路水分散體在該受損的指甲表面形成保護網而防止指甲表面角蛋白層的脫落，從而有助於指甲的恢復，並通過光澤的增加確認了該結果。 After the fingernails of 2 test objects were treated with acetone for gel nail removal once a day for 5 days to damage the fingernails, the biofiber containing biofiber prepared according to the above Example 6 was used The essence of the O/W emulsion formulation of the aqueous dispersion of the plain microfiber network was treated with the fingernails of the two test objects, twice a day for a total of 2 weeks. Then, the glossiness of the fingernails was measured using SkiN-glossymetergL200® (Courage+Khazaka ElectronicgmbH), and the results are shown in Table 9. In the case of using a serum containing an aqueous dispersion of biocellulose microfibril networks, the same The gloss of the nails was significantly improved compared to any treated control. Due to the use of organic solvents such as acetone, the nails become dry, and the surface stratum corneum is lifted and damaged. shedding, thereby contributing to the recovery of the nails, and this result was confirmed by the increase in gloss.
Claims (12)
Applications Claiming Priority (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20160025765 | 2016-03-03 | ||
| KR10-2016-0025765 | 2016-03-03 | ||
| KR10-2016-0100599 | 2016-08-08 | ||
| KR20160100603 | 2016-08-08 | ||
| KR10-2016-0100603 | 2016-08-08 | ||
| KR20160100599 | 2016-08-08 | ||
| KR10-2017-0002301 | 2017-01-06 | ||
| KR1020170002301A KR20170103628A (en) | 2016-03-03 | 2017-01-06 | Composition containing Cellulose Nanofiber water dispersions |
| KR10-2017-0027902 | 2017-03-03 | ||
| KR1020170027902A KR102399486B1 (en) | 2016-08-08 | 2017-03-03 | Composition containing biocellulose microfibril network water dispersions for blocking particulate matter |
| KR1020170027721A KR102349932B1 (en) | 2016-08-08 | 2017-03-03 | Composition containing biocellulose microfibril network water dispersions for Protecting Keratin Structure |
| KR10-2017-0027721 | 2017-03-03 | ||
| KR10-2017-0027863 | 2017-03-03 | ||
| KR1020170027863A KR101816792B1 (en) | 2016-03-03 | 2017-03-03 | Composition containing biocellulose microfibril network water dispersions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201731481A TW201731481A (en) | 2017-09-16 |
| TWI759283B true TWI759283B (en) | 2022-04-01 |
Family
ID=60479765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW106107124A TWI759283B (en) | 2016-03-03 | 2017-03-03 | Composition containing biocellulose microfibril network water dispersions, compositions, and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI759283B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114960179A (en) * | 2021-12-06 | 2022-08-30 | 细胞生物科技有限公司 | Method for manufacturing anionic cellulose non-woven fabric and mask using anionic cellulose non-woven fabric |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120308624A1 (en) * | 2010-01-22 | 2012-12-06 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Viscous composition |
| US20150216784A1 (en) * | 2014-02-06 | 2015-08-06 | Nympheas International Corp. | Cosmetic composition containing fragments of bacterial cellulose film and method for manufacturing thereof |
-
2017
- 2017-03-03 TW TW106107124A patent/TWI759283B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120308624A1 (en) * | 2010-01-22 | 2012-12-06 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Viscous composition |
| US20150216784A1 (en) * | 2014-02-06 | 2015-08-06 | Nympheas International Corp. | Cosmetic composition containing fragments of bacterial cellulose film and method for manufacturing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201731481A (en) | 2017-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104736136B (en) | Beauty and make-up is used or medicinal moisturizing ingredient | |
| DE60028435T2 (en) | Use of at least one silicone graft polymer as a tightening agent | |
| JP5600005B2 (en) | Water-soluble electrospun sheet | |
| US7771753B2 (en) | Topical formulations comprising ceramic hydroxyapatite particles | |
| TWI352595B (en) | Cosmetic and cosmeceutical compositions for restor | |
| CN103561717B (en) | The method of the usage amount of the macromolecule thickener that the manufacture method of cosmetics, the preparation method of gel used for cosmetic and minimizing are allocated in cosmetic material | |
| US20010006680A1 (en) | Skin care moisturizers and cleansers | |
| CN108904302A (en) | A kind of fullerene topical composition | |
| KR102399486B1 (en) | Composition containing biocellulose microfibril network water dispersions for blocking particulate matter | |
| KR101816792B1 (en) | Composition containing biocellulose microfibril network water dispersions | |
| JP7004387B2 (en) | Biocellulose fine fiber aqueous dispersion network composition | |
| CN104905984A (en) | Cosmetic, external skin preparation, and medical instrument | |
| KR20150005928A (en) | Exopolysaccharide for the treatment and/or care of the skin, mucous membranes and/or nails | |
| CA2378644A1 (en) | Use of fibres as an anti-irritant agent in a cosmetic or dermatological composition | |
| CN108350012A (en) | New sugar derivatives gelling agent | |
| EP1877490B1 (en) | Silicone elastomer exfoliting compositions | |
| WO2017150950A1 (en) | Networked dispersion of biocellulose microfibrils in water | |
| KR20170103628A (en) | Composition containing Cellulose Nanofiber water dispersions | |
| JP2019011287A (en) | Cosmetic composition | |
| JP2002363436A (en) | Treated water-insoluble solid particle, preparation and use thereof | |
| TWI759283B (en) | Composition containing biocellulose microfibril network water dispersions, compositions, and uses thereof | |
| DE102005030864A1 (en) | Cosmetic formulation for moisturizing skin, improving elasticity of skin, hair and nails, reducing cellulite and care of sensitive skin contains lotus blossom extract | |
| EP4257116A1 (en) | Method for producing spicule coated with active ingredient for skin improvement and diamond, and diamond spicule cosmetic composition comprising same | |
| US8357355B2 (en) | Silicone elastomer exfoliating compositions | |
| KR100584814B1 (en) | Composition for external preparation |