CN101522166A - Skin external preparation and skin cleanser - Google Patents

Abstract

The purpose of the present invention is to provide an external preparation for skin, which has an effect of improving rough skin, is excellent in feeling of use, particularly in smooth feeling, is free from sticky feeling, and is excellent in stability. Further, an object of the present invention is to provide a skin cleanser which is particularly excellent in the usability and the cosmetic removal effect. That is, the external preparation for skin of the present invention is characterized by containing a block-type oxyalkylene derivative represented by the following formula : y- [ O (EO)_a－(AO)_b－(EO)_c－R]_k(I) Wherein Y is a residue of a polyol having 3 to 6 hydroxyl groups except a hydroxyl group, k is the number of hydroxyl groups of the polyol, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 6 carbon atoms, and each is added in a block form. a x k, b x k and c x k are each an average molar number of addition of an oxyethylene group, an oxyalkylene group having 3 to 6 carbon atoms, and an oxyethylene group, 0. ltoreq. a x k.ltoreq.100, 1. ltoreq. b x k.ltoreq.100, 0. ltoreq. c x k.ltoreq.100, wherein (a + c) x k > 1. The ratio of the total oxyethylene groups in the formula (I) to the total of the total oxyethylene groups in the formula (I) and oxyalkylene groups having 3 to 6 carbon atoms is 10 to 80% by mass. R is the same or different and is a C1-4 alkyl group. The skin cleansing agent of the present invention is characterized by containing 0.01 to 70 mass% of a block-type alkylene oxide derivative represented by the above formula (I) and 0.1 to 20 mass% of a humectant.

Description

Translated fromChinese

皮肤外用剂及皮肤清洁剂External skin preparations and skin cleansers

相关申请related application

本申请要求2006年9月29日提出的日本专利申请2006-269121号和2006年9月29日提出的日本专利申请2006-269123的优先权，所述申请在本文引入供参考。This application claims the benefit of Japanese Patent Application No. 2006-269121 filed on September 29, 2006 and Japanese Patent Application No. 2006-269123 filed on September 29, 2006, which are incorporated herein by reference.

技术领域technical field

本发明涉及皮肤外用剂和皮肤清洁剂，尤其涉及含有嵌段型氧化烯衍生物作为有效成分的皮肤外用剂和皮肤清洁剂的改良。The present invention relates to external skin preparations and skin cleansers, and more particularly to improvements in skin external preparations and skin cleansers containing block type oxyalkylene derivatives as active ingredients.

背景技术Background technique

作为评价皮肤外用剂的重要要素，可以提到维持美肤状态的功能以及使用感。另一方面，作为试图提高基剂稳定性的代表性方法，可以列举配合表面活性剂。As important elements for evaluating an external preparation for skin, the function of maintaining a beautiful skin state and the feeling of use can be mentioned. On the other hand, as a typical method for attempting to improve the stability of the base, blending a surfactant can be cited.

为了维持美肤状态，防止或改善皮肤粗糙、整理皮肤的皮沟、皮丘以及使表皮细胞的更新平稳进行变得重要。皮肤粗糙是以干燥或紫外线、表面活性剂为代表的刺激性物质等外部原因或者激素平衡失调等内部原因形成诱因而产生的肌肤麻烦。由这些麻烦引起的角质层屏障功能降低、角质层水分量下降或表皮更新的亢进、鳞层产生(起鳞)所导致的角质层粗糙化成为美容上的很大烦恼。In order to maintain a beautiful skin condition, it is important to prevent or improve skin roughness, smooth out skin grooves and hillocks, and smooth the renewal of epidermal cells. Rough skin is a skin trouble caused by external factors such as dryness, irritating substances such as ultraviolet rays and surfactants, or internal factors such as hormone imbalance. The reduction of the barrier function of the stratum corneum, the reduction of the water content of the stratum corneum, the enhancement of epidermal renewal, and the roughening of the stratum corneum due to the generation of scales (squamation) caused by these troubles have become a great trouble in cosmetics.

迄今作为显示了防止和改善皮肤粗糙的效果的有效成分，在皮肤外用剂中配合山梨醇、丙二醇、甘油等多元醇化合物和透明质酸等粘多糖类等保湿剂(例如参照专利文献1)、作为NMF(自然保湿因子)的氨基酸、凝血酸等药剂(例如参照专利文献2)以及各种提取物(例如参照专利文献3)。另外，使用用凡士林软膏等封闭剂补偿角质层屏障功能的方法(例如参照专利文献4)和用维生素、激素等活化皮肤细胞的方法(例如参照专利文献5)。So far, moisturizing agents such as polyol compounds such as sorbitol, propylene glycol, and glycerin, and mucopolysaccharides such as hyaluronic acid have been blended into skin external preparations as active ingredients that have shown the effect of preventing and improving rough skin (see, for example, Patent Document 1). , agents such as NMF (Natural Moisturizing Factor), amino acids, tranexamic acid (for example, refer to Patent Document 2), and various extracts (for example, refer to Patent Document 3). In addition, a method of compensating the barrier function of the stratum corneum with a sealant such as vaseline ointment (for example, see Patent Document 4) and a method of activating skin cells with vitamins, hormones, etc. (for example, see Patent Document 5) are used.

然而，为了提高保湿效果和皮肤粗糙改善效果，必须增加以甘油为首的保湿剂的配合量，结果，基剂的稳定性和使用性能有时会降低。另外，将这种基剂应用于皮肤时，具有被皮脂排拒、肌肤的吸收差等应该解决的问题。多糖在含醇多的配方体系中产生沉淀，DL-苏氨酸等氨基酸具有着色、变臭等缺点。凝血酸等药剂随时间的稳定性方面存在问题，另外，在使用凡士林等闭塞剂的情况下，具有带来油腻感、黏腻感等不适感的缺点。此外，在使用提取物、维生素、激素等的情况下，在与副作用等有关的安全性和随时间的稳定性方面存在必需解决的问题。However, in order to enhance the moisturizing effect and rough skin improving effect, it is necessary to increase the compounding amount of humectants including glycerin, and as a result, the stability and usability of the base sometimes deteriorate. In addition, when this base is applied to the skin, there are problems that should be solved, such as sebum rejection and poor skin absorption. Polysaccharides precipitate in alcohol-rich formula systems, and amino acids such as DL-threonine have disadvantages such as coloring and odor. Drugs such as tranexamic acid have problems in terms of stability over time. In addition, when occlusive agents such as vaseline are used, there is a disadvantage of causing discomfort such as greasy feeling and sticky feeling. Furthermore, in the case of using extracts, vitamins, hormones, etc., there are problems that must be solved in terms of safety and stability over time in relation to side effects and the like.

另外，在制备皮肤外用剂、尤其乳液的情况下，为了提高基剂的稳定性，通常配合表面活性剂。表面活性剂的配合效果方面，通过配合相当量，可以提高基剂的稳定性，但有时成为使用感变差的一个原因。在减少表面活性剂的配合量时，基剂的稳定性有恶化的倾向。兼顾稳定性与使用感是乳液配制时的课题之一。In addition, when preparing an external preparation for skin, especially an emulsion, a surfactant is usually blended in order to improve the stability of the base. In terms of the compounding effect of the surfactant, the stability of the base can be improved by compounding a considerable amount, but this may cause a deterioration in the feeling of use. When the compounding amount of the surfactant is reduced, the stability of the base tends to deteriorate. Balancing stability and usability is one of the issues in emulsion formulation.

为了减轻所述使用感，即黏腻感而配合多元醇等，但不能充分改善使用感。基于以上情况，希望开发具有皮肤粗糙改善效果、使用感良好而且提高基剂稳定性的成分。In order to reduce the feeling of use, that is, a sticky feeling, a polyhydric alcohol or the like is blended, but the feeling of use cannot be sufficiently improved. Based on the above circumstances, it is desired to develop ingredients that have an effect of improving rough skin, have a good feeling of use, and improve the stability of the base.

作为皮肤外用的卸妆清洁剂，以往常用化妆水型、乳液型、油型等各种类型。As makeup remover cleansers for external use on the skin, various types such as lotion type, lotion type, and oil type have been commonly used in the past.

一般，在化妆水型卸妆清洁剂中，作为具有洗涤作用的表面活性剂，配合对皮肤无刺激的温和的非离子表面活性剂或者两性表面活性剂。另一方面，油型清洁剂通过以具有溶剂作用的溶剂作为主要成分来溶解和分散化妆品，从而获得洗涤效果，另外，乳液型清洁剂主要通过油分和水分的溶剂作用来溶解和分散化妆品，从而获得洗涤效果。Generally, in lotion-type cleansing cleansers, mild nonionic surfactants or amphoteric surfactants that are not irritating to the skin are blended as surfactants having a cleansing effect. On the other hand, oil-type cleansers dissolve and disperse cosmetics by using a solvent with a solvent action as a main component to obtain a washing effect, and emulsion-type cleansers mainly dissolve and disperse cosmetics through the solvent action of oil and water, thereby Get a wash.

然而，最近，开发了对皮肤粘合性好且难以被水分、皮脂等破坏化妆并具有良好的化妆保持性的化妆品。因此，在卸妆清洁剂中，为了提高化妆品去除效果，教导了增加醇或表面活性剂，或者配合洗涤作用好的表面活性剂或溶解力强的溶剂等方法。Recently, however, cosmetics have been developed that are good in adhesion to the skin, are difficult to damage makeup by moisture, sebum, etc., and have good makeup retention. Therefore, in order to enhance the cosmetics removal effect in makeup-removing cleansers, methods such as adding alcohol or a surfactant, or adding a surfactant with a good cleaning effect or a solvent with a strong solubility have been taught.

然而，在配合了洗涤作用强的表面活性剂或溶解力强的溶剂的清洁剂中，所存在的问题是，由于其具有的强溶解力，在洗涤后产生了刺痛或发红，或者增强了此后使用的化妆品的刺激。因此，为了避免这些问题和实现强洁净力，开发了配合环状二甲基聚硅氧烷的卸妆清洁剂，然而具有难以冲洗掉等需要解决的问题。However, in detergents formulated with surfactants with strong detergency or solvents with strong dissolving power, there is a problem that, due to their strong dissolving power, stinging or redness occurs after washing, or increased Irritation from cosmetic products used thereafter. Therefore, in order to avoid these problems and achieve strong cleansing power, a makeup remover cleanser containing cyclic dimethyl polysiloxane has been developed, but there are problems that need to be solved, such as being difficult to rinse off.

另一方面，作为安全性高、使用感和皮肤亲和性良好的油性基剂，有人报告了特定的(聚)乙二醇二烷基醚(例如参照专利文献6)。然而，在配合该(聚)乙二醇二烷基醚的情况下，化妆品洁净性、冲洗性能等许多性能不是充分令人满意的。On the other hand, a specific (poly)ethylene glycol dialkyl ether has been reported as an oil-based agent with high safety and good usability and skin compatibility (see, for example, Patent Document 6). However, when this (poly)ethylene glycol dialkyl ether is compounded, many performances, such as cosmetic cleansing property and rinsing performance, are not fully satisfactory.

此外，有人报告了安全性、使用性良好、容易洗掉的含有特定氧化烯衍生物的皮肤清洁剂(例如参照专利文献7)。然而，即使在配合该特定的氧化烯衍生物的情况下，仍然留有洗涤后的皮肤的发涩感等问题，据认为这来源于共同配合的表面活性剂。In addition, a skin cleanser containing a specific alkylene oxide derivative that is safe, usable, and easy to wash off has been reported (for example, refer to Patent Document 7). However, even when this specific oxyalkylene derivative is blended, problems such as a rough feeling on the skin after washing remain, and this is considered to be attributable to the surfactant blended together.

专利文献1：日本特开平6-32728号公报Patent Document 1: Japanese Patent Application Laid-Open No. 6-32728

专利文献2：日本特开2006-160758号公报Patent Document 2: Japanese Patent Laid-Open No. 2006-160758

专利文献3：日本特许第3667291号公报Patent Document 3: Japanese Patent No. 3667291

专利文献4：日本特开平9-100225号公报Patent Document 4: Japanese Patent Application Laid-Open No. 9-100225

专利文献5：日本特开平7-277943号公报Patent Document 5: Japanese Patent Application Laid-Open No. 7-277943

专利文献6：日本特开平10-259112号公报Patent Document 6: Japanese Patent Application Laid-Open No. 10-259112

专利文献7：日本特开2003-221310号公报Patent Document 7: Japanese Patent Laid-Open No. 2003-221310

发明内容Contents of the invention

发明要解决的问题The problem to be solved by the invention

本发明鉴于上述情况而做出，其目的是提供具有皮肤粗糙改善效果、使用感尤其润滑性优异、无黏腻感和稳定性优异的皮肤外用剂。另外，本发明的目的是提供使用性和化妆品去除效果尤其优异的皮肤清洁剂。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an external preparation for skin that has an effect of improving rough skin, excellent in use feeling, especially lubricity, non-sticky feeling, and excellent stability. In addition, an object of the present invention is to provide a skin cleanser which is particularly excellent in usability and makeup removal effect.

用于解决问题的方法method used to solve the problem

为了解决上述问题，本发明人等进行了深入研究，结果发现，通过在皮肤外用剂中配合具有特定结构的嵌段型氧化烯衍生物，可以获得具有皮肤粗糙改善效果、使用感和稳定性优异的皮肤外用剂。In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies and found that by blending a block-type oxyalkylene derivative having a specific structure in an external skin preparation, it is possible to obtain a skin roughness-improving effect and excellent usability and stability. skin topical agents.

另外，在皮肤清洁剂中配合所述嵌段型氧化烯衍生物时，与化妆品的融合性良好，在洗涤过程中容易洗掉，洗涤后无黏腻感和发涩感等使用性优异，化妆品去除效果优异，而且对皮肤刺激性小，从而完成了本发明。In addition, when the block-type oxyalkylene derivative is blended in a skin cleanser, it has good compatibility with cosmetics, is easy to wash off during washing, and has excellent usability such as no sticky or astringent feeling after washing. The removal effect is excellent and the irritation to the skin is small, thereby completing the present invention.

也就是说，本发明的皮肤外用剂特征在于包含由下式(I)所示的嵌段型氧化烯衍生物：That is, the external preparation for skin of the present invention is characterized by comprising a block type oxyalkylene derivative represented by the following formula (I):

Y-[O(EO)_a-(AO)_b-(EO)_c-R]_k  (I)Y-[O(EO)_a -(AO)_b -(EO)_c -R]_k (I)

式中，Y是具有3～6个羟基的多元醇的除去了羟基的残基，k是所述多元醇的羟基数，EO是氧化乙烯基，AO是碳原子数3～6的氧化烯基，分别加成为嵌段状。a×k、b×k和c×k各自是氧化乙烯基、碳原子数3～6的氧化烯基、氧化乙烯基的平均加成摩尔数，0≤a×k≤100，1≤b×k≤100，0≤c×k≤100，其中(a+c)×k>1。相对于式(I)中的全部氧化乙烯基和碳原子数3～6的氧化烯基的总和，式(I)中的全部氧化乙烯基的比率为10～80质量％。R相同或不同，是碳原子数1～4的烃基。In the formula, Y is a residue of a polyhydric alcohol having 3 to 6 hydroxyl groups after removal of hydroxyl groups, k is the number of hydroxyl groups in the polyol, EO is an oxyethylene group, and AO is an oxyalkylene group with 3 to 6 carbon atoms , were added block-like. a×k, b×k, and c×k are the average addition moles of oxyethylene groups, oxyalkylene groups with 3 to 6 carbon atoms, and oxyethylene groups, 0≤a×k≤100, 1≤b× k≤100, 0≤c×k≤100, where (a+c)×k>1. The ratio of all the oxyethylene groups in the formula (I) is 10 to 80% by mass relative to the total of all the oxyethylene groups in the formula (I) and the oxyalkylene groups having 3 to 6 carbon atoms. R is the same or different, and is a hydrocarbon group having 1 to 4 carbon atoms.

在上述皮肤外用剂中，用上式(I)表示的嵌段型氧化烯衍生物的AO优选是氧化丁烯基。In the aforementioned external preparation for skin, AO of the block type oxyalkylene derivative represented by the above formula (I) is preferably an oxybutylene group.

另外，在所述皮肤外用剂中，由上式(I)所示的嵌段型氧化烯衍生物的a为0，AO与EO的加成顺序优选为相对于式中的Y是(AO)-(EO)。In addition, in the external skin preparation, a of the block type oxyalkylene derivative represented by the above formula (I) is 0, and the order of addition of AO and EO is preferably (AO) with respect to Y in the formula. -(EO).

在上述皮肤外用剂中，由上式(I)所示的嵌段型氧化烯衍生物优选以0.01～70质量％的量配合。In the above-mentioned external preparation for skin, the block type oxyalkylene derivative represented by the above formula (I) is preferably blended in an amount of 0.01 to 70% by mass.

另外，本发明提供了以上式(I)所示的嵌段型氧化烯衍生物作为有效成分的皮肤粗糙改善剂。In addition, the present invention provides a rough skin improving agent having a block type oxyalkylene derivative represented by the above formula (I) as an active ingredient.

另外，本发明提供了以上式(I)所示的嵌段型氧化烯衍生物作为有效成分的使用性提高剂。In addition, the present invention provides a block-type oxyalkylene derivative represented by the above formula (I) as a usability-enhancing agent as an active ingredient.

另外，在本发明中，所述使用性提高剂是指在将其涂抹于皮肤时可以提高使用感尤其润滑感，无黏腻感。In addition, in the present invention, the usability-enhancing agent means that when it is applied to the skin, it can improve the feeling of use, especially the feeling of lubricity, without sticky feeling.

另外，本发明的皮肤清洁剂特征在于含有0.01～70质量％的由上式(I)所示的嵌段型氧化烯衍生物和0.1～20质量％的保湿剂。In addition, the skin cleanser of the present invention is characterized by containing 0.01 to 70% by mass of the block type oxyalkylene derivative represented by the above formula (I) and 0.1 to 20% by mass of a humectant.

在所述皮肤清洁剂中，所述特定结构的嵌段型氧化烯衍生物的含量优选为0.1～20质量％。In the skin cleanser, the content of the specific structure block type oxyalkylene derivative is preferably 0.1 to 20% by mass.

在所述皮肤清洁剂中，上式(I)所示的嵌段型氧化烯衍生物的AO基团优选是氧化丁烯基。In the skin cleanser, the AO group of the block type oxyalkylene derivative represented by the above formula (I) is preferably an oxybutylene group.

另外，在所述皮肤清洁剂中，上式(I)所示的嵌段型氧化烯衍生物的a为0，AO与EO的加成顺序相对于式中的Y优选是(AO)-(EO)。In addition, in the skin cleanser, a of the block type oxyalkylene derivative represented by the above formula (I) is 0, and the order of addition of AO and EO is preferably (AO)-( EO).

所述保湿剂优先是选自二丙二醇、丙二醇、1，3-丁二醇和甘油中的一种或两种以上。The humectant is preferably one or more selected from dipropylene glycol, propylene glycol, 1,3-butanediol and glycerin.

发明的效果The effect of the invention

根据本发明，通过将具有特定结构的嵌段型氧化烯衍生物配合于皮肤外用剂中，可以获得具有皮肤粗糙改善效果、使用感尤其润滑感优异、无黏腻感且稳定性优异的皮肤外用剂。According to the present invention, by blending a block-type oxyalkylene derivative having a specific structure into an external skin preparation, it is possible to obtain a skin external preparation that has an improvement effect on skin roughness, excellent feeling of use, especially lubricity, no sticky feeling, and excellent stability. agent.

另外，尤其通过配合0.01～70质量％的所述嵌段型氧化烯衍生物与0.1～20质量％的保湿剂，可以获得与化妆品的融合性良好、洗涤过程中容易冲洗掉、洗涤后无黏腻感和发涩感等的使用性优异、化妆品去除效果优异并且皮肤刺激性小的皮肤清洁剂。In addition, especially by blending 0.01 to 70% by mass of the block-type oxyalkylene derivative and 0.1 to 20% by mass of a humectant, good compatibility with cosmetics, easy rinsing during washing, and no stickiness after washing can be obtained. A skin cleanser that is excellent in usability such as greasy feeling and astringent feeling, has an excellent makeup removal effect, and is less irritating to the skin.

具体实施方式Detailed ways

以下说明本发明的优选实施方案。Preferred embodiments of the present invention are described below.

本发明的皮肤外用剂和皮肤清洁剂包括下式(I)所示的嵌段型氧化烯衍生物：The skin external preparation and skin cleanser of the present invention comprise block type oxyalkylene derivatives represented by the following formula (I):

Y-[O(EO)_a-(AO)_b-(EO)_c-R]_k     (I)Y-[O(EO)_a -(AO)_b -(EO)_c -R]_k (I)

在上式(I)所示的氧化烯衍生物中，Y是具有3～6个羟基的多元醇的除去了羟基的残基，k是所述多元醇的羟基数，为3～6。作为具有3～6个羟基的化合物，可以列举k＝3的甘油和三羟甲基丙烷，k＝4的赤藓醇和季戊四醇，k＝5的木糖醇，k＝6的山梨醇和肌醇。在本发明的皮肤外用剂和皮肤清洁剂中配合的嵌段型氧化烯衍生物以前述具有3～6个羟基的多元醇的一种或两种以上的混合物的、除去了羟基的残基为基本骨架。In the oxyalkylene derivative represented by the above formula (I), Y is a residue of a polyhydric alcohol having 3 to 6 hydroxyl groups from which hydroxyl groups have been removed, and k is 3 to 6, which is the number of hydroxyl groups in the polyhydric alcohol. Examples of compounds having 3 to 6 hydroxyl groups include glycerol and trimethylolpropane with k=3, erythritol and pentaerythritol with k=4, xylitol with k=5, and sorbitol and inositol with k=6. The block-type oxyalkylene derivative compounded in the external skin preparation and skin cleanser of the present invention is a residue of one or more mixtures of polyhydric alcohols having 3 to 6 hydroxyl groups excluding the hydroxyl groups. Basic skeleton.

在本发明中，Y更优选是具有3-4个羟基的多元醇的、除去了羟基的残基，也就是说，优选满足3≤k≤4。在k为2以下时，在皮肤外用剂中配合时，润滑感有变差的倾向，而k为7以上时，具有产生黏腻感的倾向。另外，在皮肤清洁剂中配合的情况下，在k为2以下时，洗涤后的皮肤润滑感有变差的倾向，而k为7以上时，洗涤后皮肤具有产生黏腻感的倾向。In the present invention, Y is more preferably a residue of a polyhydric alcohol having 3 to 4 hydroxyl groups from which the hydroxyl groups have been removed, that is, it is preferable to satisfy 3≦k≦4. When k is 2 or less, the lubricating feeling tends to be deteriorated when blended in an external preparation for skin, and when k is 7 or more, sticky feeling tends to be produced. In addition, when k is added to a skin cleanser, when k is 2 or less, the smoothness of the skin after washing tends to deteriorate, and when k is 7 or more, the skin tends to have a sticky feeling after washing.

EO是碳原子数为2的氧化乙烯基。AO是碳原子数3～6的氧化烯基，具体地可以列举氧化丙烯基、氧化丁烯基、氧化异丁烯基、氧化叔丁烯基、氧化戊烯基、氧化己烯基等。优选的是氧化丙烯基和氧化丁烯基，更优选的是氧化丁烯基。EO is an oxyethylene group having 2 carbon atoms. AO is an oxyalkylene group having 3 to 6 carbon atoms, and specific examples include oxypropylene group, oxybutenyl group, oxyisobutenyl group, oxytert-butenyl group, oxypentenyl group, oxyhexenyl group, and the like. Preferred are oxypropylene and oxybutenyl, more preferred are oxybutenyl.

b×k是AO的平均加成摩尔数，1≤b×k≤100，优选3≤b×k≤70。a×k和c×k是EO的平均加成摩尔数，0≤a×k≤100，0≤c×k≤100，优选3≤a×k≤70，3≤c×k≤70。另外，上式(I)中的全部氧化乙烯基的平均加成摩尔数的优选范围是1<(a+c)×k≤200，更优选6≤(a+c)×k≤140。AO在本发明的嵌段型氧化烯衍生物中成为疏水性部位，在b×k为0时，在皮肤外用剂中配合时具有稳定性变差的倾向，而在超过100时，具有湿润的使用感变差的倾向。在皮肤清洁剂中配合时，在b×k为0或超过100时，化妆品去除效果很低，洗涤后的皮肤的保湿效果感具有变差的倾向。b×k is the average added mole number of AO, 1≤b×k≤100, preferably 3≤b×k≤70. a×k and c×k are the average added moles of EO, 0≤a×k≤100, 0≤c×k≤100, preferably 3≤a×k≤70, 3≤c×k≤70. In addition, the preferred range of the average added mole number of all oxyethylene groups in the above formula (I) is 1<(a+c)×k≤200, more preferably 6≤(a+c)×k≤140. AO acts as a hydrophobic part in the block type oxyalkylene derivative of the present invention, and when b×k is 0, the stability tends to deteriorate when blended in external skin preparations, and when it exceeds 100, it has a wet Tendency to deteriorate usability. When blended in a skin cleanser, when b×k is 0 or more than 100, the makeup removal effect is low, and the skin moisturizing effect after washing tends to be poor.

另外，在a×k或c×k为0时，在皮肤外用剂中配合时具有稳定性变差的倾向，而在超过100时，具有产生黏腻感的倾向。在皮肤清洁剂中配合时，在a×k或c×k为0时，不能发挥期待的化妆品去除效果，而在超过100时，具有洗涤后皮肤产生黏腻感的倾向。In addition, when a×k or c×k is 0, the stability tends to deteriorate when blended into external skin preparations, and when it exceeds 100, a sticky feeling tends to be produced. When blended in a skin cleanser, when a×k or c×k is 0, the expected makeup removal effect cannot be exhibited, and when it exceeds 100, the skin tends to feel sticky after washing.

相对于上式(I)中的AO与EO的总量，上式(I)中的全部EO的比例是10～80质量％，更优选为20～70质量％。在皮肤外用剂中配合的情况下，在前述比例小于10质量％时，具有湿润的使用感变差的倾向，而在大于80质量％时，具有产生黏腻感的倾向。另外，在皮肤清洁剂中配合的情况下，在所述比例小于10质量％时，具有化妆品去除效果变差的倾向，而在大于80质量％时，化妆品去除效果很小，具有洗涤后皮肤产生黏腻感的倾向。The ratio of all EO in the above formula (I) is 10 to 80% by mass, more preferably 20 to 70% by mass based on the total amount of AO and EO in the above formula (I). When blended in an external preparation for skin, when the aforementioned ratio is less than 10% by mass, the wet feeling in use tends to be deteriorated, and when it exceeds 80% by mass, a sticky feeling tends to be produced. In addition, in the case of blending in a skin cleanser, when the ratio is less than 10% by mass, the effect of removing cosmetics tends to be poor, and when it exceeds 80% by mass, the effect of removing cosmetics is small, resulting in skin irritation after washing. Tendency to feel sticky.

另外，AO与EO的加成方式为嵌段状，加成顺序为：相对于式中的Y，可以是(AO)-(EO)的顺序、(EO)-(AO)的顺序、(EO)-(AO)-(EO)的顺序中的任何一种。在本发明中，相对于式中的Y，(AO)-(EO)的顺序是特别优选的。在相对于式中的Y为(AO)-(EO)的顺序的情况下，相当于式中的a为0。In addition, the addition of AO and EO is block-like, and the order of addition is: relative to Y in the formula, it can be the order of (AO)-(EO), the order of (EO)-(AO), the order of (EO )-(AO)-(EO) in any order. In the present invention, the order of (AO)-(EO) is particularly preferable with respect to Y in the formula. When Y in the formula is in the order of (AO)-(EO), it corresponds to a being 0 in the formula.

R是碳原子数1～4的烃基，作为烃基，可以列举甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基等。在本发明中，甲基和乙基是优选的。在碳原子数大于5时，在皮肤外用剂中配合的情况下，具有湿润的使用感变差的倾向，而在皮肤清洁剂中配合的情况下，具有洗涤后皮肤的保湿效果感降低的倾向。另外，在本发明的皮肤外用剂和皮肤清洁剂中配合的嵌段型氧化烯衍生物中，一个分子中的R可以是相同的或者是不同的，也可以是一种在一个分子中具有相同R的嵌段型氧化烯衍生物，或者具有不同R的两种以上的混合物。R is a hydrocarbon group having 1 to 4 carbon atoms, and examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl. In the present invention, methyl and ethyl are preferred. When the number of carbon atoms is more than 5, when blended in skin external preparations, the feeling of moist use tends to deteriorate, and when blended in skin cleansers, the feeling of moisturizing effect of the skin after washing tends to decrease. . In addition, in the block type oxyalkylene derivatives compounded in the external skin preparation and skin cleanser of the present invention, R in one molecule may be the same or different, or one with the same R in one molecule may be used. A block type oxyalkylene derivative of R, or a mixture of two or more different Rs.

作为本发明的皮肤外用剂和皮肤清洁剂中配合的氧化烯衍生物，可以具体地列举POB(30)POE(30)甘油三甲醚、POB(30)POE(35)甘油三甲醚、POB(17)POE(28)甘油三甲醚、POB(27)POE(45)甘油三甲醚、POB(14)POE(34)甘油三甲醚、POB(22)POE(55)甘油三甲醚、POB(19)POE(55)甘油三甲醚、POB(40)POE(80)甘油三甲醚、POB(80)POE(40)甘油三甲醚、POB(30)POE(30)甘油三乙醚、POB(30)POE(35)甘油三乙醚、POB(14)POE(34)甘油三乙醚、POB(30)POE(30)甘油三丙醚、POE(30)POP(30)甘油三甲醚、POE(35)POP(40)甘油三甲醚、POE(41)POP(48)甘油三甲醚等。Specific examples of the alkylene oxide derivatives blended in the external skin preparation and skin cleanser of the present invention include POB (30) POE (30) trimethyl glyceryl ether, POB (30) POE (35) trimethyl glyceryl ether, POB (17 )POE(28) Trimethylglycerol, POB(27)POE(45)Triglycerin, POB(14)POE(34)Triglycerin, POB(22)POE(55)Triglycerin, POB(19)POE (55) Trimethylglycerin ether, POB(40)POE(80)Triglycerin trimethyl ether, POB(80)POE(40)Triglycerin trimethyl ether, POB(30)POE(30)Glycerin triethyl ether, POB(30)POE(35) ) Triethyl Glycerin Ether, POB(14) POE(34) Triethyl Glycerin Ether, POB(30) POE(30) Tripropyl Glycerin Ether, POE(30)POP(30) Trimethyl Glycerin Ether, POE(35)POP(40) Glycerin trimethyl ether, POE (41) POP (48) glycerol trimethyl ether, etc.

另外，所述POE、POP和POB各自是聚氧化乙烯、聚氧化丙烯和聚氧化丁烯的简称，下文有时用该简称来描述。In addition, the POE, POP, and POB are each an abbreviation of polyethylene oxide, polypropylene oxide, and butylene oxide, which is sometimes used for description below.

在本发明的皮肤外用剂和皮肤清洁剂中配合的氧化烯衍生物可以用公知的方法制造。例如，通过将具有羟基的多元醇等化合物与氧化乙烯和碳原子数3～6的氧化烯加成聚合，然后在碱性催化剂的存在下用烷基卤进行醚化反应来获得。The oxyalkylene derivative to be blended in the skin external preparation and skin cleanser of the present invention can be produced by a known method. For example, it can be obtained by addition-polymerizing a compound such as a polyhydric alcohol having a hydroxyl group with ethylene oxide and an alkylene oxide having 3 to 6 carbon atoms, and then carrying out an etherification reaction with an alkyl halide in the presence of a basic catalyst.

通过将这样制备的特定结构的氧化烯衍生物在皮肤外用剂中配合，具有改善皮肤粗糙的效果，可以获得使用感，尤其润滑感优异，无黏腻感和稳定性优异的皮肤外用剂。在本发明的皮肤外用剂中，上述具有特定结构的氧化烯衍生物的配合量优选相对于整个组合物为0.01～70质量％，更优选是0.1～20质量％。在配合量低于0.01质量％时，配合带来的效果可能不充分，而在配合量超过70质量％时，有可能产生黏腻感。By blending the oxyalkylene derivative of the specific structure prepared in this way into the skin external preparation, it has the effect of improving skin roughness, and can obtain a skin external preparation with excellent lubricating feeling, non-sticky feeling and excellent stability in use. In the external preparation for skin of the present invention, the amount of the above-mentioned alkylene oxide derivative having a specific structure is preferably 0.01 to 70% by mass, more preferably 0.1 to 20% by mass, based on the entire composition. When the blending amount is less than 0.01% by mass, the effect of blending may be insufficient, and when the blending amount exceeds 70% by mass, a sticky feeling may be produced.

另外，通过配合上述特定结构的氧化烯衍生物和保湿剂，可以获得洗涤过程中的易冲洗性、洗涤后无黏腻感和发涩感等使用性、与化妆品的融合性和化妆品去除效果均优异的低皮肤刺激性的皮肤清洁剂。在本发明的皮肤清洁剂中，所述嵌段型氧化烯衍生物的配合量通常相对于整个皮肤清洁剂为0.01～70质量％，优选是0.1～20质量％，尤其优选为1～10质量％。在配合量低于0.01质量％时，配合产生的效果有可能不充分，而在配合量超过70质量％时，有可能在洗涤后产生黏腻感。In addition, by blending the oxyalkylene derivatives of the above-mentioned specific structures and humectants, it is possible to obtain ease of rinsing during washing, usability such as no stickiness and astringent feeling after washing, compatibility with cosmetics, and cosmetics removal effect. Excellent low skin irritation skin cleanser. In the skin cleanser of the present invention, the compounded amount of the block type oxyalkylene derivative is usually 0.01 to 70% by mass, preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass, based on the entire skin cleanser. %. When the blending amount is less than 0.01% by mass, the blending effect may be insufficient, and when the blending amount exceeds 70% by mass, a sticky feeling may be produced after washing.

作为可在本发明的皮肤清洁剂中配合的保湿剂，可以具体地列举聚乙二醇、二丙二醇、丙二醇、甘油、1，3-丁二醇、木糖醇、山梨醇、麦芽糖醇、硫酸软骨素、透明质酸、硫酸粘液素、去端胶原(atelocollagen)、胆甾醇-12-羟基硬脂酸酯、乳酸钠、胆汁酸盐、dl-吡咯烷酮羧酸盐、短链可溶性胶原、双甘油(EO)PO加成物、缫丝花提取物、欧蓍草提取物、黄木樨提取物、N-月桂酰基-N’-羧基甲基-N’-(2-羟乙基)乙二胺钠、N-肉豆蔻酰基-N’-羧甲基-N’-(2-羟乙基)乙二胺钠、N-棕榈酰基-N’-羧甲基-N’-(2-羟乙基)乙二胺钠、N-月桂酰基-N’-羧甲基-N’-(2-羟乙基)乙二胺钾、N-月桂酰基-N’-羧甲基-N’-(2-羟乙基)乙二胺镁等。尤其优选的是选自二丙二醇、丙二醇、1，3-丁二醇和甘油中的一种或两种以上。Specific examples of humectants that can be incorporated into the skin cleanser of the present invention include polyethylene glycol, dipropylene glycol, propylene glycol, glycerin, 1,3-butanediol, xylitol, sorbitol, maltitol, and sulfuric acid. Chondroitin, hyaluronic acid, mucin sulfate, atelocollagen, cholesterol-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerol ( EO)PO adduct, silk flower extract, yarrow extract, sweet clover extract, N-lauroyl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine sodium , N-myristoyl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine sodium, N-palmitoyl-N'-carboxymethyl-N'-(2-hydroxyethyl ) Sodium ethylenediamine, N-lauroyl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine potassium, N-lauroyl-N'-carboxymethyl-N'-(2 -Hydroxyethyl) magnesium ethylenediamine, etc. Especially preferred is one or two or more selected from dipropylene glycol, propylene glycol, 1,3-butanediol, and glycerin.

在本发明的皮肤外用剂和皮肤清洁剂中，除了上述各必需成分以外，在不损害本发明效果的范围内，可以适宜配合常用化妆品、医药品或者准药品中使用的成分。以下列举了具体的可配合的成分。也就是说，本发明的皮肤外用剂和皮肤清洁剂除了上述各必需成分以外可以适宜配合下列成分来制备。In addition to the above-mentioned essential ingredients, the external preparation for skin and skin cleanser of the present invention may suitably contain ingredients commonly used in cosmetics, pharmaceuticals, or quasi-drugs within the range that does not impair the effects of the present invention. Specific components that can be blended are listed below. That is, the skin external preparation and skin cleanser of the present invention can be prepared by appropriately blending the following components in addition to the above-mentioned essential components.

作为粉末成分，可以列举无机粉末(例如滑石、高岭土、云母、绢云母(sericite)、白云母、金云母、合成云母、红云母、黑云母、蛭石、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、钨酸金属盐、镁、二氧化硅、沸石、硫酸钡、煅制硫酸钙(烧石膏)、磷酸钙、氟磷灰石、羟基磷灰石、陶瓷粉末、金属皂(例如肉豆蔻酸锌、棕榈酸钙、硬脂酸铝)、氮化硼等)；有机粉末(例如聚酰胺树脂粉末(尼龙粉末)、聚乙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、苯乙烯和丙烯酸的共聚物树脂粉末、苯并胍胺树脂粉末、聚四氟乙烯粉末、纤维素粉末等)；无机白色颜料(例如氧化锌等)；无机红色系颜料(例如钛酸铁等)；无机紫色系颜料(例如锰紫、钴紫等)；无机绿色系颜料(例如氧化铬、氢氧化铬、钛酸钴等)；无机蓝色系颜料(例如群青、绀青等)；珠光颜料(例如二氧化钛被覆云母、二氧化钛被覆氧氯化铋、二氧化钛被覆滑石、着色二氧化钛被覆云母、氯氧化铋、鱼鳞箔等)；金属粉末颜料(例如铝粉、铜粉等)；锆、钡或铝色淀等有机颜料(例如红色201号、红色202号、红色204号、红色205号、红色220号、红色226号、红色228号、红色405号、橙色203号、橙色204号、黄色205号、黄色401号和蓝色404号等有机颜料，红色3号、红色104号、红色106号、红色227号、红色230号、红色401号、红色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、绿色3号和蓝色1号等)；天然色素(例如叶绿素、β-胡萝卜素等)等。Examples of powder components include inorganic powders (such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, red mica, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, Barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, fumed calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyl Apatite, ceramic powder, metal soap (such as zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.); organic powder (such as polyamide resin powder (nylon powder), polyethylene powder, poly Methyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigments (such as zinc oxide, etc.) ; Inorganic red pigments (such as iron titanate, etc.); Inorganic violet pigments (such as manganese violet, cobalt violet, etc.); Inorganic green pigments (such as chromium oxide, chromium hydroxide, cobalt titanate, etc.); Inorganic blue pigments Pigments (such as ultramarine blue, cyan blue, etc.); pearlescent pigments (such as titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, titanium dioxide coated talc, colored titanium dioxide coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (such as aluminum powder , copper powder, etc.); organic pigments such as zirconium, barium or aluminum lakes (such as red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, Organic pigments such as Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505 No., orange No. 205, yellow No. 4, yellow No. 5, yellow No. 202, yellow No. 203, green No. 3 and blue No. 1, etc.); natural pigments (such as chlorophyll, β-carotene, etc.), etc.

作为液体油脂，例如可举出鳄梨油、山茶油、海龟油、澳洲坚果油、玉米油、貂油、橄榄油、菜籽油、蛋黄油、芝麻油、桃仁油、小麦胚芽油、山茶花油、蓖麻油、亚麻籽油、红花油、棉籽油、紫苏子油、大豆油、花生油、茶籽油、榧籽油、米糠油、桐油、日本泡桐油、霍霍巴油、胚芽油、三甘油等。Examples of liquid fats and oils include avocado oil, camellia oil, turtle oil, macadamia oil, corn oil, mink oil, olive oil, rapeseed oil, egg oil, sesame oil, peach kernel oil, wheat germ oil, camellia oil, Castor Oil, Linseed Oil, Safflower Oil, Cottonseed Oil, Perilla Seed Oil, Soybean Oil, Peanut Oil, Tea Seed Oil, Torreya Seed Oil, Rice Bran Oil, Tung Oil, Paulownia Oil, Jojoba Oil, Germ Oil, Triglycerin wait.

作为固体油脂，例如可以列举可可脂、椰子油、马脂、氢化椰子油、棕榈油、牛脂、羊脂、氢化牛脂、棕榈仁油、猪脂、牛骨脂、木蜡仁油、氢化油、牛脚油、野漆树蜡、氢化蓖麻油等。Examples of solid fats and oils include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, tallow, suet, hydrogenated tallow, palm kernel oil, lard, tallow, wood wax kernel oil, hydrogenated oil, Cow foot oil, wild sumac wax, hydrogenated castor oil, etc.

作为蜡，例如可以列举蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、杨梅蜡、中国蜡、鲸蜡、褐煤蜡、米糠蜡、羊毛脂、木棉蜡、乙酰化羊毛脂、液状羊毛脂、甘蔗蜡、羊毛脂酸异丙酯、月桂酸己酯、还原羊毛脂、希蒙德木蜡、硬质羊毛脂、紫胶蜡、POE羊毛脂醇醚、POE羊毛脂醇乙酸酯、POE胆甾醇醚、羊毛脂酸聚乙二醇、POE加氢羊毛脂醇醚等。Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, Chinese wax, spermaceti wax, montan wax, rice bran wax, lanolin, kapok wax, acetylated lanolin, liquid lanolin, Sugarcane wax, isopropyl lanolate, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE gall Sterol ether, polyethylene glycol lanolin acid, POE hydrogenated lanolin alcohol ether, etc.

作为烃油，例如可以列举液体石蜡、地蜡、角鲨烷、姥鲛烷、石蜡、纯地蜡、角鲨烯、凡士林、微晶蜡等。Examples of hydrocarbon oils include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresine, squalene, petrolatum, microcrystalline wax, and the like.

作为高级脂肪酸，例如可以列举月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山嵛酸、油酸、十一碳烯酸、异硬脂酸、亚油酸、亚麻酸、二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)等。Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, isostearic acid, linoleic acid, linolenic acid, eicosapenta enoic acid (EPA), docosahexaenoic acid (DHA), etc.

作为高级醇，例如可以列举直链醇(例如月桂醇、鲸蜡醇、硬脂醇、山嵛醇、肉豆蔻醇、油醇、十八十六醇(CetostearylAlcohol)等)；支链醇(例如单硬脂基甘油醚(鲨肝醇)、2-癸基十四醇、羊毛脂醇、胆甾醇、植物甾醇、十六烷醇、异硬脂醇、十八烷醇等)等。Examples of higher alcohols include linear alcohols (such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.); branched chain alcohols (such as Monostearyl glyceryl ether (batyl alcohol), 2-decyltetradecyl alcohol, lanolin alcohol, cholesterol, phytosterol, cetyl alcohol, isostearyl alcohol, stearyl alcohol, etc.) and the like.

作为酯油，可以列举肉豆蔻酸异丙酯、辛酸十六烷基酯、肉豆蔻酸十八烷基酯、棕榈酸异丙酯、硬脂酸丁酯、月桂酸己酯、肉豆蔻酸肉豆蔻酯、油酸癸酯、二甲基辛酸十六烷基酯、乳酸十六烷基酯、乳酸肉豆蔻酯、乙酰化羊毛脂、硬脂酸异十六烷基酯、异硬脂酸异十六烷基酯、12-羟基硬脂酸胆甾醇酯、二-2-乙基己酸乙二醇酯、二季戊四醇脂肪酸酯、单异硬脂酸N-烷二醇、二癸酸新戊二醇酯、苹果酸二异硬脂酯、二-2-庚基十一烷酸甘油酯、三-2-乙基己酸三羟甲基丙烷、三异硬脂酸三羟甲基丙烷、四-2-乙基己酸季戊四醇酯、三-2-乙基己酸甘油酯、三辛酸甘油酯、三异棕榈酸甘油酯、三异硬脂酸三羟甲基丙烷、鲸蜡基2-乙基己酸酯、2-乙基己基棕榈酸酯、三肉豆蔻酸甘油酯、三-2-庚基十一烷酸甘油酯、蓖麻油脂肪酸甲酯、油酸油酯、乙酰甘油酯、棕榈酸2-庚基十一烷基酯、己二酸二异丁酯、N-月桂酰基-L-谷氨酸-2-十八烷基酯、己二酸二-2-庚基十一烷基酯、月桂酸乙酯、癸二酸二-2-乙基己酯、肉豆蔻酸2-十六烷基酯、棕榈酸2-十六烷基酯、己二酸2-十六烷基酯、癸二酸二异丙酯、琥珀酸2-乙基己酯、柠檬酸三乙酯等。Examples of ester oils include isopropyl myristate, cetyl caprylate, stearyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate Myristyl, Decyl Oleate, Cetyl Dimethyl Caprylate, Cetyl Lactate, Myristyl Lactate, Acetylated Lanolin, Isocetyl Stearate, Isostearate Cetyl Ester, Cholesteryl 12-Hydroxystearate, Ethylene Glycol Di-2-Ethylhexanoate, Dipentaerythritol Fatty Acid Ester, N-Alkanediol Monoisostearate, Neodicapric Acid Pentylene Glycol Ester, Diisostearyl Malate, Glyceryl Di-2-heptylundecanoate, Trimethylolpropane Tri-2-Ethylhexanoate, Trimethylolpropane Triisostearate , Pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprylate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2 -Ethylhexanoate, 2-Ethylhexylpalmitate, Trimyristin, Tri-2-heptylundecanoate, Castor Oil Fatty Acid Methyl Ester, Oleate, Acetylglycerides , 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octadecyl ester, di-2-heptyldecyl adipate Monoalkyl esters, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexadecyl myristate, 2-hexadecyl palmitate, 2-hexadecyl adipate Alkyl esters, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, etc.

作为硅油，例如可以列举链状聚硅氧烷(例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、二苯基聚硅氧烷等)；环状聚硅氧烷(例如八甲基环状四聚硅氧烷、十甲基环状五聚硅氧烷、十二甲基环状六聚硅氧烷等)、形成3维网格结构的有机硅树脂、有机硅橡胶、各种改性聚硅氧烷(氨基改性聚硅氧烷、聚醚改性聚硅氧烷、烷基改性聚硅氧烷、氟改性聚硅氧烷等)、丙烯酸有机硅类等。As the silicone oil, for example, chain polysiloxane (such as dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane, etc.); Methyl cyclic tetrapolysiloxane, decamethyl cyclic pentapolysiloxane, dodecamethyl cyclic hexapolysiloxane, etc.), silicone resin forming a three-dimensional grid structure, silicone rubber, Various modified silicones (amino-modified silicones, polyether-modified silicones, alkyl-modified silicones, fluorine-modified silicones, etc.), acrylic silicones, etc. .

另外，在本发明的皮肤外用剂和皮肤清洁剂中，可以配合各种表面活性剂。In addition, various surfactants can be blended in the skin external preparation and skin cleansing agent of the present invention.

作为阴离子表面活性剂，例如可以列举脂肪酸皂(例如月桂酸钠、棕榈酸钠等)；高级烷基硫酸酯盐(例如月桂基硫酸钠、月桂基硫酸钾等)；烷基醚硫酸酯盐(例如POE-月桂基硫酸三乙醇胺、POE-月桂基硫酸钠等)；N-酰基肌氨酸(例如月桂酰基肌氨酸钠等)；高级脂肪酰胺磺酸盐(例如N-肉豆蔻酰-N-甲基牛磺酸钠、甲基椰油酸牛磺酸钠、月桂基甲基牛磺酸钠等)；磷酸酯盐(POE-油基醚磷酸钠、POE-硬脂酰基醚磷酸等)；硫代琥珀酸盐(例如二-2-乙基己基硫代琥珀酸钠、单月桂酰基单乙醇酰胺聚氧亚乙烯基硫代琥珀酸钠、月桂基聚丙二醇硫代琥珀酸钠等)；烷基苯磺酸盐(例如链十二烷基苯磺酸钠、链十二烷基苯磺酸三乙醇胺、链十二烷基苯磺酸等)；高级脂肪酸酯硫酸酯盐(例如氢化椰油酸甘油硫酸钠等)；N-酰基谷氨酸盐(例如N-月桂酰基谷氨酸单钠、N-硬脂酰基谷氨酸二钠、N-肉豆蔻酰基-L-谷氨酸单钠等)；硫酸化油(例如土耳其红油等)；POE-烷基醚羧酸；POE-烷基烯丙醚羧酸盐；α-烯烃磺酸盐；高级脂肪酸酯磺酸盐；仲醇硫酸酯盐；高级脂肪酸烷醇酰胺硫酸酯盐；月桂酰基单乙醇酰胺琥珀酸钠；N-棕榈酰基天冬氨酸双三乙醇胺；酪蛋白钠等。As anionic surfactants, for example, fatty acid soaps (such as sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (such as sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates ( Such as POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine (such as sodium lauroyl sarcosinate, etc.); higher fatty amide sulfonate (such as N-myristoyl-N -sodium methyl taurate, sodium methyl cocoate taurate, sodium lauryl methyl taurate, etc.); phosphate ester salts (POE-sodium oleyl ether phosphate, POE-stearyl ether phosphoric acid, etc.) ;Sulphosuccinate (such as di-2-ethylhexyl sodium sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium, lauryl polypropylene glycol sodium sulfosuccinate, etc.); Alkylbenzenesulfonates (such as sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, dodecylbenzenesulfonic acid, etc.); higher fatty acid ester sulfates (such as hydrogenated Sodium Cocoyl Glyceryl Sulfate, etc.); N-acyl glutamate (such as monosodium N-lauroyl glutamate, disodium N-stearyl glutamate, N-myristoyl-L-glutamate monosodium, etc.); sulfated oil (such as Turkish red oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; Secondary alcohol sulfate ester salt; higher fatty acid alkanolamide sulfate ester salt; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid bis-triethanolamine; sodium caseinate, etc.

作为阳离子表面活性剂，例如可以列举烷基三甲基铵盐(例如硬脂基三甲基氯化铵、月桂基三甲基氯化铵等)；烷基吡啶鎓盐(例如氯化十六烷基吡啶等)；二硬脂基二甲基氯化铵、二烷基二甲基铵盐；氯代聚(N，N’-二甲基-3，5-亚甲基哌啶)；烷基季铵盐；烷基二甲基苄基铵盐；烷基异喹啉鎓盐；二烷基吗啉鎓盐；POE-烷基胺；烷基胺盐；多胺脂肪酸衍生物；戊醇脂肪酸衍生物；苯扎氯铵；氯苄乙铵等。As the cationic surfactant, for example, alkyl trimethyl ammonium salts (such as stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, etc.); alkylpyridinium salts (such as cetyl chloride Alkylpyridine, etc.); Distearyldimethylammonium chloride, dialkyldimethylammonium salt; Chlorinated poly(N,N'-dimethyl-3,5-methylenepiperidine); Alkyl quaternary ammonium salts; alkyl dimethyl benzyl ammonium salts; alkyl isoquinolinium salts; dialkylmorpholinium salts; POE-alkylamines; alkylamine salts; polyamine fatty acid derivatives; alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride, etc.

作为两性表面活性剂，例如可以列举咪唑啉系两性表面活性剂(例如2-十一烷基-N，N，N-(羟乙基羧甲基)-2-咪唑啉钠、2-椰油基-2-咪唑啉氢氧化物-1-羧乙氧基-2钠盐等)；甜菜碱系表面活性剂(例如2-十七烷基-N-羧甲基-N-羟乙基咪唑啉甜菜碱、月桂基二甲基氨基乙酸甜菜碱、烷基甜菜碱、酰胺基甜菜碱、硫代甜菜碱等)等。As the amphoteric surfactant, for example, imidazoline-based amphoteric surfactants (such as 2-undecyl-N, N, N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-coco base-2-imidazoline hydroxide-1-carboxyethoxy-2 sodium salt, etc.); betaine-based surfactants (such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazole betaine, lauryl dimethyl glycine betaine, alkyl betaine, amido betaine, thiobetaine, etc.) etc.

作为亲油性非离子表面活性剂，例如可以列举失水山梨醇脂肪酸酯类(例如失水山梨醇单油酸酯、失水山梨醇单异硬脂酸酯、失水山梨醇单月桂酸酯、失水山梨醇单棕榈酸酯、失水山梨醇单硬脂酸酯、失水山梨醇倍半油酸酯、失水山梨醇三油酸酯、五-2-乙基己酸二甘油失水山梨醇、四-2-乙基己酸二甘油失水山梨醇等)；甘油聚甘油脂肪酸类(例如单棉籽油脂肪酸甘油酯、单芥酸甘油酯、倍半油酸甘油酯、单硬脂酸甘油酯、α，α’-油酸焦谷氨酸甘油酯、单硬脂酸甘油苹果酸等)；丙二醇脂肪酸酯类(例如单硬脂酸丙二醇等)；氢化蓖麻油衍生物；甘油烷基醚等。Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (such as sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, Sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexanoic acid diglycerol dehydration Sorbitol, tetra-2-ethylhexanoic acid diglyceride sorbitan, etc.); glycerol polyglycerol fatty acids (such as mono-cottonseed oil fatty acid glyceride, monoerucinate, sesquiolein glyceride, monostearin glyceryl monostearate, α,α'-oleic acid pyroglutamic acid glyceride, glyceryl monostearate malic acid, etc.); propylene glycol fatty acid esters (such as propylene glycol monostearate, etc.); hydrogenated castor oil derivatives; glycerol alkane base ether etc.

作为亲水性非离子表面活性剂，例如可以列举POE-失水山梨醇脂肪酸酯类(例如POE-失水山梨醇单油酸酯、POE-失水山梨醇单硬脂酸酯、POE-失水山梨醇单油酸酯、POE-失水山梨醇四油酸酯等)；POE山梨醇脂肪酸酯类(例如POE-山梨醇单月桂酸酯、POE-山梨醇单油酸酯、POE-山梨醇五油酸酯、POE-山梨醇单硬脂酸酯等)；POE-甘油脂肪酸酯类(例如POE-甘油单硬脂酸酯、POE-甘油单异硬脂酸酯、POE-甘油三异硬脂酸酯等POE-单油酸酯等)；POE-脂肪酸酯类(例如POE-二硬脂酸酯、POE-二油酸酯、二硬脂酸乙二醇等)；POE-烷基醚类(例如POE-月桂基醚、POE-油基醚、POE-硬脂基醚、POE-山嵛基醚、POE-2-十八烷基醚、POE-胆甾醇醚等)；普朗尼克(Poloxanlene)类(例如普朗尼克等)；POE-POP-烷基醚类(POE-POP-鲸蜡醚、POE-POP-2-癸基十四烷基醚、POE-POP-单丁基醚、POE-POP-氢化羊毛脂、POE-POP-甘油醚等)；四POE-四POE-乙二胺缩合物类(例如Tetronic等)；POE-蓖麻油氢化蓖麻油衍生物(例如POE-蓖麻油、POE-氢化蓖麻油、POE-氢化蓖麻油单异硬脂酸酯、POE-氢化蓖麻油三异硬脂酸酯、POE-氢化蓖麻油单焦谷氨酸单异硬脂酸二酯、POE-氢化蓖麻油马来酸等)；POE-蜂蜡-羊毛脂衍生物(例如POE-山梨醇蜂蜡等)；烷醇酰胺(例如椰油酸二乙醇酰胺、月桂酸单乙醇酰胺、脂肪酸异丙醇酰胺等)；POE-丙二醇脂肪酸酯；POE-烷基胺；POE-脂肪酰胺；蔗糖脂肪酸酯；烷基乙氧基二甲基胺氧化物；三油基磷酸等。As the hydrophilic nonionic surfactant, for example, POE-sorbitan fatty acid esters (such as POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan Sorbitan Monooleate, POE-Sorbitan Tetraoleate, etc.); POE Sorbitan fatty acid esters (such as POE-Sorbitan Monolaurate, POE-Sorbitan Monooleate, POE-Sorbitan alcohol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerol fatty acid esters (such as POE-glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triiso POE-monooleate, etc.); POE-fatty acid esters (such as POE-distearate, POE-dioleate, distearic acid ethylene glycol, etc.); POE-alkyl Ethers (such as POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-stearyl ether, POE-cholesteryl ether, etc.); Nick (Poloxanlene) class (such as Pluronic, etc.); POE-POP-alkyl ethers (POE-POP-cetyl ether, POE-POP-2-decyl tetradecyl ether, POE-POP-monobutyl base ether, POE-POP-hydrogenated lanolin, POE-POP-glycerin ether, etc.); tetraPOE-tetraPOE-ethylenediamine condensates (such as Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (such as POE -Castor Oil, POE-Hydrogenated Castor Oil, POE-Hydrogenated Castor Oil Monoisostearate, POE-Hydrogenated Castor Oil Triisostearate, POE-Hydrogenated Castor Oil Monopyroglutamic Monoisostearate Di esters, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax-lanolin derivatives (such as POE-sorbitol beeswax, etc.); alkanolamides (such as coconut acid diethanolamide, lauric acid monoethanolamide, fatty acid Isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty amide; sucrose fatty acid ester; alkyl ethoxy dimethylamine oxide; trioleyl phosphoric acid, etc.

作为天然水溶性高分子，例如可以列举植物系高分子(例如阿拉伯橡胶、黄蓍胶、半乳聚糖、瓜尔胶、卡罗布胶、刺梧桐树胶、卡拉胶、果胶、琼脂、榅桲籽(marmelo)、海藻溶胶(褐藻提取物)、淀粉(大米、玉米、马铃薯、小麦)、甘草酸)；微生物系高分子(例如黄原胶、糊精、琥珀酰聚糖、支链淀粉等)；动物系高分子(例如胶原、酪蛋白、白蛋白、明胶等)等。Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seeds (marmelo), seaweed sol (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (such as xanthan gum, dextrin, succinoglycan, pullulan, etc. ); animal-based polymers (such as collagen, casein, albumin, gelatin, etc.), etc.

作为半合成的水溶性高分子，例如可以列举淀粉系高分子(例如羧甲基淀粉、甲基羟丙基淀粉等)；纤维素系高分子(甲基纤维素、乙基纤维素、甲基羟丙基纤维素、羟乙基纤维素、纤维素硫酸钠、羟丙基纤维素、羧甲基纤维素、羧甲基纤维素钠、结晶纤维素、纤维素粉末等)；藻酸系高分子(例如藻酸钠、藻酸丙二醇酯等)等。As semi-synthetic water-soluble polymers, for example, starch-based polymers (such as carboxymethyl starch, methyl hydroxypropyl starch, etc.); Hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); high alginic acid Molecules (such as sodium alginate, propylene glycol alginate, etc.), etc.

作为合成的水溶性高分子，例如可以列举乙烯基系高分子(例如聚乙烯醇、聚乙烯基甲基醚、聚乙烯基吡咯烷酮、羧基乙烯基聚合物等)；聚氧化乙烯系高分子(例如聚乙二醇20000、40000、60000等)；丙烯酸系高分子(例如聚丙烯酸钠、聚丙烯酸乙酯、聚丙烯酰胺等)；聚乙烯亚胺；阳离子聚合物等。As a synthetic water-soluble polymer, for example, vinyl-based polymers (such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyethylene oxide-based polymers (such as polyethylene glycol 20000, 40000, 60000, etc.); acrylic polymers (such as sodium polyacrylate, polyethylacrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers, etc.

作为增稠剂，例如可以列举阿拉伯胶、卡拉胶、刺梧桐树胶、黄蓍胶、卡罗布胶、榅桲籽、酪蛋白、糊精、明胶、果胶酸钠、藻酸钠、甲基纤维素、乙基纤维素、CMC、羟乙基纤维素、羟丙基纤维素、PVA、PVM、PVP、聚丙烯酸钠、羧基乙烯基聚合物、刺槐豆胶、瓜尔胶、罗望子胶、二烷基二甲基硫酸铵纤维素、黄原胶、硅酸铝镁、膨润土、锂蒙脱石、硅酸铝镁(Veegum)、锂藻土、硅酸酐等。Examples of thickeners include gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum, quince seeds, casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose cellulose, ethyl cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, di Alkyl dimethyl ammonium sulfate cellulose, xanthan gum, aluminum magnesium silicate, bentonite, hectorite, aluminum magnesium silicate (Veegum), lithium diatomaceous earth, silicic anhydride, etc.

作为紫外线吸收剂，例如可以列举苯甲酸系紫外线吸收剂(例如对氨基苯甲酸(以下略记为PABA)、PABA单甘油酯、N，N-二丙氧基PABA乙基酯、N，N-二乙氧基PABA乙基酯、N，N-二甲基PABA乙基酯、N，N-二甲基PABA丁基酯、N，N-二甲基PABA乙基酯等)；氨茴酸系紫外线吸收剂(例如三甲环己基-N-乙酰基氨茴酸酯)、水杨酸系紫外线吸收剂(例如水杨酸戊酯、水杨酸三甲环己酯、高水杨酸酯、水杨酸辛酯、水杨酸苯酯、水杨酸苄酯、水杨酸对-异丙醇苯酯等)；肉桂酸系紫外线吸收剂(例如肉桂酸辛酯、肉桂酸乙基-4-异丙酯、肉桂酸甲基-2，5-二异丙酯、肉桂酸乙基-2，4-二异丙酯、肉桂酸甲基-2，4-二异丙酯、对甲氧基肉桂酸丙酯、对甲氧基肉桂酸异丙酯、对甲氧基肉桂酸异戊酯、对甲氧基肉桂酸辛酯(对甲氧基肉桂酸2-乙基己酯)、对甲氧基肉桂酸2-乙氧基乙酯、对甲氧基肉桂酸环己酯、乙基-α-氰基-β苯基肉桂酸酯、2-乙基己基-α-氰基-β苯基肉桂酸酯、甘油单-2-乙基己酰基-二对甲氧基肉桂酸酯等)；二苯甲酮系紫外线吸收剂(例如2，4-二羟基二苯甲酮、2，2’-二羟基-4-甲氧基二苯甲酮、2，2’-二羟基-4，4’-二甲氧基二苯甲酮、2，2’，4，4’-四羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4’-甲基二苯甲酮、2-羟基-4-甲氧基二苯甲酮-5-磺酸盐、4-苯基二苯甲酮、2-乙基己基-4’-苯基-二苯甲酮-2-羧酸酯、2-羟基-4-正辛氧基二苯甲酮、4-羟基-3-羧基二苯甲酮等)；3-(4’-甲基苯亚甲基)-d，1-樟脑、3-苯亚甲基-d，1-樟脑；2-苯基-5-甲基苯并噁唑；2，2’-羟基-5’-甲基苯基苯并三唑；2-(2’-羟基-5’-叔辛基苯基)苯并三唑；2-(2’-羟基-5’-甲基苯基)苯并三唑；二苄连氮；二茴香酰基甲烷；2-甲氧基-2’-叔丁基二苯甲酰基甲烷；5-(3，3-二甲基-2-亚降冰片烯基)-3-戊烷-2-酮等。As the ultraviolet absorber, for example, benzoic acid-based ultraviolet absorbers (such as p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N- Diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); anthranilic acid UV absorbers (such as trimethylcyclohexyl-N-acetyl anthranilate), salicylic acid UV absorbers (such as amyl salicylate, trimethylcyclohexyl salicylate, homosalicylate, water octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (such as octyl cinnamate, ethyl-4-isopropyl cinnamate Esters, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, p-methoxycinnamic acid Propyl ester, Isopropyl p-methoxycinnamate, Isoamyl p-methoxycinnamate, Octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), p-methoxycinnamate 2-Ethoxyethyl Acid, Cyclohexyl p-Methoxycinnamate, Ethyl-α-Cyano-β-Phenyl Cinnamate, 2-Ethylhexyl-α-Cyano-β-Phenyl Cinnamate esters, glycerol mono-2-ethylhexanoyl-di-p-methoxycinnamate, etc.); benzophenone-based UV absorbers (such as 2,4-dihydroxybenzophenone, 2,2'-bis Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone ketone, 4-hydroxy-3-carboxybenzophenone, etc.); 3-(4'-methylbenzylidene)-d, 1-camphor, 3-benzylidene-d, 1-camphor; 2 -Phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5'-methylphenylbenzotriazole; 2-(2'-hydroxy-5'-tert-octylphenyl)benzene Triazole; 2-(2'-Hydroxy-5'-methylphenyl)benzotriazole; Dibenzylazine; Dianisylmethane; 2-Methoxy-2'-tert-butylbenzotriazole Acylmethane; 5-(3,3-dimethyl-2-norbornenylidene)-3-pentan-2-one, etc.

作为低级醇，例如可以列举乙醇、丙醇、异丙醇、异丁醇、叔丁醇等。As a lower alcohol, ethanol, propanol, isopropanol, isobutanol, tert-butanol etc. are mentioned, for example.

作为有机胺，例如可以列举单乙醇胺、二乙醇胺、三乙醇胺、吗啉、三异丙醇胺、2-氨基-2-甲基-1，3-丙二醇、2-氨基-2-甲基-1-丙醇等。Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1 - propanol etc.

作为螯合剂，例如可以列举1-羟基乙烷-1，1-二膦酸、1-羟基乙烷-1，1-二膦酸四钠盐、乙二胺四乙酸二钠、乙二胺四乙酸三钠、乙二胺四乙酸四钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡萄糖酸、磷酸、柠檬酸、抗坏血酸、琥珀酸、乙二胺四乙酸、乙二胺羟乙基三醋酸三钠等。As the chelating agent, for example, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, ethylenediaminetetra Trisodium Acetate, Tetrasodium EDTA, Sodium Citrate, Sodium Polyphosphate, Sodium Metaphosphate, Gluconic Acid, Phosphoric Acid, Citric Acid, Ascorbic Acid, Succinic Acid, EDTA, EDTA Trisodium acetate, etc.

作为抗氧化剂，例如可以列举生育酚、二丁基羟基甲苯、丁基羟基茴香醚、没食子酸酯类等。Examples of antioxidants include tocopherol, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

作为抗氧化助剂，例如可以列举磷酸、柠檬酸、抗坏血酸、马来酸、丙二酸、琥珀酸、富马酸、脑磷脂、六偏磷酸盐、植酸、乙二胺四乙酸等。Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid and the like.

尤其，作为皮肤外用剂中的任意成分，可以列举下述保湿剂、多元醇、单糖和寡糖。In particular, as optional components in external preparations for skin, the following humectants, polyhydric alcohols, monosaccharides, and oligosaccharides can be cited.

作为保湿剂，例如可以列举聚乙二醇、丙二醇、甘油、1，3-丁二醇、木糖醇、山梨醇、麦芽糖醇、硫酸软骨素、透明质酸、硫酸粘液素、去端胶原(atelocollagen)、胆甾醇-12-羟基硬脂酸酯、乳酸钠、胆汁酸盐、dl-吡咯烷酮羧酸盐、短链可溶性胶原、双甘油(EO)PO加成物、缫丝花提取物、欧蓍草提取物、黄木樨提取物等。As a humectant, for example, polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucin sulfate, decapitated collagen ( atelocollagen), cholesterol-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerol (EO) PO adduct, silk flower extract, yarrow Grass Extract, Chrysanthemum Extract, etc.

作为多元醇，例如可以列举二元醇(例如乙二醇、丙二醇、三亚甲基二醇、1，2-丁二醇、1，3-丁二醇、四亚甲基二醇、2，3-丁二醇、戊二醇、2-丁烯-1，4-二醇、己二醇、辛二醇等)；3元醇(例如甘油、三羟甲基丙烷等)；4元醇(例如1，2，6-己三醇等季戊四醇等)；5元醇(例如木糖醇等)；6元醇(例如山梨醇、甘露醇)；多元醇聚合物(例如二乙二醇、二丙二醇、三乙二醇、聚丙二醇、四乙二醇、二甘油、聚乙二醇、三甘油、四甘油、聚甘油等)；2元醇烷基醚类(例如乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、乙二醇单苯基醚、乙二醇单己基醚、乙二醇单2-甲基己基醚、乙二醇异戊基醚、乙二醇苄基醚、乙二醇异丙基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚等)；2元醇烷基醚类(例如二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇单丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇丁基醚、二乙二醇甲基乙基醚、三乙二醇单甲基醚、三乙二醇单乙基醚、丙二醇单甲基醚、丙二醇单乙基醚、丙二醇单丁基醚、丙二醇异丙基醚、二丙二醇甲基醚、二丙二醇乙基醚、二丙二醇丁基醚等)；2元醇醚酯(例如乙二醇单甲基醚乙酸酯、乙二醇单乙基醚乙酸酯、乙二醇单丁基醚乙酸酯、乙二醇单苯基醚乙酸酯、乙二醇二己二酸酯、乙二醇二琥珀酸酯、二乙二醇单乙基醚乙酸酯、二乙二醇单丁基醚乙酸酯、丙二醇单甲基醚乙酸酯、丙二醇单乙基醚乙酸酯、丙二醇单丙基醚乙酸酯、丙二酸单苯基醚乙酸酯等)；甘油单烷基醚(例如鲛肝醇、鲨油醇、鲨肝醇等)；糖醇(例如山梨醇、麦芽糖醇、麦芽三糖、甘露醇、蔗糖、赤藓糖醇、葡萄糖、果糖、淀粉分解糖、麦芽糖、木糖、淀粉分解糖还原醇等)；四氢糠醇；POE-四氢糠醇；POP-丁基醚；POP-POE-丁基醚；三聚氧亚丙基甘油醚；POP-甘油醚；POP-甘油醚磷酸；POP-POE-季戊四醇醚、聚甘油等。Examples of polyhydric alcohols include dihydric alcohols (such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol, 2,3 -butanediol, pentanediol, 2-butene-1,4-diol, hexanediol, octanediol, etc.); 3-hydric alcohols (such as glycerin, trimethylolpropane, etc.); 4-hydric alcohols ( Such as 1,2,6-hexanetriol and other pentaerythritol, etc.); 5-hydric alcohols (such as xylitol, etc.); 6-hydric alcohols (such as sorbitol, mannitol); polyol polymers (such as diethylene glycol, Propylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerol, etc.); dihydric alcohol alkyl ethers (such as ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, Ethylene glycol monohexyl ether, Ethylene glycol mono 2-methylhexyl ether, Ethylene glycol isopentyl ether , ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.); dihydric alcohol alkyl ethers ( For example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); Dihydric alcohol ether esters (such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ether Acetate, Ethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monophenyl Ether Acetate, Ethylene Glycol Diadipate, Ethylene Glycol Disuccinate, Diethylene Glycol Monoethylene Diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, monophenyl malonate Ether acetate, etc.); Glycerol monoalkyl ethers (such as chimeryl alcohol, batyl alcohol, batyl alcohol, etc.); sugar alcohols (such as sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol Sugar alcohol, glucose, fructose, amylolytic sugar, maltose, xylose, amylolytic sugar reducing alcohol, etc.); tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP-POE-butyl ether; trimerization Oxypropylene glyceryl ether; POP-glyceryl ether; POP-glyceryl ether phosphoric acid; POP-POE-pentaerythritol ether, polyglycerin, etc.

单糖例如可举出三碳糖(例如D-甘油醛、二羟基丙酮)；四碳糖(例如D-赤藓糖、D-赤藓酮糖、D-苏糖、赤藓糖醇等)；五碳糖(例如L-阿拉伯糖、D-木糖、L-来苏糖、D-阿拉伯糖、D-核糖、D-核酮糖、D-木酮糖、L-木酮糖等)；六碳糖(例如D-葡萄糖、D-塔罗糖、D-阿洛酮糖、D-半乳糖、D-果糖、L-半乳糖、L-甘露糖、D-塔格糖等)；七碳糖(例如庚醛糖、庚糖等)；八碳糖(例如辛酮糖等)；脱氧糖(例如2-脱氧-D-核糖、6-脱氧-L-半乳糖、6-脱氧-L-甘露糖等)；氨基糖(例如D-葡萄糖胺、D-半乳糖胺、唾液酸、氨基糖醛酸、胞壁糖等)；糖醛酸(例如D-葡糖醛酸、D-甘露糖醛酸、L-古洛糖醛酸、D-半乳糖醛酸、L-艾杜糖醛酸等)等。Examples of monosaccharides include three-carbon sugars (such as D-glyceraldehyde, dihydroxyacetone); four-carbon sugars (such as D-erythrose, D-erythrulose, D-threose, erythritol, etc.) ;Five-carbon sugars (such as L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.) ; Six-carbon sugars (such as D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); Seven-carbon sugars (such as aldoheptose, heptose, etc.); eight-carbon sugars (such as octulose, etc.); deoxysugars (such as 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy- L-mannose, etc.); amino sugars (such as D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramose, etc.); uronic acids (such as D-glucuronic acid, D- mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.), etc.

寡糖例如可举出蔗糖、龙胆三糖、伞形糖、乳糖、车前糖、α，α-海藻糖、蜜三糖、水苏糖、毛蕊花糖类等。Examples of oligosaccharides include sucrose, gentiotriose, umbelliferose, lactose, psyllose, α,α-trehalose, raffinose, stachyose, and verbascose.

作为氨基酸，例如列举中性氨基酸(例如苏氨酸、半胱氨酸等)；碱性氨基酸(例如羟基赖氨酸等)等。另外，作为氨基酸衍生物，例如可以列举酰基肌氨酸钠(月桂酰基肌氨酸钠)、酰基谷氨酸盐、酰基β-丙氨酸钠、谷胱甘肽、吡咯烷酮羧酸等。Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Moreover, examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

尤其，作为皮肤清洁剂中的任意成分，可以列举下述氨基酸、高分子乳液、pH调节剂和维生素类。In particular, the following amino acids, polymer emulsions, pH regulators, and vitamins are exemplified as optional components in the skin cleanser.

作为氨基酸，例如列举中性氨基酸(例如苏氨酸、半胱氨酸等)；碱性氨基酸(例如羟基赖氨酸等)等。另外，作为氨基酸衍生物，例如可以列举酰基肌氨酸钠(月桂酰基肌氨酸钠)、酰基谷氨酸盐、酰基β-丙氨酸钠、谷胱甘肽、吡咯烷酮羧酸等。Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Moreover, examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

作为高分子乳液，例如可以列举丙烯酸树脂乳液、聚丙烯酸乙酯乳剂、丙烯酸树脂液、聚丙烯酸烷基酯乳液、聚醋酸乙烯酯树脂乳液、天然胶乳等。Examples of polymer emulsions include acrylic resin emulsions, polyethylacrylate emulsions, acrylic resin liquids, polyalkylacrylate emulsions, polyvinyl acetate resin emulsions, natural rubber latex, and the like.

作为pH调节剂，例如可以列举乳酸-乳酸钠、柠檬酸-柠檬酸钠、琥珀酸-琥珀酸钠等缓冲剂等。Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

作为维生素类，例如可以列举维生素A、B1、B2、B6、C、E及其衍生物、泛酸及其衍生物、生物素等。Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin, and the like.

作为可以在本发明的皮肤外用剂和皮肤清洁剂中配合的其它成分，例如可以列举防腐剂(对羟基苯甲酸乙酯、对羟基苯甲酸丁酯等)；美白剂(例如胎盘提取物、虎耳草提取物、熊果苷等)；消炎药(例如甘草酸衍生物、甘草次酸衍生物、水杨酸衍生物、日扁柏素(hinokitiol)、氧化锌、尿囊素等)；促进血液循环剂(例如壬酸香草酰胺、烟酸、烟酸苄酯、烟酸生育酚酯、烟酸β-丁氧基酯、烟酸β-丁氧基乙酯、米诺地尔或其类似物、维生素E类、γ-谷维素、烷氧基羰基吡啶N-氧化物、卡普氯铵、乙酰胆碱或其衍生物、辣椒素、姜油酮、斑螯酊、鱼石脂、鞣酸、α-龙脑、烟酸肌醇酯、环扁桃酯、肉桂苯哌嗪、苯甲唑啉、戊脉胺、顶花防己碱等)；各种提取物(例如生姜、关黄柏、黄柏、黄莲、紫色素、芍药、印度当药、桦木、鼠尾草、枇杷、人参、芦荟、锦葵、鸢尾草、葡萄、薏苡仁、丝瓜、百合、藏红花、川芎、金丝桃、芒柄花根、大蒜、辣椒、陈皮、当归、牡丹、海藻等)；赋活剂(例如泛醇基乙醚、烟酰胺、生物素、泛酸、蜂王浆、感光素、胆甾醇衍生物等)；抗脂溢剂(例如吡多辛、硫磺、二甲硫蒽等)；抗炎剂(例如氨甲环酸、硫代牛磺酸、亚牛磺酸等)等。As other ingredients that can be mixed in the skin external preparation and skin cleanser of the present invention, for example, preservatives (ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, etc.); whitening agents (such as placenta extract, tiger ear grass extract, arbutin, etc.); anti-inflammatory drugs (such as glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); Circulatory agents (such as nonanoic vanillamide, niacin, benzyl nicotinate, tocopheryl nicotinate, beta-butoxy nicotinate, beta-butoxyethyl nicotinate, minoxidil, or their analogs , vitamin E, γ-oryzanol, alkoxycarbonylpyridine N-oxide, carpronium chloride, acetylcholine or its derivatives, capsaicin, zingerone, canola tincture, ichthyol, tannic acid, α-borneol , inositol nicotinate, cyclomandelic ester, cinnamon phenylpiperazine, benzoline, pentameramine, tetrandrine, etc); , peony, Indian herbal medicine, birch, sage, loquat, ginseng, aloe, mallow, orris, grape, coix seed, loofah, lily, saffron, chuanxiong, hypericum, formonice root, garlic, pepper , tangerine peel, angelica, peony, seaweed, etc.); active agents (such as panthenyl ether, nicotinamide, biotin, pantothenic acid, royal jelly, photosensitive pigment, cholesterol derivatives, etc.); anti-seborrheic agents (such as pyridoxine , sulfur, dimethylthioanthrene, etc.); anti-inflammatory agents (such as tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.

本发明的皮肤外用剂和皮肤清洁剂可以是任意剂型，例如可以列举溶液系、增溶系、乳化系、粉末分散系、水-油二相系、水-油-粉末三相系剂型。The skin external preparation and skin cleansing agent of the present invention can be in any dosage form, for example, solution type, solubilization type, emulsification type, powder dispersion type, water-oil two-phase system, water-oil-powder three-phase system dosage form can be mentioned.

本发明的皮肤外用剂可以是化妆水、凝胶、雾化剂、喷雾、慕司、走珠、膏(stick)等形式。The skin external preparation of the present invention may be in the form of lotion, gel, atomizer, spray, mousse, roll-on, stick or the like.

本发明的皮肤清洁剂适宜用于皮肤的清洁，尤其化妆后和涂抹防晒剂后的皮肤的清洁，优选为凝胶状或霜状的形式。The skin cleanser according to the invention is suitable for cleansing the skin, especially after makeup and sunscreen application, preferably in the form of a gel or a cream.

以下结合实施例来更具体地说明本发明。另外，本发明不限于这些实施例。只要没有特别说明，配合量以质量％表示。The present invention is described more specifically below in conjunction with embodiment. In addition, the present invention is not limited to these Examples. Unless otherwise specified, the compounding quantity is shown by mass %.

实施例1Example 1

首先，进行本发明的皮肤外用剂的使用性和稳定性的评价试验。First, evaluation tests for usability and stability of the external preparation for skin of the present invention were performed.

首先，说明本试验中使用的皮肤外用剂的评价方法。皮肤外用剂的涂抹部位是脸颊。First, the evaluation method of the external preparation for skin used in this test will be described. The application site of the skin external preparation is the cheek.

另外，用作对照的现有皮肤外用剂的组成如下所示：In addition, the composition of the conventional skin external preparation used as a control is as follows:

(水相部分)(water phase part)

(1)甘油                     10.0质量％(1) Glycerin 10.0% by mass

(2)羧基乙烯基聚合物          0.1(2) carboxy vinyl polymer 0.1

(3)氢氧化钾                  5.0(3) Potassium hydroxide 5.0

(4)山梨醇                    3.0(4) Sorbitol 3.0

(5)乙醇                      4.0(5) Ethanol 4.0

(6)纯化水                    余量(6) Balance of purified water

(油相部分)(oil phase part)

(7)液体石蜡                  5.0(7) Liquid paraffin 5.0

(8)三-2-乙基己酸甘油酯       4.0(8) Glyceryl tri-2-ethylhexanoate 4.0

(9)辛酸十六醇酯              2.0(9) Cetyl octanoate 2.0

(10)防腐剂                   适量(10) Appropriate amount of preservatives

(11)香料                     适量(11) Appropriate amount of spices

(评价1)：皮肤的润滑感(Evaluation 1): Skin lubricating feeling

关于皮肤外用剂的使用过程中和使用后的皮肤的润滑感，由10名专业受试者实际使用以下所示试验例的皮肤外用剂和作为对照的现有皮肤外用剂(作为保湿剂配合甘油的组成)，根据以下评分基准来评定分数。这里的分数评定以对照皮肤外用剂为0来实施。另外，计算各受试者的分数的总和除以受试者人数的平均值，根据以下评价基准给出评价结果。With regard to the lubricating feeling of the skin during and after use of the external preparation for skin, 10 professional subjects actually used the external preparation for skin of the following test example and the existing external preparation for skin as a control (glycerin was mixed as a moisturizing agent) Composition), according to the following scoring criteria to assess the score. Here, the point evaluation is carried out with the reference skin external preparation being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤外用剂相比感觉非常润滑。+3: Feels very lubricious compared with the control skin external preparation.

+2：与对照皮肤外用剂相比感觉润滑。+2: Feels lubricated compared with the control skin external preparation.

+1：与对照皮肤外用剂相比感觉稍润滑。+1: Feels slightly lubricated compared with the control skin external preparation.

0：基本相同。0: Basically the same.

-1：与对照皮肤外用剂相比感觉不太润滑。-1: Felt less slippery than the control external skin preparation.

-2：与对照皮肤外用剂相比感觉不润滑。-2: Feeling less lubricious compared with the control skin external preparation.

-3：与对照皮肤外用剂相比感觉完全不润滑。-3: Feels not lubricated at all compared with the control skin external preparation.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(2)：无黏腻感Evaluation (2): No sticky feeling

关于皮肤外用剂在皮肤上涂抹后的无黏腻感，由10名专业受试者实际使用以下所示试验例的皮肤外用剂和作为对照的现有皮肤外用剂(作为保湿剂配合甘油的组成)，根据以下评分基准来评定分数。这里的分数评定以对照皮肤外用剂为0来实施。另外，计算各受试者的分数的总和除以受试者人数的平均值，根据以下评价基准给出评价结果。With regard to the non-sticky feeling after application of the external skin preparation on the skin, 10 professional test subjects actually used the external skin preparation of the test example shown below and the existing external skin preparation (composition of glycerin as a moisturizing agent) as a control. ), according to the following scoring criteria to assess the score. Here, the point evaluation is carried out with the reference skin external preparation being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤外用剂相比感觉完全无黏腻感。+3: Compared with the control external preparation for skin, there is no feeling of stickiness at all.

+2：与对照皮肤外用剂相比感觉无黏腻感。+2: No sticky feeling compared with the control skin external preparation.

+1：与对照皮肤外用剂相比感觉不太有黏腻感。+1: It feels less sticky than the control external skin preparation.

0：基本相同。0: Basically the same.

-1：与对照皮肤外用剂相比感觉稍微有黏腻感。-1: Slightly stickier than the control external preparation for skin.

-2：与对照皮肤外用剂相比感觉到黏腻感。-2: A sticky feeling is felt compared with the control external preparation for skin.

-3：与对照皮肤外用剂相比感觉到显著的黏腻感。-3: Remarkable stickiness was felt compared with the control external preparation for skin.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(3)：湿润感(保湿效果感)Evaluation (3): Moist feeling (moisturizing effect feeling)

由10名专业受试者实际使用以下所示试验例的皮肤外用剂和作为对照的现有皮肤外用剂(配合甘油作为保湿剂的组成)来取得皮肤外用剂在皮肤上涂抹2小时后的湿润感(保湿效果感)，根据以下评分基准来评定分数。这里的分数评定以对照皮肤外用剂为0来实施。另外，计算各受试者的分数的总和除以受试者人数的平均值，根据以下评价基准给出评价结果。10 professional subjects actually used the skin external preparation of the test example shown below and the existing skin external preparation (composition containing glycerin as a moisturizing agent) as a control to obtain the moisture content of the skin external preparation 2 hours after applying the skin external preparation. Feeling (moisturizing effect feeling), the score was evaluated according to the following scoring criteria. Here, the point evaluation is carried out with the reference skin external preparation being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤外用剂相比有显著的湿润感。+3: Significant moist feeling compared with the control skin external preparation.

+2：与对照皮肤外用剂相比有湿润感。+2: Moist feeling compared with the control external preparation for skin.

+1：与对照皮肤外用剂相比稍有湿润感。+1: Slightly moister than the control external preparation for skin.

0：基本相同。0: Basically the same.

-1：与对照皮肤外用剂相比感觉不太有湿润感。-1: Compared with the control external preparation for skin, it feels less moist.

-2：与对照皮肤外用剂相比感觉无湿润感。-2: Compared with the control external preparation for skin, there is no moist feeling.

-3：与对照皮肤外用剂相比感觉完全无湿润感。-3: Compared with the control external preparation for skin, there is no moist feeling at all.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

(评价4)皮肤粗糙改善效果试验(Evaluation 4) Rough skin improvement effect test

由面部(部位：脸颊)产生皮肤粗糙的10名被试者涂抹皮肤外用剂，根据以下所示的方法进行皮肤粗糙改善效果试验。The skin external preparation was applied to 10 test subjects who had rough skin on the face (site: cheek), and the skin roughness improving effect test was conducted according to the method shown below.

试验方法：每日一次在左右脸颊上涂抹不同的皮肤外用剂(各试验例的皮肤外用剂和对照皮肤外用剂)，连续涂抹1周，该期间结束后的第二天根据以下评分基准来评定分数。这里的分数评定以对照皮肤外用剂为0来实施。另外，计算各受试者的分数的总和除以受试者人数的平均值，根据以下评价基准给出评价结果。Test method: Apply different skin external preparations (skin external preparations of each test example and control skin external preparation) on the left and right cheeks once a day for 1 week, and evaluate according to the following scoring criteria on the second day after the end of the period Fraction. Here, the point evaluation is carried out with the reference skin external preparation being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤外用剂相比感觉皮肤粗糙显著改善。+3: Compared with the control external preparation for skin, skin roughness is felt to be significantly improved.

+2：与对照皮肤外用剂相比感觉皮肤粗糙改善。+2: Improvement in skin roughness was felt compared to the control skin external preparation.

+1：与对照皮肤外用剂相比感觉皮肤粗糙稍改善。+1: Compared with the control external preparation for skin, skin roughness was felt to be slightly improved.

0：基本相同。0: Basically the same.

-1：与对照皮肤外用剂相比感觉皮肤粗糙没怎么改善。-1: Compared with the control external preparation for skin, roughness of the skin is felt to be little improved.

-2：与对照皮肤外用剂相比感觉不到皮肤粗糙改善。-2: No improvement in skin roughness was felt compared to the control external preparation for skin.

-3：与对照皮肤外用剂相比完全感觉不到皮肤粗糙改善。-3: Compared with the control external preparation for skin, no improvement in roughness of the skin was sensed at all.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(5)：皮肤刺激试验Evaluation (5): Skin irritation test

在10名被试者的上臂内侧部进行24小时的封闭贴片试验，此后根据以下评分基准计算平均值。评价基准如下所述。The closed patch test was performed on the inner upper arm of 10 test subjects for 24 hours, and the average value was calculated based on the following scoring criteria thereafter. The evaluation criteria are as follows.

评分基准scoring benchmark

0分：完全没有见到异常。0 points: No abnormality was observed at all.

1分：见到稍微发红。1 point: Slight redness is seen.

2分：见到发红。2 points: Redness is seen.

3分：见到发红和丘疹。3 points: Redness and papules are seen.

评价基准Evaluation benchmark

A：10名受试者的平均值为低于0.15分。A: The average value of 10 subjects is less than 0.15 points.

B：10名受试者的平均值为0.15分以上到低于0.2分。B: The average value of 10 subjects is 0.15 points or more and less than 0.2 points.

C：10名受试者的平均值为0.2分以上到低于0.3分。C: The average value of 10 subjects is 0.2 or more points and less than 0.3 points.

D：10名受试者的平均值为0.3分以上。D: The average value of 10 subjects was 0.3 or more.

评价(6)：稳定性Evaluation (6): Stability

通过在刚制造之后和在填充到玻璃瓶之后在50℃下放置6周之后目测，根据以下基准评价各试验例的皮肤外用剂的稳定性。The stability of the external preparation for skin of each test example was evaluated according to the following criteria by visual observation immediately after manufacture and after being filled into a glass bottle and left at 50° C. for 6 weeks.

A：外观没有见到变化。A: No change was observed in the appearance.

B：发现油相或水相轻度分离。B: Slight separation of the oil phase or the water phase was found.

C：发现油相或水相明显分离。C: The oil phase or water phase was clearly separated.

本发明根据以下表1～3所示的配合组成通过常规方法制造皮肤外用剂，根据上述评价项目(1)～(6)进行评价试验。According to the present invention, external preparations for skin were produced by conventional methods based on the compounding compositions shown in Tables 1 to 3 below, and evaluation tests were performed based on the above evaluation items (1) to (6).

首先，研究将以往的保湿剂和嵌段型氧化烯衍生物分别配合而成的皮肤外用剂。结果在下表1中示出。First, a skin external preparation in which a conventional moisturizer and a block-type oxyalkylene derivative were separately blended was studied. The results are shown in Table 1 below.

另外，下表中的嵌段型氧化烯衍生物具有下式(II)的结构，例如在a+c+e＝30、b+d+f＝30的情况下，表示为(BO)₃₀(EO)₃₀。In addition, the block-type oxyalkylene derivatives in the following table have the structure of the following formula (II), for example, in the case of a+c+e=30, b+d+f=30, it is expressed as (BO)₃₀ ( EO)₃₀ .

表1Table 1

从以上表1的结果可以看出，将作为对照而使用的甘油作为保湿剂配合的皮肤外用剂稳定性差。在降低甘油的配合量时(试验例2)，以湿润感为代表的保湿效果和皮肤粗糙改善效果降低。As can be seen from the results in Table 1 above, the skin external preparations in which glycerin used as a control was blended as a moisturizer were poor in stability. When the blending amount of glycerin was reduced (Test Example 2), the moisturizing effect represented by a moist feeling and the rough skin improving effect decreased.

另一方面，可以认为配合嵌段型氧化烯衍生物的试验例1的皮肤外用剂的上述所有评价均是优异的，获得了使用感、保湿效果、皮肤粗糙改善效果和稳定性的平衡。另外，在没有配合甘油等保湿剂和氧化烯衍生物的组成(试验例4)中，当然不能期望保湿效果和皮肤粗糙改善效果，而且稳定性也是差的。On the other hand, the skin external preparation of Test Example 1 containing a block-type oxyalkylene derivative is considered to be excellent in all the above evaluations, and it is considered that the feeling in use, moisturizing effect, skin roughness improving effect, and stability are well-balanced. In addition, in the composition (Test Example 4) in which no humectant such as glycerin and an alkylene oxide derivative was added, the moisturizing effect and rough skin improving effect could not be expected, and the stability was also poor.

接着，本发明人研究了各种氧化烯衍生物。结果在下表2中示出。Next, the present inventors studied various alkylene oxide derivatives. The results are shown in Table 2 below.

表2Table 2

所配合的氧化烯衍生物的结构仅仅由氧化乙烯部分构成，或者仅仅由氧化丁烯部分构成(试验例11和12)，由于这些物质没有表面活性剂的作用，稳定性是非常差的。此外，配合仅仅为氧化乙烯部分的氧化烯衍生物的试验例11在使用感和皮肤粗糙改善效果上是特别差的，另外，配合仅仅为氧化丁烯部分的氧化烯衍生物的试验例12在保湿效果感和皮肤粗糙改善效果上是差的。The compounded oxyalkylene derivatives have a structure consisting only of oxyethylene moieties, or only of butylene oxide moieties (Test Examples 11 and 12), and since these substances have no surfactant action, their stability is very poor. In addition, Test Example 11 in which an oxyalkylene derivative containing only an oxyethylene moiety was particularly inferior in terms of the feeling of use and the effect of improving skin roughness, and Test Example 12 in which an oxyalkylene derivative containing only an oxybutylene moiety was mixed The moisturizing effect and the skin roughness improvement effect are poor.

此外，在配合末端为氢的氧化烯衍生物的试验例13中，使用感和皮肤粗糙改善效果不充分。还发现了皮肤刺激性方面的问题。另外，在配合无规型的氧化烯衍生物的情况下(试验例14)，由于作为表面活性剂的作用不良，稳定性是差的。In addition, in Test Example 13 in which a hydrogen-terminated alkylene oxide derivative was blended, the feeling of use and the effect of improving rough skin were insufficient. Problems with skin irritation were also found. In addition, in the case of compounding a random-type oxyalkylene derivative (Test Example 14), the stability was poor due to poor action as a surfactant.

此外，为了获得稳定性即使在皮肤外用剂中配合以往作为表面活性剂使用的POE(60)氢化蓖麻油(试验例15)，也不能获得保湿效果感和皮肤粗糙改善效果。In addition, even when POE (60) hydrogenated castor oil (Test Example 15) conventionally used as a surfactant was blended in the skin external preparation for stability, the moisturizing effect and the skin roughness improvement effect could not be obtained.

另一方面，在配合各种嵌段型氧化烯衍生物的试验例5～10中，(1)～(6)的任何一项评价均是优异的。On the other hand, in Test Examples 5 to 10 in which various block-type oxyalkylene derivatives were blended, any of evaluations (1) to (6) were excellent.

从以上结果可以看出，在皮肤外用剂中配合具有特定结构的嵌段型氧化烯衍生物时，具有皮肤粗糙改善效果，而且使用感尤其润滑感优异，无黏腻感，保湿效果感优异，此外由于兼有表面活性剂作用，可以形成稳定性优异的基剂。From the above results, it can be seen that when a block-type oxyalkylene derivative having a specific structure is blended in an external skin preparation, it has an effect of improving rough skin, and the feeling of use is particularly excellent in lubricity, non-sticky, and excellent in moisturizing effect. In addition, it can form a base with excellent stability due to the function of a surfactant.

接下来，下表3示出了特定结构的嵌段型氧化烯衍生物在皮肤外用剂中的适合优选量的研究结果。Next, Table 3 below shows the results of studies on suitable and preferred amounts of block type oxyalkylene derivatives of specific structures in external skin preparations.

表3table 3

从以上表3的结果可以看出，在具有特定结构的嵌段型氧化烯衍生物的配合量为0.01～70质量％的范围内时，与以往的皮肤外用剂相比，具有皮肤粗糙改善效果，而且保湿效果感也是优异的。考虑到皮肤的润滑感和无黏腻感等使用感，所述氧化烯衍生物的配合量特别优选是0.1～20质量％。As can be seen from the results in Table 3 above, when the blending amount of the block-type oxyalkylene derivative having a specific structure is within the range of 0.01 to 70% by mass, it has an effect of improving rough skin compared to conventional external skin preparations. , and the sense of moisturizing effect is also excellent. The content of the alkylene oxide derivative is particularly preferably in the range of 0.1 to 20% by mass in consideration of a lubricious feeling on the skin and a non-sticky feeling.

下面给出了上述试验例的皮肤外用剂中配合的各种氧化烯衍生物的一部分合成例。Some synthesis examples of various alkylene oxide derivatives compounded in the external skin preparations of the above test examples are given below.

(合成例1)(Synthesis Example 1)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三甲基甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Trimethylglyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为49，氧化烯衍生物1的羟基值为0.4，相对于末端甲基数的氢原子数的比例为0.008，氢原子几乎全部转换为甲基。The hydroxyl value of the sampled and purified substance before reacting methyl chloride was 49, the hydroxyl value of the oxyalkylene derivative 1 was 0.4, the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.008, and almost all of the hydrogen atoms were converted For methyl.

(合成例2)(Synthesis Example 2)

聚氧化乙烯(57mol)三甲基甘油醚(氧化烯衍生物)的合成Synthesis of Polyoxyethylene (57mol) Trimethylglyceryl Ether (Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2508g的环氧乙烷，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2508 g of ethylene oxide was dripped with a dripping device, and stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt generated after the treatment, filtration was performed to obtain an alkylene oxide derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为66，氧化烯衍生物1的羟基值为0.6，相对于末端甲基数的氢原子数的比例为0.009，氢原子几乎全部转换为甲基。The hydroxyl value of the sampled and purified substance before reacting methyl chloride was 66, the hydroxyl value of the oxyalkylene derivative 1 was 0.6, the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.009, and almost all of the hydrogen atoms were converted For methyl.

(合成例3)(Synthesis Example 3)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Glyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

(合成例4)(Synthesis Example 4)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三丁基甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Tributyl Glyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。然后加入800g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入1200g的丁基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Then add 800g of potassium hydroxide, replace the system with dry nitrogen, then press-in 1200g of butyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

在使丁基氯反应之前取样和提纯后的物质的羟基值为50，氧化烯衍生物1的羟基值为1.5，相对于末端丁基数的氢原子数的比例为0.03，氢原子几乎全部转换为丁基。The hydroxyl value of the sampled and purified substance before reacting butyl chloride was 50, the hydroxyl value of the oxyalkylene derivative 1 was 1.5, the ratio of the number of hydrogen atoms to the number of terminal butyl groups was 0.03, and almost all of the hydrogen atoms were converted to butyl.

(合成例5)(Synthesis Example 5)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三甲基甘油醚(无规型氧化烯衍生物)的合成Synthesis of polyoxybutylene (30mol) polyoxyethylene (30mol) trimethylglyceryl ether (random oxyalkylene derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷和1320g的环氧乙烷的混合物，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得无规型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, a mixture of 2,160 g of butylene oxide and 1,320 g of ethylene oxide was dropped through a dropping device, and stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a random type oxyalkylene derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为47，所得无规型氧化烯衍生物5的化合物的羟基值为0.5，相对于末端甲基数的氢原子数的比例为0.011，氢原子几乎全部转换为甲基。The hydroxyl value of the substance sampled and purified before reacting methyl chloride was 47, the hydroxyl value of the obtained random-type oxyalkylene derivative 5 compound was 0.5, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.011 , the hydrogen atoms are almost completely converted to methyl groups.

以下例举了本发明的皮肤外用剂的配方例，然而本发明的技术范围不限于这些配方例。另外，所得皮肤外用剂具有皮肤粗糙改善效果，使用感尤其润滑感优异，无黏腻感，并且乳化稳定性优异。Although the formulation examples of the external skin preparation of this invention are mentioned below, the technical scope of this invention is not limited to these formulation examples. In addition, the obtained external preparation for skin has an effect of improving rough skin, has excellent feeling of use, especially lubricious feeling, no sticky feeling, and excellent emulsification stability.

配方例1：乳液Recipe Example 1: Emulsion

(配合成分)                        (质量％)(combined ingredients) (mass%)

A相Phase A

(1)角鲨烷                          4.0(1) Squalane 4.0

(2)油酸油酯                        2.5(2) Olein 2.5

(3)凡士林                          1.5(3) Vaseline 1.5

(4)POB(30)POE(35)三甲基甘油醚       2.0(4)POB(30)POE(35)trimethylglyceryl ether 2.0

(在式(III)中，a+c+e＝30，b+d+f＝35，BO是氧化丁烯基，EO是氧化乙烯基。)(In formula (III), a+c+e=30, b+d+f=35, BO is oxybutylene group, EO is oxyethylene group.)

(5)月见草油                        0.2(5) Evening primrose oil 0.2

(6)香料                            0.1(6) spices 0.1

(7)防腐剂                          适量(7) Appropriate amount of preservatives

B相Phase B

(8)1，3-丁二醇                     1.5(8) 1,3-Butanediol 1.5

(9)乙醇                            2.0(9) Ethanol 2.0

(10)羧基乙烯基聚合物               0.2(10) Carboxyvinyl polymer 0.2

(11)氢氧化钾                       0.1(11) Potassium hydroxide 0.1

(12)L-精氨酸L-天冬氨酸盐           0.01(12) L-Arginine L-Aspartate 0.01

(13)乙二胺四乙酸盐                 0.05(13) Ethylenediaminetetraacetic acid salt 0.05

(14)纯化水                         余量(14) Purified water balance

(制备方法)(Preparation)

将A相和B相各自加热至70℃溶解，然后，将A相加入到B相中，使用乳化器乳化。用热交换器将所得乳化物冷却，获得目的乳液。Heat phase A and phase B to 70°C to dissolve each, then add phase A to phase B and emulsify with an emulsifier. The obtained emulsion was cooled with a heat exchanger to obtain the desired emulsion.

配方例2：霜Recipe Example 2: Cream

(配合成分)                       (质量％)(combined ingredients) (mass%)

A相Phase A

(1)硬脂酸                        10.0(1) Stearic acid 10.0

(2)硬脂醇                        3.5(2) Stearyl Alcohol 3.5

(3)硬脂酸丁酯                    6.0(3) Butyl stearate 6.0

(4)POB(30)POE(35)三甲基甘油醚    1.5(4)POB(30)POE(35)trimethylglyceryl ether 1.5

(在上述式(III)中，a+c+e＝30，b+d+f＝35，BO是氧化丁烯基，EO是氧化乙烯基。)(In the above formula (III), a+c+e=30, b+d+f=35, BO is an oxybutylene group, and EO is an oxyethylene group.)

(5)单硬脂酸甘油酯                   2.5(5) Glyceryl monostearate 2.5

(6)维生素E乙酸酯                    0.5(6) Vitamin E acetate 0.5

(7)维生素A棕榈酸酯                  0.1(7) Vitamin A palmitate 0.1

(8)澳洲坚果油                       0.5(8) Macadamia oil 0.5

(9)香料                             0.15(9) Spices 0.15

(10)防腐剂                          适量(10) Appropriate amount of preservatives

B相Phase B

(11)甘油                            6.0(11) Glycerin 6.0

(12)1，2-戊二醇                     2.0(12) 1,2-pentanediol 2.0

(13)透明质酸钠                      1.5(13) Sodium hyaluronate 1.5

(14)氢氧化钾                        2.0(14) Potassium hydroxide 2.0

(15)抗坏血酸磷酸镁                  0.1(15) Magnesium Ascorbyl Phosphate 0.1

(16)L-精氨酸盐酸盐                  0.01(16)L-arginine hydrochloride 0.01

(17)乙二胺四乙酸三钠                0.05(17) Trisodium edetate 0.05

(18)纯化水                     余量(18) Balance of purified water

(制备方法)(Preparation)

将A相和B相各自加热至70℃溶解，然后，将A相加入到B相中，使用乳化器乳化。用热交换器将所得乳化物冷却，获得目的霜剂。Heat phase A and phase B to 70°C to dissolve each, then add phase A to phase B and emulsify with an emulsifier. The obtained emulsion was cooled with a heat exchanger to obtain the intended cream.

配方例3：化妆水Recipe Example 3: Lotion

(配合成分)                    (质量％)(combined ingredients) (mass%)

A相Phase A

(1)乙醇                       5.0(1) Ethanol 5.0

(2)POB(32)POE(52)三甲基甘油醚  0.2(2) POB(32)POE(52) trimethyl glyceryl ether 0.2

(在前述式(III)中，a+c+e＝32，b+d+f＝52，BO是氧化丁烯基，EO是氧化乙烯基。)(In the aforementioned formula (III), a+c+e=32, b+d+f=52, BO is an oxybutylene group, and EO is an oxyethylene group.)

(3)对二甲氨基苯甲酸2-乙基己基酯             0.1(3) 2-ethylhexyl p-dimethylaminobenzoate 0.1

(4)防腐剂                                   适量(4) Appropriate amount of preservatives

(5)香料                                     0.1(5) spices 0.1

B相Phase B

(6)吡咯烷酮羧酸钠                           0.3(6) Sodium pyrrolidone carboxylate 0.3

(7)烟酰胺                                   0.2(7) Nicotinamide 0.2

(8)二吗啉代哒嗪酮                           0.1(8) Dimorpholinopyridazinone 0.1

(9)芦荟提取液                               0.2(9) Aloe Vera Extract 0.2

(10)纯化水                                  余量(10) Purified water Balance

(制备方法)(Preparation)

将A相和B相各自溶解后，将A相加入到B相中，增溶，获得目的化妆水。After dissolving phase A and phase B respectively, add phase A into phase B to solubilize and obtain the target lotion.

配方例4：粉底Recipe Example 4: Foundation

(配合成分)              (质量％)(combined ingredients) (mass%)

A相Phase A

(1)鲸蜡醇                     3.5(1) Cetyl alcohol 3.5

(2)脱臭羊毛脂                 4.0(2) Deodorized lanolin 4.0

(3)霍霍巴油                   5.0(3) Jojoba Oil 5.0

(4)凡士林                     2.0(4) Vaseline 2.0

(5)角鲨烷                     6.0(5) Squalane 6.0

(6)单硬脂酸甘油酯             2.5(6) Glyceryl monostearate 2.5

(7)POB(17)POE(28)三甲基甘油醚 1.5(7)POB(17)POE(28)Triglyceryl trimethyl ether 1.5

(在上述式(III)中，a+c+e＝17，b+d+f＝28，BO是氧化丁烯基，EO是氧化乙烯基。)(In the above formula (III), a+c+e=17, b+d+f=28, BO is an oxybutylene group, and EO is an oxyethylene group.)

(8)吡哆醇三棕榈酸酯                  0.1(8) Pyridoxine tripalmitate 0.1

(9)香料                              0.3(9) spices 0.3

(10)防腐剂                           适量(10) Appropriate amount of preservatives

B相Phase B

(11)丙二醇                           10.0(11) Propylene glycol 10.0

(12)球状尼龙粉末                     2.0(12)Spherical nylon powder 2.0

(13)硅酮处理的二氧化钛               5.0(13) Silicone-treated titanium dioxide 5.0

(14)硅酮处理的氧化铁                 2.0(14) Silicone treated iron oxide 2.0

(15)硅酮处理的云母                   1.0(15) Silicone treated mica 1.0

(16)金属皂处理的滑石粉               2.0(16) Talc powder treated with metal soap 2.0

(17)乙二胺四乙酸三钠                 0.5(17) Trisodium edetate 0.5

(18)纯化水                           余量(18) Purified water balance

(制备方法)(Preparation)

将A相和B相各自加热至70℃溶解，然后，将A相加入到B相中，使用乳化器乳化。用热交换器将所得乳化物冷却，获得目的粉底。Heat phase A and phase B to 70°C to dissolve each, then add phase A to phase B and emulsify with an emulsifier. The obtained emulsion was cooled with a heat exchanger to obtain the desired foundation.

配方例5：面膜(lotion mask)Recipe Example 5: lotion mask

(配合成分)                      (质量％)(combined ingredients) (mass%)

A相Phase A

(1)乙醇                           8.0(1) Ethanol 8.0

(2)POE(41)POP(48)三甲基甘油醚      0.5(2)POE(41)POP(48)trimethylglyceryl ether 0.5

(在上述式(III)中，a+c+e＝41，b+d+f＝48，BO是氧化丁烯基，EO是氧化乙烯基。)(In the above formula (III), a+c+e=41, b+d+f=48, BO is an oxybutylene group, and EO is an oxyethylene group.)

(3)乳酸薄荷酯               0.002(3) Menthyl Lactate 0.002

(4)香料                     0.01(4) spices 0.01

(5)防腐剂                   适量(5) Appropriate amount of preservatives

B相Phase B

(6)桦木提取液               0.2(6) Birch extract 0.2

(7)苛性钾                   适量(7) Appropriate amount of caustic potash

(8)纯化水                   余量(8) Balance of purified water

(制备方法)(Preparation)

将A相加入到B相中，配制化妆水，进一步将该化妆水浸渍到无纺布中，制备目的面膜。Add phase A to phase B to prepare lotion, and further impregnate the lotion into non-woven fabric to prepare the target mask.

实施例2Example 2

接着，评价本发明的皮肤清洁剂。首先，说明本发明中所使用的评价方法。Next, the skin cleansers of the present invention were evaluated. First, the evaluation method used in the present invention will be described.

首先示出了试验中使用的化妆品(防晒剂和成膜性强的粉底)的配方。First, the formulations of the cosmetics (sunscreen and strong film-forming foundation) used in the test are shown.

对于以下评价(1)～(5)，配制以下组成的对照皮肤清洁剂，用作评价基准。For the following evaluations (1) to (5), a control skin cleanser of the following composition was prepared and used as an evaluation standard.

对照皮肤清洁剂组成Composition of Control Skin Cleanser

(1)羧基乙烯基聚合物                      0.5质量％(1) Carboxyvinyl polymer 0.5% by mass

(2)羟乙基纤维素                          0.02(2) Hydroxyethylcellulose 0.02

(3)丙烯酸/甲基丙烯酸烷基酯共聚物          0.1(3) Acrylic acid/alkyl methacrylate copolymer 0.1

(4)十甲基环状五聚硅氧烷          10.0(4) Decamethylcyclopentasiloxane 10.0

(5)液体石蜡                      3.0(5) Liquid paraffin 3.0

(6)POE(10)异硬脂酸酯             5.0(6) POE(10) isostearate 5.0

(7)1，3-丁二醇                   5.0(7) 1,3-Butanediol 5.0

(8)氢氧化钾                      适量(8) Potassium hydroxide Appropriate amount

(9)香料                          适量(9) Appropriate amount of spices

(10)纯化水                       余量(10) Balance of purified water

(制备方法)(Preparation)

将(1)～(3)和(6)～(8)均匀地在(10)中混合和溶解，向其中搅拌混合将(4)和(5)混合而获得的油相成分。进一步添加(9)，用均质搅拌机乳化，获得霜状的清洁剂(O/W类型)。(1)-(3) and (6)-(8) are uniformly mixed and dissolved in (10), and the oil phase component obtained by mixing (4) and (5) is stirred thereinto. Add (9) further and emulsify with a homomixer to obtain a creamy cleanser (O/W type).

评价(1)：皮肤清洁剂与化妆品的易融合性Evaluation (1): Easy Fusion of Skin Cleanser and Cosmetics

反复涂抹防晒剂和成膜性强的粉底，经2小时后使用试样洗脸，由10名专业受试者通过实际使用试验来评价皮肤清洁剂与化妆品的易融合性的有无。根据以下评分基准评定分数。这里的分数评定以对照皮肤清洁剂与化妆品的易融合性为0来进行。另外，计算各受试者的分数的总和除以受试人数的平均值，按照以下评价基准给出评价结果。Apply sunscreen and strong film-forming foundation repeatedly, wash your face with the sample after 2 hours, and evaluate the compatibility between the skin cleanser and cosmetics by 10 professional subjects through actual use tests. Scores are awarded according to the following scoring criteria. The score evaluation here is carried out with the ease of fusion of the control skin cleanser and cosmetics being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤清洁剂相比，认为非常适应。+3: Considered very adaptable compared to the control skin cleanser.

+2：与对照皮肤清洁剂相比，认为适应。+2: Considered adaptable compared to a control skin cleanser.

+1：与对照皮肤清洁剂相比，认为稍微适应。+1: Considered slightly adapting compared to the control skin cleanser.

0：基本相同。0: Basically the same.

-1：与对照皮肤清洁剂相比不太适应。-1: Less adaptable compared to control skin cleanser.

-2：与对照皮肤清洁剂相比不适应。-2: Unsuitable compared to control skin cleanser.

-3：与对照皮肤清洁剂相比完全不适应。-3: Completely unacceptable compared to the control skin cleanser.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(2)：皮肤清洁剂的易冲洗性Evaluation (2): Ease of rinsing of skin cleanser

反复涂抹防晒剂和成膜性强的粉底，经2小时后使用试样洗脸，由10名专业受试者通过实际使用试验来评价皮肤清洁剂的易冲洗性的有无。根据以下评分基准评定分数。这里的分数评定以对照皮肤清洁剂的易冲洗性为0来进行。另外，计算各受试者的分数的总和除以受试人数的平均值，按照以下评价基准给出评价结果。Apply sunscreen and strong film-forming foundation repeatedly, use the sample to wash your face after 2 hours, and evaluate the ease of rinsing of the skin cleanser through actual use tests by 10 professional subjects. Scores are awarded according to the following scoring criteria. The scoring here is based on the ease of rinsing of the control skin cleanser as 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤清洁剂相比，认为非常易冲洗。+3: Considered to be very easy to rinse off compared to control skin cleansers.

+2：与对照皮肤清洁剂相比，认为容易冲洗。+2: Considered easy to rinse off compared to control skin cleansers.

+1：与对照皮肤清洁剂相比，认为稍微容易冲洗。+1: Considered slightly easier to rinse off compared to the control skin cleanser.

0：基本相同。0: Basically the same.

-1：与对照皮肤清洁剂相比不太容易冲洗。-1: Rinse off less easily than control skin cleanser.

-2：与对照皮肤清洁剂相比不容易冲洗。-2: Does not rinse off easily compared to control skin cleanser.

-3：与对照皮肤清洁剂相比完全不容易冲洗。-3: Not easy to rinse off at all compared to control skin cleanser.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(3)：无洗涤后黏腻感Evaluation (3): No sticky feeling after washing

反复涂抹防晒剂和成膜性强的粉底，经2小时后使用试样洗脸，由10名专业受试者通过实际使用试验来评价有无洗涤后的黏腻感。根据以下评分基准评定分数。这里的分数评定以对照皮肤清洁剂使用后的无黏腻感为0来进行。另外，计算各受试者的分数的总和除以受试人数的平均值，按照以下评价基准给出评价结果。Apply sunscreen and strong film-forming foundation repeatedly, use the sample to wash your face after 2 hours, and evaluate whether there is any sticky feeling after washing by 10 professional subjects through actual use tests. Scores are awarded according to the following scoring criteria. The score evaluation here is based on the non-sticky feeling after use of the control skin cleanser as 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤清洁剂相比，认为洗涤后明显无黏腻感。+3: Considered significantly less sticky after wash compared to the control skin cleanser.

+2：与对照皮肤清洁剂相比，认为洗涤后无黏腻感。+2: No sticky feel after wash compared to control skin cleanser.

+1：与对照皮肤清洁剂相比，认为洗涤后稍微无黏腻感。+1: Considered slightly less sticky after wash compared to control skin cleanser.

0：基本相同。0: Basically the same.

-1：与对照皮肤清洁剂相比洗涤后稍微黏腻。-1: Slightly sticky after washing compared with the control skin cleanser.

-2：与对照皮肤清洁剂相比洗涤后黏腻。-2: Stickiness after washing compared to control skin cleanser.

-3：与对照皮肤清洁剂相比洗涤后非常黏腻。-3: Very sticky after washing compared to the control skin cleanser.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(4)：洗涤后的发涩感Evaluation (4): Astringent feeling after washing

反复涂抹防晒剂和成膜性强的粉底，经2小时后使用试样洗脸，由10名专业受试者通过实际使用试验来评价有无洗涤后的发涩感。根据以下评分基准评定分数。这里的分数评定以对照皮肤清洁剂的发涩感为0来进行。另外，计算各受试者的分数的总和除以受试人数的平均值，按照以下评价基准给出评价结果。Apply sunscreen and strong film-forming foundation repeatedly, use the sample to wash your face after 2 hours, and evaluate whether there is any astringent feeling after washing by 10 professional subjects through actual use tests. Scores are awarded according to the following scoring criteria. The score evaluation here is carried out with the harsh feeling of the control skin cleanser being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤清洁剂相比，认为洗涤后明显无发涩感。+3: Compared to the control skin cleanser, post-wash is perceived to be significantly less harsh.

+2：与对照皮肤清洁剂相比，认为洗涤后无发涩感。+2: No harsh feeling after washing compared to control skin cleanser.

+1：与对照皮肤清洁剂相比，认为洗涤后稍微无发涩感。+1: Considered slightly less harsh after wash compared to the control skin cleanser.

0：基本相同。0: Basically the same.

-1：与对照皮肤清洁剂相比，洗涤后稍微有发涩感。-1: Compared with the control skin cleanser, there is a slightly harsh feeling after washing.

-2：与对照皮肤清洁剂相比，洗涤后有发涩感。-2: Compared with the control skin cleanser, there is a harsh feeling after washing.

-3：与对照皮肤清洁剂相比，洗涤后发涩感显著。-3: Compared with the control skin cleanser, the harsh feeling after washing is remarkable.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(5)：化妆品去除效果Evaluation (5): Makeup removal effect

反复涂抹防晒剂和成膜性强的粉底，经2小时后使用试样洗脸，由10名专业受试者通过实际使用试验来评价有无洗涤后的化妆品去除效果。根据以下评分基准评定分数。这里的分数评定以对照皮肤清洁剂的去除效果为0来进行。另外，计算各受试者的分数的总和除以受试人数的平均值，按照以下评价基准给出评价结果。Apply sunscreen and strong film-forming foundation repeatedly, use the sample to wash your face after 2 hours, and evaluate whether there is any cosmetic removal effect after washing by 10 professional subjects through actual use tests. Scores are awarded according to the following scoring criteria. The score evaluation here is carried out with the removal effect of the control skin cleanser being 0. In addition, the sum of the scores of each test subject was calculated and divided by the average value of the number of test subjects, and the evaluation results were given according to the following evaluation criteria.

评分基准scoring benchmark

+3：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果非常好。+3: Considered to be very good at removing make-up after washing compared to a control skin cleanser.

+2：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果好。+2: Considered to be good at removing make-up after washing compared to a control skin cleanser.

+1：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果稍好。+1: Considered slightly better at removing make-up after wash than a control skin cleanser.

0：基本相同。0: Basically the same.

-1：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果稍差。-1: Post-wash make-up removal is considered slightly less effective compared to the control skin cleanser.

-2：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果差。-2: Post-wash make-up removal is considered poor compared to the control skin cleanser.

-3：与对照皮肤清洁剂相比，认为洗涤后化妆品去除效果很差。-3: Post-wash make-up removal is considered to be poor compared to the control skin cleanser.

评价基准Evaluation benchmark

A：10名受试者的平均值为+1.5分以上。A: The average value of 10 subjects was +1.5 or more.

B：10名受试者的平均值为0以上到低于1.5分。B: The average value of 10 subjects ranged from 0 or more to less than 1.5 points.

C：10名受试者的平均值为-1.5分以上到低于0分。C: The average value of 10 subjects ranged from -1.5 or more to less than 0.

D：10名受试者的平均值为低于-1.5分。D: The average value of 10 subjects is less than -1.5 points.

评价(6)：皮肤刺激试验Evaluation (6): Skin irritation test

在10名被试者的上臂内侧部进行24小时的封闭贴片试验，此后根据以下评分基准计算平均值。评价基准如下所述。The closed patch test was performed on the inner upper arm of 10 test subjects for 24 hours, and the average value was calculated based on the following scoring criteria thereafter. The evaluation criteria are as follows.

评分基准scoring benchmark

0分：完全没有见到异常。0 points: No abnormality was observed at all.

1分：见到稍微发红。1 point: Slight redness is seen.

2分：见到发红。2 points: Redness is seen.

3分：见到发红和丘疹。3 points: Redness and papules are seen.

评价基准Evaluation benchmark

A：10名受试者的平均值为低于0.15分。A: The average value of 10 subjects is less than 0.15 points.

B：10名受试者的平均值为0.15分以上到低于0.2分。B: The average value of 10 subjects is 0.15 points or more and less than 0.2 points.

C：10名受试者的平均值为0.2分以上到低于0.3分。C: The average value of 10 subjects is 0.2 or more points and less than 0.3 points.

D：10名受试者的平均值为0.3分以上。D: The average value of 10 subjects was 0.3 or more.

本发明人使用配合各种氧化烯衍生物的下述试验用基本组成，实际配制皮肤清洁剂，进行评价。另外，用以下基本组成的清洁剂洗脸是通过将清洁剂直接在脸上融合和然后用水冲走来进行。The present inventors actually prepared and evaluated skin cleansers using the following test basic compositions in which various alkylene oxide derivatives were blended. Alternatively, washing the face with the cleanser of the following basic composition is performed by directly blending the cleanser on the face and then rinsing away with water.

试验用基本组成Basic composition for testing

(1)羧基乙烯基聚合物             0.5质量％(1) Carboxyvinyl polymer 0.5% by mass

(2)羟乙基纤维素                          0.02(2) Hydroxyethylcellulose 0.02

(3)丙烯酸/甲基丙烯酸烷基酯共聚物         0.1(3) Acrylic acid/alkyl methacrylate copolymer 0.1

(4)十甲基环状五聚硅氧烷                  10.0(4) Decamethylcyclopentasiloxane 10.0

(5)液体石蜡                              3.0(5) Liquid paraffin 3.0

(6)氧化烯衍生物                          0.1～20.0(6) Alkylene oxide derivatives 0.1～20.0

(7)保湿剂                                5.0(7) Moisturizer 5.0

(8)氢氧化钾                              适量(8) Potassium hydroxide Appropriate amount

(9)香料                                  适量(9) Appropriate amount of spices

(10)纯化水                               余量(10) Purified water balance

(制备方法)(Preparation)

将(1)～(3)和(6)～(8)均匀地在(10)中混合和溶解，向其中搅拌混合将(4)和(5)混合而获得的油相成分。进一步添加(9)，用均质搅拌器乳化，获得霜状的清洁剂(O/W类型)。(1)-(3) and (6)-(8) are uniformly mixed and dissolved in (10), and the oil phase component obtained by mixing (4) and (5) is stirred thereinto. Add (9) further and emulsify with a homomixer to obtain a creamy cleanser (O/W type).

本发明人研究了配合各种氧化烯衍生物的各种皮肤清洁剂。结果在表4～6中示出。The present inventors studied various skin cleansers containing various alkylene oxide derivatives. The results are shown in Tables 4-6.

另外，下表中的嵌段型氧化烯衍生物具有下式(II)的结构，例如在a+c+e＝30、b+d+f＝30的情况下，表示为(BO)₃₀(EO)₃₀。In addition, the block-type oxyalkylene derivatives in the following table have the structure of the following formula (II), for example, in the case of a+c+e=30, b+d+f=30, it is expressed as (BO)₃₀ ( EO)₃₀ .

表4Table 4

另外，在上表4中的试验例1～10中，配合5质量％的1，3-丁二醇作为保湿剂。In addition, in Test Examples 1 to 10 in Table 4 above, 5% by mass of 1,3-butanediol was blended as a humectant.

作为对照，即使配合用于提高洗涤性的以往使用的表面活性剂异硬脂酸POE(10)酯，也不能充分满足洗涤后的黏腻感和皮肤刺激性。In contrast, even if POE (10) isostearate, a conventionally used surfactant for improving detergency, was added, the sticky feeling and skin irritation after washing could not be fully satisfied.

在所配合的氧化烯衍生物的结构仅仅由氧化乙烯部分构成或者仅仅由氧化丁烯部分构成时(试验例7和8)，由于这些物质没有表面活性剂的作用，与化妆品的易融合性、洗涤中的易冲洗性和化妆品去除效果均是非常差的。When the structure of the compounded oxyalkylene derivative is only composed of oxyethylene or only oxybutylene (Test Examples 7 and 8), since these substances do not have the effect of surfactant, the compatibility with cosmetics, Both the ease of rinsing and the removal of makeup in the wash were very poor.

此外，在配合末端为氢的氧化烯衍生物的试验例9中，洗涤后的黏腻感和皮肤刺激性评价是不良的。另外，在配合无规型氧化烯衍生物的情况下(试验例10)，由于表面活性剂作用弱，不能充分满足与化妆品的融合性、洗涤中的易冲洗性和化妆品去除效果。In addition, in Test Example 9 in which a hydrogen-terminated alkylene oxide derivative was blended, the evaluation of stickiness and skin irritation after washing was poor. In addition, in the case of blending a random type oxyalkylene derivative (Test Example 10), the compatibility with cosmetics, the ease of rinsing during washing, and the cosmetics removal effect could not be fully satisfied due to the weak action of the surfactant.

另一方面，在配合各种嵌段型氧化烯衍生物的试验例1～6中，(1)～(6)中任一项评价均为优异的。On the other hand, in Test Examples 1 to 6 in which various block type oxyalkylene derivatives were blended, any of evaluations (1) to (6) were excellent.

从以上结果可以看出，在皮肤清洁剂中配合具有特定结构的嵌段型氧化烯衍生物时，可以形成与化妆品的融合性良好、洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异、化妆品去除效果优异且皮肤刺激性低的皮肤清洁剂。From the above results, it can be seen that when a block-type oxyalkylene derivative with a specific structure is blended in a skin cleanser, it can form a good compatibility with cosmetics, easy rinsing during washing, no sticky feeling and no skin after washing. A skin cleanser with excellent usability such as astringent feeling, excellent makeup removal effect, and low skin irritation.

接下来研究在皮肤清洁剂中配合的保湿剂。结果在以下表5中示出。Next, look at moisturizers that are incorporated into skin cleansers. The results are shown in Table 5 below.

表5table 5

在没有配合特定结构的嵌段型氧化烯衍生物的情况下(试验例14)，可以看出洗涤中的易冲洗性、洗涤后的发涩感和皮肤刺激性是差的。另外，在没有配合丙二醇、甘油等保湿剂的情况下(试验例15)，洗涤后的发涩感尤其不良。In the case where no block-type oxyalkylene derivative of a specific structure was blended (Test Example 14), it was found that the ease of rinsing during washing, the harsh feeling after washing, and the skin irritation were poor. In addition, when no humectant such as propylene glycol or glycerin was blended (Test Example 15), the dry feeling after washing was particularly bad.

另一方面，在组合试验例11～13中配合的特定结构的嵌段型氧化烯衍生物与保湿剂时，(1)～(6)中任一项评价均是优异的。On the other hand, when the block-type oxyalkylene derivatives of the specific structure compounded in Test Examples 11 to 13 were combined with a humectant, any of the evaluations (1) to (6) was excellent.

接下来，在下表6中示出了特定结构的嵌段型氧化烯衍生物在皮肤清洁剂中的优选配合量的研究结果。Next, Table 6 below shows the results of studies on the preferred blending amounts of block type oxyalkylene derivatives of specific structures in skin cleansers.

表6Table 6

根据以上表6的结果，虽然具有特定结构的嵌段型氧化烯衍生物的配合量从大约0.1质量％起被认可，但在1.0质量％以上时效果是特别显著的。然而，在20.0质量％以上时，由于开始产生一定的洗涤后的黏腻感等，因此大约10质量％的配合量是特别优选的。因此，具有特定结构的嵌段型氧化烯衍生物的配合量优选是0.1～20.0质量％。From the results in Table 6 above, it is recognized that the blending amount of the block-type oxyalkylene derivative having a specific structure is from about 0.1% by mass, but the effect is particularly remarkable when it is 1.0% by mass or more. However, when it is 20.0% by mass or more, a certain amount of stickiness after washing starts to be produced, so a compounding amount of about 10% by mass is particularly preferable. Therefore, the blending amount of the block type oxyalkylene derivative having a specific structure is preferably 0.1 to 20.0% by mass.

以下给出了在以上试验例的皮肤清洁剂中配合的各种氧化烯衍生物的一部分合成例。Some synthesis examples of various alkylene oxide derivatives blended in the skin cleansers of the above test examples are shown below.

(合成例1)(Synthesis Example 1)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三甲基甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Trimethylglyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为49，氧化烯衍生物1的羟基值为0.4，相对于末端甲基数的氢原子数的比例为0.008，氢原子几乎全部转换为甲基。The hydroxyl value of the sampled and purified substance before reacting methyl chloride was 49, the hydroxyl value of the oxyalkylene derivative 1 was 0.4, the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.008, and almost all of the hydrogen atoms were converted For methyl.

(合成例2)(Synthesis Example 2)

聚氧化乙烯(57mol)三甲基甘油醚(氧化烯衍生物)的合成Synthesis of Polyoxyethylene (57mol) Trimethylglyceryl Ether (Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2508g的环氧乙烷，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2508 g of ethylene oxide was dripped with a dripping device, and stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt generated after the treatment, filtration was performed to obtain an alkylene oxide derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为66，氧化烯衍生物1的羟基值为0.6，相对于末端甲基数的氢原子数的比例为0.009，氢原子几乎全部转换为甲基。The hydroxyl value of the sampled and purified substance before reacting methyl chloride was 66, the hydroxyl value of the oxyalkylene derivative 1 was 0.6, the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.009, and almost all of the hydrogen atoms were converted For methyl.

(合成例3)(Synthesis Example 3)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Glyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

(合成例4)(Synthesis Example 4)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三丁基甘油醚(嵌段型氧化烯衍生物)的合成Synthesis of Polyoxybutylene (30mol) Polyoxyethylene (30mol) Tributyl Glyceryl Ether (Block Type Oxyalkylene Derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷，搅拌2小时。然后，通过滴加装置滴入1320g的环氧乙烷，搅拌2小时。然后加入800g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入1200g的丁基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得嵌段型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, 2160 g of butylene oxide was dripped with a dripping device, and stirred for 2 hours. Then, 1320 g of ethylene oxide was dripped with a dripping apparatus, and it stirred for 2 hours. Then add 800g of potassium hydroxide, replace the system with dry nitrogen, then press-in 1200g of butyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a block type oxyalkylene derivative.

在使丁基氯反应之前取样和提纯后的物质的羟基值为50，氧化烯衍生物1的羟基值为1.5，相对于末端丁基数的氢原子数的比例为0.03，氢原子几乎全部转换为丁基。The hydroxyl value of the sampled and purified substance before reacting butyl chloride was 50, the hydroxyl value of the oxyalkylene derivative 1 was 1.5, the ratio of the number of hydrogen atoms to the number of terminal butyl groups was 0.03, and almost all of the hydrogen atoms were converted to butyl.

(合成例5)(Synthesis Example 5)

聚氧化丁烯(30mol)聚氧化乙烯(30mol)三甲基甘油醚(无规型氧化烯衍生物)的合成Synthesis of polyoxybutylene (30mol) polyoxyethylene (30mol) trimethylglyceryl ether (random oxyalkylene derivative)

将92g甘油与18g作为催化剂的氢氧化钾加入到高压釜内，在用干燥氮气置换高压釜内的空气后，在搅拌的同时在140℃下使催化剂完全溶解。接着通过滴加装置滴入2160g的环氧丁烷和1320g的环氧乙烷的混合物，搅拌2小时。然后加入400g氢氧化钾，体系内用干燥氮气置换后，在80～130℃的温度下压入300g的甲基氯，反应5小时。此后，从高压釜排出反应组合物，用盐酸中和，调节pH至6～7，为了除去所含的水分，在减压-0.088MPa(表压)和100℃下处理1小时。此外，为了除去处理后生成的盐，进行过滤，获得无规型氧化烯衍生物。92 g of glycerin and 18 g of potassium hydroxide as a catalyst were put into the autoclave, and after replacing the air in the autoclave with dry nitrogen, the catalyst was completely dissolved at 140° C. while stirring. Next, a mixture of 2,160 g of butylene oxide and 1,320 g of ethylene oxide was dropped through a dropping device, and stirred for 2 hours. Then add 400g of potassium hydroxide, replace the inside of the system with dry nitrogen, press-in 300g of methyl chloride at a temperature of 80-130°C, and react for 5 hours. Thereafter, the reaction composition was discharged from the autoclave, neutralized with hydrochloric acid, adjusted to pH 6 to 7, and treated at 100° C. under reduced pressure -0.088 MPa (gauge pressure) for 1 hour to remove contained water. In addition, in order to remove the salt produced after the treatment, filtration was performed to obtain a random type oxyalkylene derivative.

在使甲基氯反应之前取样和提纯后的物质的羟基值为47，所得无规型氧化烯衍生物5的化合物的羟基值为0.5，相对于末端甲基数的氢原子数的比例为0.011，氢原子几乎全部转换为甲基。The hydroxyl value of the substance sampled and purified before reacting methyl chloride was 47, the hydroxyl value of the obtained random-type oxyalkylene derivative 5 compound was 0.5, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.011 , the hydrogen atoms are almost completely converted to methyl groups.

以下例举了本发明的皮肤清洁剂的配方例，然而本发明的技术范围不限于这些配方例。另外，可以确定所得皮肤清洁剂与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外，皮肤刺激性小。The formulation examples of the skin cleansing agent of the present invention are listed below, but the technical scope of the present invention is not limited to these formulation examples. In addition, it was confirmed that the resulting skin cleanser had good compatibility with cosmetics, was excellent in ease of rinsing during washing, and had excellent usability such as no sticky feeling and no astringent feeling after washing, excellent cosmetic removal effect, and low skin irritation.

以下是配合例。The following is a combination example.

配合例1：卸妆凝胶(Make Cleansing gel)Combination example 1: Make Cleansing gel

(1)羟乙基纤维素                           0.1质量％(1) Hydroxyethylcellulose 0.1% by mass

(2)羧基乙烯基聚合物                       0.4(2) Carboxyvinyl polymer 0.4

(3)丙烯酸/甲基丙烯酸烷基酯共聚物           0.2(3) Acrylic acid/alkyl methacrylate copolymer 0.2

(4)乙二胺四乙酸三钠                       适量(4) Trisodium edetate Appropriate amount

(5)甲基椰油酰基牛磺酸钠                  0.1(5) Sodium methyl cocoyl taurate 0.1

(6)单异硬脂酸聚乙二醇酯                  0.5(6) Polyethylene glycol monoisostearate 0.5

(7)POB(30)POE(35)三甲基甘油醚(嵌段)       5.0(7)POB(30)POE(35)Triglyceryl trimethyl ether (block) 5.0

(在式(III)中，a+c+e＝30，b+d+f＝35，BO表示氧化丁烯基，EO表示氧化乙烯基。)(In the formula (III), a+c+e=30, b+d+f=35, BO represents a butylene oxide group, and EO represents an oxyethylene group.)

(8)氢氧化钾                      适量(8) Potassium hydroxide Appropriate amount

(9)乙醇                          5.0(9)Ethanol 5.0

(10)防腐剂                       适量(10) Appropriate amount of preservatives

(11)十甲基环状五聚硅氧烷          18.0(11) Decamethylcyclopentasiloxane 18.0

(12)甲基聚硅氧烷                  3.0(12) Methylpolysiloxane 3.0

(13)香料                          适量(13) Appropriate amount of spices

(14)纯化水                        余量(14) Balance of purified water

(制备方法和评价)(Preparation method and evaluation)

将(1)～(8)添加到(14)中，搅拌，溶解，作为水相部分。此后，将(10)溶解在(9)中，将其添加到水相部分中，进一步添加(11)～(13)，用乳化器乳化，获得卸妆凝胶。直接使所得卸妆凝胶融合后用水冲走时，确认该卸妆凝胶与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外皮肤刺激性小。Add (1) to (8) to (14), stir and dissolve, and use it as the water phase. Thereafter, (10) was dissolved in (9), added to the water phase, and (11) to (13) were further added and emulsified with an emulsifier to obtain a cleansing gel. When the obtained cleansing gel was directly fused and rinsed away with water, it was confirmed that the cleansing gel had good compatibility with cosmetics, was excellent in ease of rinsing during washing, and had excellent usability such as no stickiness and no astringent feeling after washing, and the cosmetics were removed. Excellent effect and less skin irritation.

配合例2：卸妆凝胶Matching Example 2: Cleansing Gel

(1)羟乙基纤维素                     0.05质量％(1) Hydroxyethylcellulose 0.05% by mass

(2)羧基乙烯基聚合物                 0.45(2) carboxy vinyl polymer 0.45

(3)丙烯酸/甲基丙烯酸烷基酯共聚物     0.1(3) Acrylic acid/alkyl methacrylate copolymer 0.1

(4)乙二胺四乙酸三钠                   适量(4) Trisodium edetate Appropriate amount

(5)甲基椰油酰基牛磺酸钠               0.01(5) Sodium methyl cocoyl taurate 0.01

(6)POB(32)POE(52)三甲基甘油醚(嵌段)   7.0(6) POB(32)POE(52) Trimethyl glyceryl ether (block) 7.0

(在式(III)中，a+c+e＝32，b+d+f＝52，BO表示氧化丁烯基，EO表示氧化乙烯基。)(In formula (III), a+c+e=32, b+d+f=52, BO represents a butylene oxide group, and EO represents an oxyethylene group.)

(7)聚天冬氨酸钠液                  适量(7) Sodium polyaspartate solution Appropriate amount

(8)春黄菊提取物                    适量(8) Chamomile extract Appropriate amount

(9)氢氧化钾                        适量(9) Potassium hydroxide Appropriate amount

(10)乙醇                           5.0(10)Ethanol 5.0

(11)聚氧化乙烯氢化蓖麻油            0.1(11) Polyoxyethylene hydrogenated castor oil 0.1

(12)防腐剂                         适量(12) Appropriate amount of preservatives

(13)十甲基环状五聚硅氧烷            18.0(13) Decamethylcyclopentasiloxane 18.0

(14)甲基聚硅氧烷                    3.0(14) Methyl polysiloxane 3.0

(15)香料                            适量(15) Appropriate amount of spices

(16)纯化水                          余量(16) Balance of purified water

(制备方法和评价)(Preparation method and evaluation)

将(1)～(9)添加到(16)中，搅拌，溶解，作为水相部分。此后，将(11)～(12)溶解在(10)中，将其添加到水相部分中，进一步添加(13)～(15)，用乳化器乳化，获得卸妆凝胶。在直接使所得卸妆凝胶融合后用水冲走时，确认该卸妆凝胶与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外皮肤刺激性小。Add (1) to (9) to (16), stir and dissolve, and use it as the water phase. Thereafter, (11) to (12) were dissolved in (10), added to the water phase, and (13) to (15) were further added and emulsified with an emulsifier to obtain a cleansing gel. When the obtained cleansing gel was directly fused and rinsed away with water, it was confirmed that the cleansing gel had good compatibility with cosmetics, and was excellent in usability such as ease of rinsing during washing, no stickiness and no astringent feeling after washing, and cosmetics. Excellent removal effect and less skin irritation.

配合例3：洗澡液Coordination example 3: bath liquid

(1)羟丙基甲基纤维素               0.1质量％(1) Hydroxypropylmethylcellulose 0.1% by mass

(2)甘油                           10.0(2) Glycerin 10.0

(3)二丙二醇                       5.0(3) Dipropylene glycol 5.0

(4)月桂酸三乙醇胺                 12.0(4) Triethanolamine laurate 12.0

(5)月桂基二甲基氨基醋酸甜菜碱       5.0(5) Betaine Lauryl Dimethylaminoacetate 5.0

(6)椰油酸二乙醇酰胺                 3.0(6) Diethanolamide Cocoate 3.0

(7)POB(17)POE(28)三甲基甘油醚(嵌段)  5.0(7) POB(17)POE(28) Trimethyl glyceryl ether (block) 5.0

(在式(III)中，a+c+e＝17，b+d+f＝28，BO表示氧化丁烯基，EO表示氧化乙烯基。)(In the formula (III), a+c+e=17, b+d+f=28, BO represents a butylene oxide group, and EO represents an oxyethylene group.)

(8)春黄菊提取物                 适量(8) Chamomile extract Appropriate amount

(9)乙二胺四乙酸三钠             适量(9) Trisodium edetate Appropriate amount

(10)防腐剂                      适量(10) Appropriate amount of preservatives

(11)色素                        适量(11) Appropriate amount of pigment

(12)香料                        适量(12) Appropriate amount of spices

(13)纯化水                      余量(13) Balance of purified water

(制备方法和评价)(Preparation method and evaluation)

将(1)添加到(13)中，搅拌分散，然后加热至70℃，添加(2)～(12)，搅拌溶解。此后，使用热交换器冷却，获得洗澡液。在所得洗澡液在水中起泡和融合之后用水冲洗时，确认该洗澡液与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外皮肤刺激性小。Add (1) to (13), stir to disperse, then heat to 70°C, add (2) to (12), stir to dissolve. Thereafter, it is cooled using a heat exchanger to obtain a bath liquid. When the resulting bath liquid was foamed and fused in water and rinsed with water, it was confirmed that the bath liquid had good compatibility with cosmetics, and was excellent in usability such as ease of rinsing during washing, no sticky feeling and no astringent feeling after washing, and cosmetics. Excellent removal effect and less skin irritation.

配合例4：研制皂Coordination Example 4: Development of Soap

(1)钠皂                              余量(1) Sodium soap balance

(2)钾皂                              5.0质量％(2) Potassium soap 5.0% by mass

(3)氯化钠                            0.3(3) Sodium chloride 0.3

(4)甘油                              0.5(4) Glycerin 0.5

(5)月桂酸                            5.0(5) Lauric acid 5.0

(6)POB(41)POE(48)三甲基甘油醚(嵌段)   3.0(6) POB(41)POE(48) Trimethyl glyceryl ether (block) 3.0

(在式(III)中，a+c+e＝41，b+d+f＝48，BO表示氧化丁烯基，EO表示氧化乙烯基。)(In the formula (III), a+c+e=41, b+d+f=48, BO represents a butylene oxide group, and EO represents an oxyethylene group.)

(7)色料                    适量(7) Appropriate amount of pigment

(8)乙二胺四乙酸三钠        适量(8) Trisodium edetate Appropriate amount

(9)香料                    适量(9) Appropriate amount of spices

(制备方法和评价)(Preparation method and evaluation)

将(1)～(9)在60℃下加热和混合，将该液体流入到框内，冷却和固化，获得研制皂。所得皂在水中起泡和融合后用水冲洗时，可以确认该皂与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外皮肤刺激性小。(1) to (9) were heated and mixed at 60° C., the liquid was poured into a frame, cooled and solidified, and ground soap was obtained. When the obtained soap was foamed in water and rinsed with water after merging, it was confirmed that the soap had good compatibility with cosmetics, was excellent in ease of rinsing during washing, and had excellent usability such as no stickiness or astringency after washing, and the effect of removing cosmetics Excellent, in addition to being less irritating to the skin.

配合例5：卸妆凝胶Coordination Example 5: Cleansing Gel

(1)羟乙基纤维素                         0.1质量％(1) Hydroxyethylcellulose 0.1% by mass

(2)羧基乙烯基聚合物                     0.3(2) Carboxyvinyl polymer 0.3

(3)丙烯酸/甲基丙烯酸烷基酯共聚物         0.3(3) Acrylic acid/alkyl methacrylate copolymer 0.3

(4)乙二胺四乙酸三钠                     适量(4) Trisodium edetate Appropriate amount

(5)单异硬脂酸聚乙二醇酯                 0.5(5) Polyethylene glycol monoisostearate 0.5

(6)POB(14)POE(34)三甲基甘油醚(嵌段)      3.0(6)POB(14)POE(34)Triglyceryl trimethyl ether (block) 3.0

(在式(III)中，a+c+e＝14，b+d+f＝34，BO表示氧化丁烯基，EO表示氧化乙烯基。)(In the formula (III), a+c+e=14, b+d+f=34, BO represents a butylene oxide group, and EO represents an oxyethylene group.)

(7)氢氧化钾                    适量(7) Potassium hydroxide Appropriate amount

(8)乙醇                        5.0(8) Ethanol 5.0

(9)POE氢化蓖麻油               0.3(9) POE hydrogenated castor oil 0.3

(10)防腐剂                     适量(10) Appropriate amount of preservatives

(11)十甲基环状五聚硅氧烷       10.0(11) Decamethylcyclopentasiloxane 10.0

(12)甲基聚硅氧烷               10.0(12) Methyl polysiloxane 10.0

(13)香料                       适量(13) Appropriate amount of spices

(14)纯化水                     余量(14) Balance of purified water

(制备方法和评价)(Preparation method and evaluation)

将(1)～(7)添加到(14)中，搅拌溶解，作为水相部分。此后，将(9)～(10)溶解在(8)中而得到的物质添加到水相部分中，进一步添加(11)～(13)，用乳化器乳化，获得卸妆凝胶。在直接使所得卸妆凝胶融合后用水冲走时，确认该卸妆凝胶与化妆品的融合性良好，洗涤中的易冲洗性、洗涤后无黏腻感和无发涩感等使用性优异，化妆品去除效果优异，此外皮肤刺激性小。Add (1) to (7) to (14), stir and dissolve, and use it as the water phase. Thereafter, what dissolved (9) to (10) in (8) was added to the water phase, and (11) to (13) were further added and emulsified with an emulsifier to obtain a cleansing gel. When the obtained cleansing gel was directly fused and rinsed away with water, it was confirmed that the cleansing gel had good compatibility with cosmetics, and was excellent in usability such as ease of rinsing during washing, no stickiness and no astringent feeling after washing, and cosmetics. Excellent removal effect and less skin irritation.

Claims (11)

1. a skin preparations for extenal use is characterized in that, comprises the block type oxyalkylene derivative shown in the following formula (I):

Y-[O(EO)_a-(AO)_b-(EO)_c-R]_k (I)

In the formula, Y is the residue of having removed hydroxyl with polyhydric alcohol of 3～6 hydroxyls, and k is described hydroxyl groups number, and EO is that oxyethylene group, AO are the oxyalkylene group of carbon number 3～6, and EO and AO add respectively becomes block-wise; A * k, b * k and c * k each oxyalkylene group, the average addition molal quantity of oxyethylene group of oxyethylene group, carbon number 3～6 naturally, 0≤a * k≤100,1≤b * k≤100,0≤c * k≤100, wherein (a+c) * k〉1; With respect to the summation of the oxyalkylene group of whole oxyethylene groups in the formula (I) and carbon number 3～6, the ratio of the whole oxyethylene groups in the formula (I) is 10～80 quality %; R is identical or different, is the alkyl of carbon number 1～4.

2. skin preparations for extenal use according to claim 1 is characterized in that, the AO of the block type oxyalkylene derivative shown in the described formula (I) is the butylene oxide base.

3. skin preparations for extenal use according to claim 1 and 2 is characterized in that, a of the block type oxyalkylene derivative shown in the following formula (I) is 0, the addition of AO and EO is in proper order for being (AO)-(EO) with respect to the Y in the formula.

4. according to each described skin preparations for extenal use in the claim 1～3, it is characterized in that the block type oxyalkylene derivative shown in the described formula (I) of cooperation 0.01～70 quality %.

5. pachylosis improving agent, with the block type oxyalkylene derivative shown in the described formula (I) as effective ingredient.

6. usability improving agent, with the block type oxyalkylene derivative shown in the described formula (I) as effective ingredient.

7. a skin cleaner is characterized in that, contains block type oxyalkylene derivative shown in the described formula (I) of 0.01～70 quality % and the wetting agent of 0.1～20 quality %.

8. skin cleaner according to claim 7 is characterized in that, the content of the block type oxyalkylene derivative shown in the described formula (I) is 0.1～20 quality %.

9. according to claim 7 or 8 described skin cleaners, it is characterized in that the AO base of the block type oxyalkylene derivative shown in the described formula (I) is the butylene oxide base.

10. according to each described skin cleaner in the claim 7～9, it is characterized in that a of the block type oxyalkylene derivative shown in the described formula (I) is 0, the addition of AO and EO is in proper order for being (AO)-(EO) with respect to the Y in the formula.

11., it is characterized in that described wetting agent is to be selected from dipropylene glycol, propylene glycol, 1,3 butylene glycol and the glycerol one or more according to each described skin cleaner in the claim 7～10.