商丘润滑油价格联盟

【综述】矿物油对皮肤的广泛益处

2022-05-12 08:37:46


A review on the extensive skin benefits of mineral oil

综述:矿物油对皮肤的广泛益处


作者 | A.V. Rawlings and K. J. Lombard

AVR Consulting Ltd, Northwich, Cheshire, U.K. and Union Swiss, Cape Town, South Africa

来源 | International Journal of Cosmetic Science (IF=1.581)

编译 | Aaron


Keywords: mineral oil, moisturisation, occlusivity

关键词:矿物油,滋润,封闭性


Synopsis

概要


This review was initially prepared in 2011 before Professor Johann Wiechers tragically passed away. It has been updated and is being published in his memory. It discusses the importance of mineral oil and its benefits to skin. Its source, structure, properties and efficacy are discussed. Mineral oil has been shown to improve skin softness and barrier function better than some other emollients using the gas-bearing dynamometer and standard water vapour transmission testing as well as in vivo studies showing its effects on suppressing transepidermal water loss (TEWL). It has also been subjected to the rigour of the newer in vivo confocal microscopic measurements now used for testing the performance of moisturizers by following the swelling characteristics of the stratum corneum and been found favourable compared with many vegetable oils. Its introduction as a cosmetic oil was in the late 1800s, and still today, it is used as one of the main components of moisturizers, a true testament to its cost to efficacy window. Naturally, it has physical effects on the stratum corneum, but it is expected that these will translate into biological effects simply through its mechanism of hydrating and occluding the stratum corneum from which many benefits are derived.

本篇综述最初是在2011年准备的,在Johann Wiechers教授不幸去世之前。它已经更新了,并为了纪念他而发表。文章论述了矿物油的对皮肤的重要性和益处。对其来源、结构、性能和功效进行了探讨。已经证明矿物油比一些其他的润肤剂可以更好地改善皮肤柔软度和屏障功能,使用含气测力计和标准水蒸气传输测试以及体内研究,表明对抑制表皮水分流失(TEWL)的作用。它也受到了新的体内共焦显微镜测量的严格考验,这种方法现在用来测试润肤霜的性能,依循角质层的膨胀特征,并发现与许多植物油相比是有利的。它成为一种化妆品用油在19世纪后期,现在仍然作为一种保湿的主要成分使用,这是对其功效的真正证明。自然地,它对角质层有物理影响,但预期这些将仅仅通过角质层吸水和封闭转化为生物效应,从中获得许多益处。


Mineral oil: its source, its connection to the petrochemical industry, the process used to extract it and its usage

矿物油:来源,与石化行业的联系,用于提取及使用的过程


It is not known when mineral oil was first produced, but as a derivative of petroleum, it must have been after the discovery of crude oil, but even that is already known for thousands of years. The industrial drilling for petroleum started around 1852 with production rates increasing exponentially over the first decades. According to generally accepted theory (the biogenic petroleum origin theory), petroleum is derived from ancient fossilized organic materials. Crude oil and natural gas are products of heating ancient organic materials over geological time. Formation of petroleum occurs from the decomposition of organic material at elevated temperatures in the absence of oxygen. Today’s oil is formed from the preserved remains of prehistoric zooplankton and algae, which had settled to a sea or lake bottom in large quantities at depths where oxygen is no longer dissolved (the remains of prehistoric terrestrial plants, on the other hand, tended to form coal). Over geological time, the organic matter mixed with mud and was buried under heavy layers of sediment resulting in high levels of heat and pressure. This process caused the organic matter to change, first into a waxy material known as kerogen, which is found in various oil shales around the world, and then with more heat into liquid and gaseous hydrocarbons. This is the crude oil and gas that are being recovered nowadays in oil and gas fields, respectively. Petroleum is thus fossil plankton and algae derived material and hence a natural material. Its diverse biological origin and the wide variety of conditions under which petroleum is formed explain why petroleum is a complex mixture of many different materials, mainly hydrocarbons. Its generalized weight composition is paraffins (30%; range 15–60%), naphthenes (49%; range 30–60%), aromatics (15%; range 3–30%) and asphaltics (6%; range: remainder). Crude oil therefore needs to be refined before it can be used in modern applications such as petrol for cars, kerosene for planes, lubricants for engines or oil for heating homes, to name but a few.

目前尚不清楚矿物油是什么时候被生产出来的,但作为石油的一种衍生物,一定是在发现原油之后,但即使是那样也已经有数千年了。石油的工业钻探开始于大约1852年,在最初的几十年里,产量呈指数增长。根据普遍接受的理论(源于生物的石油起源理论),石油起源于远古的化石有机材料。原油和天然气是在地质时期加热远古有机材料的产物。石油是由于在没有氧气的情况下,有机物在高温下分解而形成的。今天的石油是由史前浮游动物和藻类保存下来的遗骸形成的,这些浮游生物和藻类大量沉积在海底或湖底深处,在那里氧气不再被溶解(另一方面,史前陆生植物的遗骸则倾向于形成煤)。在地质时期,有机物和泥沙混合,被埋在厚层的沉积物下,导致了高温和高压。这一过程引起了有机物的变化,首先转变为一种称为油母岩质的蜡质材料,它在存在于世界各地的油页岩中,然后更多的热量将其转化成液态和气态的烃类。这是目前在油气田中分别被回收的原油和天然气。因此,石油是浮游生物和藻类衍生的材料,所以是一种天然材料。它的多样化生物起源以及形成石油的各种各样条件解释了为什么石油是中许多不同材料组成的复杂混合物,主要是烃类。它的一般重量组成是石蜡(30%;范围为15-60%),环烷烃(49%,范围为30-60%),芳香烃(15%,范围3-30%)和沥青(6%;范围:剩余物)。因此在现代应用中,原油需要经过精炼,例如车用汽油,航空用煤油,发动机润滑油或者家庭采暖用油,仅举这几个例子。


Mineral oil, which is the topic of this report, is a complex mixture of highly refined saturated hydrocarbons, which are derived from petroleum through various refining steps and subsequent purification by acid or catalytic hydrotreatment. As the most purified form of petroleum that exists, mineral oil is not merely a by-product of petroleum but a specifically isolated and prepared fraction of petroleum with highly specialized product applications, among others, in food, cosmetics and pharmaceutics. A complex series of processing steps is needed to produce mineral oils with the physical properties and the level of purity required for use in cosmetics, food and pharmaceuticals. Crude petroleum oils are distilled and processed by various methods to make finished mineral oils. Distillation of the crude oil produces fractions that differ in boiling range, average molecular weight and viscosity. The fractions obtained following distillation can be further refined by solvent extraction that removes polar and polycyclic compounds. The refining process used to make the mineral oil discussed in this report consists of treatment with sulphuric acid or hydrogenation (i.e. treatment with hydrogen in the presence of a catalyst at high pressure and temperature). Both processes are designed to remove polycyclic aromatic hydrocarbons, which are believed to be responsible for the historical finding of carcinogenicity of rodents after treatment with petroleum derivatives. Refined mineral oil is composed of two hydrocarbon types: parraffinics, which are branched-chain alkanes, and naphthenics, which are alkanes containing one or more saturated cyclic structures. For the non-chemist readers of this report, alkanes are saturated hydrocarbons, chemical compounds that consist only of the elements carbon (C) and hydrogen (H). In mineral oil, especially, the longer-chained hydrocarbons are present. The parraffinics (i.e. the saturated straight-chain or branched hydrocarbons) are characterized by a higher viscosity and cloud point than the naphthenics (the cyclo-paraffinic hydrocarbons) that are characterized by their non-waxy nature.

矿物油,作为文章的主题,是一种高度精炼饱和烃的复杂混合物,是通过各种精炼步骤从石油中提炼出来的,然后通过酸化或催化加氢精制而成。作为最精制的石油,矿物油不仅仅是石油的副产品,而是石油的一种特别分离和制备的部分,具有高度专业化的产品应用,包括食品、化妆品和医药等。需要一系列复杂的处理步骤来生产矿物油,使其物理性质和纯度符合化妆品、食品和药品的使用需要。原油经过蒸馏和各种方法加工,制得最终的矿物油。原油的蒸馏产生的馏分在沸腾范围、平均分子量和粘度上有所不同。蒸馏后得到的馏分可以用溶剂萃取法进一步精炼,去除极性和多环化合物。本文探讨的矿物油所使用的的精炼过程包括硫酸化或氢化处理(也就是高温高压和催化剂存在下加氢处理)。这两个过程都被设计用来去除多环芳烃,这类石油衍生物被认为是啮齿动物经其处理后,对致癌性的历史上的发现负有责任。精制矿物油由两类烃组成:属于支链烷烃的石蜡烃,和有一个或多个饱和环状结构的烷烃。对于本文的非化学读者,烷烃是饱和烃,仅由碳(C)和氢(H)构成的化合物。尤其是在矿物油中,存在更长链的烃类。石蜡烃(也就是饱和直链或支链烃类)相较于特点是不含蜡的性质的环烷烃(脂环烃类),以更高的粘度和浊点为特征。


The two hydrocarbon types can be separated via distillation and other physical processes. The ratio of these two chemical families and their molecular weight determines the physical properties of the resulting oils. Because of their complex chemical compositions, mineral oils are classified by their viscosities. Medicinal, cosmetic and food-grade oils are highly refined white mineral oils with a carbon number range from 15 to 25 for light and 25 to 50 heavy oils.

这两种烃类型可以通过蒸馏和其他物理过程分离。这两种化学同系物的比例和它们的分子量决定了由此产生的油的物理性质。由于它们的复杂化学组成,矿物油按粘度分类。医药级,化妆品级和食品级油类是高度精制的白油,其碳的数量范围在15-25之间为轻矿物油,25-50为重矿物油。


Mineral oil has been used in cosmetics for more than a hundred years, but the exact date of the introduction of mineral oil in cosmetics could not be found. It has also been used in electrical and food applications. As extreme refining of crude petroleum is necessary, its introduction is estimated to have been around 1870–1880, as around that time the production of mineral oil was high enough at low costs. This combination of high production at low cost is probably also the reason why it was used as a cheaper alternative for vegetable oils. Table I lists a number of differences and similarities between vegetable oils and mineral oils used in cosmetics. This table indicates that both types of oil have their advantages and disadvantages. Although both products are nature-derived, the chemical process of manufacturing mineral oil is such that it does not meet the standards of ‘naturals’ in cosmetics. However, its ‘inertness’ makes it an extremely safe chemical that can even be used in food and pharmaceuticals. One can conclude from this that when mineral oil is used, it is more often than not used at high percentages in the formulations in which it is included.

矿物油已经在化妆品中使用超过了100年,但是将矿物油引入化妆品的确切日期却不得而知。它也被用于电气和食品的应用。由于原油的极度精炼是必要的,它的引入时间估计在大约1870-1880年之间,因为在那段时间,矿物油的产量足够高,价格便宜。高产量、低价格的组合可能也是它用作更廉价的植物油替代物的原因。表1列出了化妆品中使用的植物油和矿物油的一些不同和相似之处。这张表表明两种油都有各自的优点和缺点。尽管两种产品都是天然来源的,生产矿物油这样的化学过程,导致了它不能满足化妆品中“天然成分”的标准。然而,它的“惰性”使它成为一种非常安全的化学物质,甚至可以用于食品和药物。由此可以得出结论:当使用矿物油时,配方中通常包含有更高百分比的含量。

 


Mineral oil is used in many topical applications and with added fragrance is marketed as baby oil. Although baby oil is primarily marketed as a generic skin ointment, other applications exist in common use. It is often used on infant ‘diaper rashes’ to ease the inflammation. Similarly, it may alleviate mild eczema, particularly when the use of corticosteroid creams is not desirable. Mineral or baby oil can also be employed in small quantities (two to three drops daily) to clean inside ears.

矿物油有许多外部应用,在加入香精之后,成为市场中的婴儿油。尽管婴儿油主要作为一般的皮肤油膏来销售,也有其他的常用用途。它常被用于婴儿“尿布疹”来减轻炎症反应。类似的,它可以缓解轻度湿疹,尤其是使用皮质类固醇药膏是不合适的时候。矿物油或者婴儿油也能少量使用(每天2-3滴)来清理耳朵内部。


Mineral oil: its structure and properties 

矿物油:结构与性质


Mineral oil is known under many different names. The reason for this is probably historical as the product was created long before common nomenclature was implemented. Synonyms include heavy mineral oil, light mineral oil, liquid paraffin, liquid petrolatum, mineral oil mist, paraffin oil, paraffinum liquidum, petrolatum liquid, petroleum oil, white mineral oil and white oil. To avoid any confusion, this mixture of hydrocarbons will be referred to in this report as mineral oil. It is known by CAS as 8012-95-1; 8020-83- 5 (wh.); 8042-47-5 (wh.); 39355-35-6; 79956-36-8; 83046-05-3; EINECS/ELINCS 232-384-2; 232-455-8 (wh.); INS905a.

矿物油有许多不同的名称。其原因可能是由历史造成的,因为这类产品在通用命名法实施很久之前就产生了。别名包括:重矿物油,轻矿物油,液体石蜡,液体凡士林,矿物质油雾,石蜡油,矿脂,凡士林液体,石油,白矿物油和白油。为了避免混淆,本篇报告中提到的这类烃混合物叫做矿物油。它被CAS称为8012-95-1;8020-83- 5(wh.);8042-47-5(wh.);39355-35-6;79956-36-8;83046-05-3;EINECS/ELINCS 232-384-2;232-455-8(wh.);INS905a。


According to the Specialty Chemicals Source Book, 4th Edition, the definition of mineral oil is ‘a liquid mixture of hydrocarbons obtained from petroleum by intensive treatment with sulphuric and oleum, or by hydrogenation, or a combination, and consisting predominantly of saturated C15–C50 hydrocarbons’. It is a colourless, transparent, oily liquid that is odourless and tasteless. It is insoluble in water and ethanol, soluble in benzene, ether, petroleum ether, carbon disulphide and volatile oils. Its density is 0.83–0.86 kg L-1 for the light mineral oil variant and 0.875–0.905 kg L-1 for the heavy mineral oil variant. Its flashpoint is 229°C (or 444°F), whereas its surface tension is <35 dynes cm-1. The LD50 (oral, mouse) is 22 g kg-1, whereas the highly purified food grades are to be of low toxicity. Many uses are known, of which the most common have already been described previously but others include protectant, binder, extender, pharmaceutical vehicle, corrosion inhibitor, viscosity modifier in metal treatment, etc. It is FDA approved for ophthalmics, orals and topical and is listed in many different pharmacopeia. It is sold by more than 45 different suppliers, many of which are known in the cosmetic industry and is sold under at least 123 different registered trade names.

根据《特种化学品源书》第4版,矿物油的定义为“一种烃类的液体混合物,从被硫酸和发烟硫酸强化处理过的、或通过加氢作用的,或两者组合强化处理后的石油中获得,主要由饱和C15-C50的烃类组成”。它是无色透明油状液体,且无色无味。不溶于水和乙醇,可溶于苯,乙醚,石油醚,二硫化碳和挥发性油。轻矿物油型密度在0.83-0.86 kg L-1间,重矿物油型密度在0.875–0.905 kg L-1间。闪点为229°C(或444°F),表面张力为<35达因cm-1。LD50(口服,小鼠)为22 g kg-1,而高纯度食品级则是低毒性的。许多的用途是众所周知的,其中最常见的在前文已经描述过,但其他的包括保护剂、粘结剂、增稠剂、药物载体、缓蚀剂、粘度调节剂等。它被FDA批准用于眼科,口试和外用,并在许多不同的药典中列出。它被超过45家不同的供应商销售,其中许多是在化妆品行业中所知的,并且至少有123个不同的注册商标名称在销售。


The popularity of mineral oil as a cosmetic ingredient emerged in the last quarter of the nineteenth century because of its low cost and abundant supply. In the first quarter of the twenty-first century, we see a ‘Back-to-Nature’ movement that is purely based on the perception of the consumer that anything derived from nature is better, safer and more efficacious, whereas anything synthetic is chemical, dangerous and toxic. Table II therefore lists the efficacy/capacity of vegetable oils and mineral oil for a series of physical and biological parameters. Again, as with Table I, the reader should keep in mind that ‘the’ vegetable oil does not exist and that therefore only a range can be given for ‘vegetable oils’. 

矿物油作为化妆品的一种成分而普及出现在19世纪后四分之一,因为它成本低,供应充足。在21世纪的前四分之一,我们看到了“回归自然”的运动,纯粹是基于消费者的感知,即任何来自自然的事物都是更好,更安全和更有效的,而任何合成的事物是化学的,危险的和有毒的。因此表2列出了植物油和矿物油的功效/能力的一系列物理和生物参数。再一次的提醒,和表1一样,读者应当记住“特指的”植物油是不存在的,因此只能给“植物油”提供一个范围。

 


Based on the findings in this table, the differences between vegetable oils and mineral oil are only marginal. The efficacy of mineral oil is mainly ‘external’, that is, on top of the skin (where it leads to emolliency and skin moisturization via occlusivity), whereas vegetable oils as a class of chemicals are smaller and, even within a single oil, more chemically diverse; hence, they offer less occlusivity but a higher biological efficacy in specific applications (such as skin whitening, anti-itch, etc.). The sensory profile of mineral oil has been well described through the work of Wiechers and co-workers.

根据这张表的调查结果,植物油和矿物油之间的差别是很小的。矿物油的功效主要是“外部的”,即在皮肤上(通过封闭性,它导致滋润和皮肤保湿),而植物油作为一种化学物质是比较小的,即使在一种油中,化学成分也是多样化的;因此,它们提供了较少的封闭性,但在特定应用(比如皮肤美白,止痒等)具有较高的生物功效。矿物油的感官特性已经通过Wiechers和同事的工作得到了很好的描述。


Efficacy of mineral oil

矿物油的功效


Skin moisturization: Blank first identified the importance of water in softening the stratum corneum but excluded the benefits of oils having this effect. Peck and Glick came to similar conclusions demonstrating that mineral oil had no effect on the hardness of the stratum corneum. Similarly, Rieger and Deem found that mineral oil alone had no effect on stratum corneum extensibility, but they did show its effects on reducing water loss in vivo much like the early studies of Powers and Fox in vivo. The interpretation of the original studies on stratum corneum flexibility was erroneous as the authors did not take the effect of mineral oil as a mildly occlusive agent into account. In fact, it was not the mineral oil that improved stratum corneum flexibility but the water that was trapped because of the occlusive property of mineral oil.

皮肤保湿:Blank首先确认了水分在软化角质层方面的重要性,但是排除了油类具有这种效果的好处。Peck和Glick得出了类似的结论:证明矿物油对角质层的硬度没有影响。类似地,Rieger和Deem发现单独的矿物油对扩展角质层没有影响,但是他们确实显示它在减少体内水分流失的影响,就像Powers和Fox早期的体内研究一样。最初关于角质层柔韧性的研究解释是不正确的,因为作者并没有把作为一种温和的封闭介质的矿物油的影响考虑进去。实际上,不是矿物油提高了角质层的灵活性,而是由于矿物油的封闭特性,水被锁住了。


Although new mechanisms of action of active ingredients are being identified all the time, emolliency, occlusion and humectancy are the mainstay of action of moisturizers. Mineral oil possesses the first two of these benefits. Occlusion will deliver the greater efficacy as it helps to retain water in the skin rather than just masking superficial problems. To obtain occlusion from a cosmetic ingredient, two aspects are important: alkyl chain length and distribution as well as substantivity.

尽管有效成分的新作用机制一直被鉴别,润滑性、封闭性和保湿性是保湿霜的主要作用。矿物油具有前两种好处。封闭将带来更大的功效,因为它帮助把水保持在皮肤中,而不是仅仅遮蔽表面问题。为了获得化妆品成分中的封闭性,重要的是两方面:烷基链的长度和分布以及亲和力。


First of all, the molecules must all align and in doing so, form a tight ‘palisade’ that prevents the passage of other molecules. This can be achieved by having straight alkyl chains of the same length. In contrast to vegetable oils where the molecules can be extremely diverse, mineral oil is almost nothing else but straight-chain alkyl chains. The difference between light and heavy mineral oil (the low- and high-viscosity variants, respectively) is that the light variant contains more cyclic (saturated) molecules that prevent the consistent build-up of the palisade. Light mineral oil is therefore less occlusive than heavy mineral oil. But the presence of (only) straight alkyl chains alone is not enough. If there are different alkyl chains with different chain lengths, this also allows for the existence of ‘holes’ in the palisade fence. Heavy mineral oil may be predominantly straight-chain alkyl chains, but the chain length is highly variable, ranging from 25 to 50 carbon atoms. This is the reason that the occlusive nature of mineral oil is good, but not perfect.

首先,所有的分子都必须排列整齐,在这过程中,形成一道紧密的“栅栏”阻止其他分子通过,这可以通过具有相同长度的直链烷基来获得。与分子结构可能极其多样化的植物油相反,矿物油几乎就是直链烷基链。轻矿物油和重矿物油(分别为低粘度和高粘度型)的区别是轻型包含了更多的环状分子(饱和的)结构,阻止了栅栏的持续堆积。但仅仅只存在直链烷基是不够的。如果有不同链长的不同烷基链,这也会允许在栅栏上存在孔洞。重矿物油可能主要是直链烷基,但是链长变化很大,范围从25到50个碳原子。这就是矿物油的封闭性是很好的,但不是最好的原因。


The second aspect is the substantivity of the occluding oil. If the molecule penetrates the skin very well, the palisade disappears very quickly, so the resulting occlusion is not very high. This removal from the site of application is mainly caused by diffusion, both into the skin (skin permeability) as well as lateral diffusion on top of the skin. This is easily understood from the waxy nature of the latter.

第二部分是封闭油的亲和性。如果分子能很好的穿透皮肤,那么栅栏会非常快的消失,从而产生的封闭不是非常高。这种从应用地点的消除主要由扩散作用引起,进入皮肤(渗透进皮肤)和在皮肤上横向扩散。这一点很容易从后者的蜡质特性中得到理解。


The viscosity of this waxy material is that high that it has no lateral diffusion and it is too big to penetrate, whereas mineral oil has some lateral diffusion but hardly any skin penetration. A disadvantage of vaseline petroleum jelly, however, is its unfavourable sensory profile. It is an effective moisturizer but absolutely not an elegant product. Mineral oil seems to be at the optimum of two opposing forces: it still has enough substantivity and occlusivity left to create skin moisturization but not enough substantivity to become unacceptable from a sensory point of view. Most other commonly used cosmetic emollients are too light (i.e. not viscous enough) to have this degree of substantivity, or if viscous, they are not sufficiently regularly shaped to allow the ‘palisade’ formation. Fixed vegetable oils, however, tend to be a little bit heavier, and they may also hydrate skin to some extent, provided they are used in high enough concentrations. And this introduces the final proviso: concentration. You may have an oil that is sufficiently straight chained to give the ‘palisade’ structure and sufficiently substantive to provide occlusivity, but if this oil is only present at small amounts in a formulation, there is still not enough occlusivity. 

这种蜡质材料的粘度很高,没有横向扩散,并且它太大了,无法穿透,而矿物油有一些横向扩散,但几乎没有皮肤穿透。然而,凡士林的一个缺点,是它的不佳的感官外形。它是一种有效的保湿剂,但绝对不是一种高雅的产品。矿物油似乎处于两种对立力量的最佳状态:它仍然有足够的亲和力和封闭性来创造皮肤的保湿但从感官的角度并没有到难以接受程度的亲和力。大多数其他常用的化妆品润肤剂都太轻了(也就是粘性不足)以致于没有这种程度的亲和力,或者粘性够了,它们不能形成有规则而又足够的栅栏结构。然而,固定植物油往往要重一些,只要它们的浓度足够高,在某种程度上,它们也会滋润皮肤。这就引进了最后的限制条件:浓度。你可能有一种油,它有足够的直链形成栅栏结构并且足够实质性的提供封闭性,但是如果配方中存在的这种油仅是少量的,仍然没有足够的封闭性。


Strubmann et al. used polytetrafluoroethylene membranes to mimic skin and examined the effects of a variety of emollients on its water vapour permeability in which mineral oil was shown to be very occlusive compared with other ‘fluid’ emollients (Fig. 1). Fromder et al. also compared a variety of emollients/gelatin mixtures for their occlusive properties in which mineral oil performed very well. However, it must be borne in mind that real skin was not used in either of these examples. Indeed, comparing the efficacy from the in vitro data to the in vivo TEWL measurements, the performance of all the emollients was less with mineral oil reducing baseline transepidermal water loss (TEWL) by 16% (for comparison, petroleum jelly reduced TEWL by 43%). Tsutsumi et al. demonstrated in vivo using TEWL that mineral oil gave an occlusivity to forearm skin of about 25% at and above 2 mg cm2, similar to the work of Osborne and Gerraughty. Lieb et al. [18] provided even better occlusivity from mineral oil in hamster skin in vitro. Changing the viscosity of the mineral oil can improve efficacy. By reducing its diffusion, even greater efficacy has been reported by Morrison with gelled mineral oils. The rationale for these effects was already explained previously.

Strubmann等使用聚四氟乙烯膜模拟皮肤,调研了一些润肤剂的水蒸气透湿性,其中矿物油与其他的液体润肤剂相比,展现出非常的封闭性(图1)。Fromder等也比较了一些润肤剂/凝胶混合物的封闭性能,其中矿物油表现非常好。然而,必须记住这些例子中都没有使用真正的皮肤。实际上,比较体外数据和体内表皮水分流失测量的功效,所有润肤剂的表现都少于矿物油,它可以减少16%的表皮水分流失基线(相比而言,凡士林减少表皮水分流失为43%)。Tsutsumi等证明在体内使用表皮水分流失,矿物油对前臂皮肤的封闭性为25%左右,超过2 mg/cm2,与Osborne和Gerraughty的工作类似。Lieb等提供了矿物油在仓鼠体外皮肤上更好的封闭性。通过减少扩散,Morrison发表了关于稠化矿物油更高的功效。这些影响的原理在前文已经解释过了。

 

(图1)各种润肤剂的水蒸汽传输率(1 肉豆蔻酸异丙酯;2 油酸乙酯;3 棕榈酸异丙酯;4 硬脂酸异丙酯;5 2-乙基椰油酸己酯;6 2-乙基棕榈酸己酯;7 油酸癸酯;8 2-乙基牛脂酸己酯;9 2-乙基硬脂酸己酯;10 油酸油醇酯;11 2-辛基十二烷基豆蔻酸酯;12 油醇芥酸酯;13 2-辛基十二烷基棕榈酸酯;14 2-辛基十二烷基硬脂酸酯;15 矿物油。


Mineral oil, Johnson’s Baby Oil as reported by Jolly and Sloughfy, has been used to treat dry skin. However, to date, it has been reported to have similar efficacy to other oils. Nevertheless, the barrier effects of mineral oil can also be observed in the skin’s susceptibility to stinging from lactic acid. Sahlin et al. have reported that increasing the concentration of mineral oil in formulations containing the same concentration of lactic acid tended to decrease the stinging effect thereof, as the concentration of mineral oil increased from 10% to 50%. This suggests that the lactic acid was less capable of penetrating the additional barrier created by the mineral oil. The results of this experiment are shown in Fig. 2. Mineral oil has many applications in bath oils. Knox et al. described superior water dispersible bath oils in 1958. Taylor went on to prove that mineral oil type bath oils are better absorbed into skin than vegetable oils. Stolar came to similar conclusions but also found that mineral oils with increasing viscosities (and therefore reducing naphthenic content) deposited less onto skin in vivo. In vivo, mineral oil binds to skin better than vegetable oils, whereas Bollinger et al. and Knox et al. found conflicting results in vitro with the latter studies correlating with in vivo findings.

矿物油,由Jolly和Sloughfy 报道的强生婴儿油,已经被用来治疗干燥的皮肤。然而,迄今为止,其他油类也被报道有类似的功效。虽然如此,矿物油的栅栏效应在皮肤对乳酸刺痛的敏感性方面也可以被观察到。Sahlin等报道了随着矿物油浓度从10%增加到50%,提高含有相同乳酸浓度的配方中矿物油的浓度,倾向于降低它的刺痛效果。这表明了乳酸较弱的穿透矿物油制造的额外障碍的能力。实验结果如图2所示。矿物油在沐浴油中有很多应用。1958年Knox等描述了一种优质水分散浴油。Taylor继续证明了矿物油型沐浴油比植物油更易被皮肤吸收。Stolar得出了类似的结论,但也发现提升粘度的矿物油(因此减少环烷基含量)在体内较少的沉积在皮肤上。在体内,矿物油比植物油更好的与皮肤结合,而Bollinger等和Konx等发现了在体外的矛盾结果,后者的研究与体外的发现有关。

    

(图2)在10%的矿物油和50%的矿物油中,用15%的乳酸水包油乳液混合在一起,感知刺痛随着时间的程度。在9厘米的视觉模拟尺度上标记了刺痛的程度。中值,n = 19。最大程度(P = 0.077)之间存在显著差异的趋势,而在两种配方之间曲线下区域的不明显差异(AUC;P = 0.251)。


(图3)应用一种含有脂肪酸或矿物油的乳状液后皮肤柔软度的改善。


Improvements in skin softness are an additional benefit that consumers can perceive from the application of oils. These improvements can be measured objectively using sensitive biomechanical techniques. Using the Dermaflex, Overgaard and Jemec showed the positive effects on improving skin extensibility for mineral oil, which lasted longer than treatment with water alone. Increased skin extensibility means a more flexible or elastic skin, a skin that can be stretched further but will still return to its original position. The highly sensitive gas-bearing electrodynamometer has also been used by Maes et al. to discriminate the effects of emollients on stratum corneum in vivo. Applied in emulsions, mineral oil was shown to induce greater skin softness compared with wax esters, triglycerides and fatty acids (Fig. 3). This effect may relate to its superior effects as an occlusive ingredient.

皮肤柔软度的改善是消费者可以从使用油脂中感受到的额外好处。这些改善可以使用敏感生物力学技术来客观的测量。通过使用利多卡因乙醇凝胶,Overgaard和Jemec展示了矿物油在他改善皮肤延展性的积极效应,比单独使用水处理持续时间更长。皮肤延展性的提升意味着柔韧有弹性的皮肤,皮肤可以伸展的更长,但仍将回到原来的状态。高敏含气电测力计也被Maes等人用来区别润肤剂对体内角质层的影响。与蜡酯、甘油三酯和脂肪酸相比,矿物油可引起更大的皮肤柔软度(图3)。这种影响可能与它作为一种封闭成分的优越作用有关。


Very long chain hydrocarbons have been reported by Brown et al. not to penetrate the skin to any large degree. Using radiolabelled hexadecane (C16H34) and docosane (C22H46) as n-alkanes of different chain length, they found that when applied in mineral oil, they hardly penetrated beyond the stratum corneum layer of pig skin in vitro with only 1.2% and 2.1% of the applied dose being in the epidermal and dermal layers. There was no penetration into the receptor fluids. Thus, these studies indicate the safety of these ingredients. However, it must be borne in mind that straight-chain alkanes were used in these studies and that branched together with cyclic alkanes are also found in mineral oil, and their delivery characteristics may be different.

Brown等报道了长链烃在很大程度上不穿透皮肤。通过使用放射性标记的十六烷和二十二烷作为不同链长的n-烷烃,它们发现应用于矿物油中时,它们在体外几乎不穿透过猪皮肤的角质层,仅仅是在表皮和真皮层用量的1.2%和2.1%。没有渗透到受体的体液中。因此,这些研究表明了这些成分的安全性。然而,必须牢记这些研究中使用的长链烷烃和支链环烷烃也在矿物油中存在,它们的传递特性可能不同。


Backhouse et al. came to similar conclusions regarding the limited penetration of mineral oil into skin. Stamatas et al. have also shown limited penetration of mineral oil into the stratum corneum. Using their method of in vivo Raman spectroscopy, they also showed an increase in stratum corneum thickness of around 10% further demonstrating the effect of occlusion leading to the reported effects on skin softness discussed previously. Figure 4 illustrates the results of this investigation. When using vegetable oils (in this study, sweet almond oil and jojoba oil) and mineral oil (called paraffin oil in this publication), the increase in stratum corneum thickness (which is a measure for its water uptake) is increased to the same extent, namely 10%. The application of petrolatum, which is much more occlusive, results in a significantly larger increase in stratum corneum thickness.

Backhouse等得出了关于矿物油有限度的渗入皮肤的类似结论。Stamatas等也展示了矿物油有限度的渗入角质层。他们的方法中使用体内拉曼光谱,也发现了角质层厚度大约10%的增加,进一步地证明了封闭作用对前文所讨论的皮肤柔软度引起的已报道的影响。图4举例说明了这次调查的结果。当使用植物油(本研究中为甜杏仁油和霍霍巴油)和矿物油(为石蜡油),角质层厚度的增加(一种对其水吸收的测量方法)达到了相同的程度,也就是10%。更为封闭的矿脂的应用,导致角质层厚度显著增加。

 

(图4)由于两种植物油和矿物油(石蜡油)的应用,角质层厚度的增加(角质层吸水量的测量)。


In this process of interacting with the stratum corneum lipids, mineral oil, like all other oils, will disrupt its structure to some extent. However, when examined by electron microscopy as reported by Warner et al., a more homogeneous structure than that present in soap-induced dry skin was found.

在与角质层脂质相互作用的过程中,矿物油和其他的油类一样,将在某种程度上破坏它的结构。然而,由Warner等报道当用电子显微镜检查时,发现了比先前肥皂引起的干性皮肤更均匀的结构。


However, Patzelt et al. found minimal penetration of mineral oil and other oils into the stratum corneum (Fig. 5) and that mineral oil’s behaviour on suppressing TEWL was similar to vegetable oils, but that jojoba oil was the worst performing vegetable oil tested (Table III).

然而,Patzelt等发现了矿物油和其他油类进入角质层的最小渗透量(图5),矿物油的抑制表皮水分流失的表现与植物油类似,但霍霍巴油是测试的植物油中表现最差的(表3)。

 

(图5)用荧光激光扫描显微镜分析了大豆油(a)、杏仁油(b)、荷荷巴油(c)、鳄梨油(d)、石蜡油(e)、矿脂(f)在皮肤上的分布情况。



Mineral oil and comedogenicity

矿物油及其致粉刺性


‘Acne cosmetica’ was coined in the early 1970s to describe the association between cosmetic use and acne breakouts. A variety of oils, including mineral oil, at the time were thought to be inducing this effect by blocking pores. Animal models were quickly developed. Fulton described the comedogenicity of an extensive list of commonly used ingredients in skincare products of which mineral oil was reported to be mildly comedogenic but nowhere near as much as other ingredients. Conflicting results were found by Mills and Kligman in their rabbit and human models, in which mineral oil was reported not to be comedogenic. The American Academy of Dermatology proposed guidelines to try to interpret the differences in the animal to human data, and they concluded that 1–2 comedones in animal testing would be unlikely to be an indicator of comedogenicity in humans. This is precisely the comedogenic activity of 100% mineral oil reported in five studies, that is, zero. Furthermore, DiNardo tested in humans the formulations containing mineral oil up to 30% and found that there was no comedogenicity potential of mineral oil. A wide series of products were tested that showed a comedogenic activity in the same range as the negative control. The overall conclusion is that mineral oil is not comedogenic. But this article also reveals that there is a difference between animal models and human models: the rabbit model is much more prone to comedogenicity than the human model, but all the earlier data that condemned mineral oil originate from animal models, a situation scientists even say will be difficult to correct.

“化妆品性痤疮”在二十世纪七十年代早期被创造出来描述化妆品的使用与粉刺的联系。各种油类,包括矿物油,在那时都被认为因为阻塞毛孔引起了这种影响。动物模型很快被开发出来。Fulton描述了一份广泛使用的护肤产品中成分清单的致粉刺性,其中矿物油被报道为温和的致粉刺成分,但远远不及其他成分。Mills和Kligman在他们的兔子和人体模型中发现了矛盾的结果,其中矿物油被报道不会引起粉刺。美国皮肤科学会提出了试图解释动物和人体数据差异的指导方针,他们总结为动物试验中的1-2个粉刺不太可能是人体实验中致粉刺性的指标。而这正是矿物油100%致粉刺性5份研究中已报道的,也就是0。此外,DiNardo在人体上测试了含有多达30%矿物油的配方,并发现矿物油没有致粉刺的可能性。一系列产品经过测试,显示出与阴性对照相同范围内的致粉刺性。总体的结论是矿物油不会引起粉刺。但本文也揭示了动物模型和人体模型的区别:兔子模型比人体模型更易产生粉刺,但所有早期的数据都是来自动物模型的,科学家们甚至认为这种情况很难纠正。


Mineral oil: UVB irradiation and photocarcinogenesis

矿物油:紫外辐射和光致癌


As mineral oil has a high refractive index close to that of skin, it actually improves the optical behaviour of skin, that is, it allows slightly more light to penetrate into the skin rather than the skin reflecting it.

因为矿物油和皮肤接近的高折射率,它实际上改善了皮肤的光学行为,也就是说,它允许稍微多一点的光线进入皮肤,而不是皮肤反射它。


Several publications have reported on the effects of emollients increasing skin UV sensitivity and thereby photocarcinogenesis. The most relevant publication to mineral oil is that from Kligman and Kligman. The latter studies have only been conducted in mice, are of limited size, and the human relevance has not been determined. Although animal studies cannot be ignored, they are still insufficient as a risk assessment tool. The hairless mouse model used is a mutant mouse that is highly sensitive towards the development of skin tumours, and the decades’ long-term usage of moisturizers without any relationship to tumour development exemplifies the lack of relevance of these mouse models. Nevertheless, the studies are in the public domain. Equally, they are contradictory in that acute application of mineral oil increased UVB-induced damage, but chronic applications actually provided protection against UV. The human studies show that typical moisturizers containing 10% mineral oil or glycerol decrease the minimal erythemal dose (MED) of skin to UVB irradiation by 5–7.6% (i.e. they make the skin slightly more sensitive to UV). However, to put this in context, shaving or using an exfoliating treatment such as sponges or cosmetic uses of alpha hydroxyacids is reported to decrease MED by approximately 12–13.2%. Although this may sound rather dramatic, it should also be realized that the average MED increase between January and April was 14%. However, Schleider et al. reported that mineral oil only had a small effect (5–13% reduction of MED), whereas peanut oil and corn oil had no effect and petrolatum was actually beneficial. Equally, Hudson-Peacock et al. found a reduction in MED by 16% for mineral oil. Conversely, Behrens-Williams et al. found that an emulsion containing35% mineral oil, 30% cetyl stearyl alcohol and vaseline had no effect on UVB-induced erythema, and Otman et al. found that a variety of mineral oil-containing emulsions decreased the sensitivity to UV, but it should be realized that these formulations also contained soft paraffin waxes.

一些出版物报道了润肤剂对增加皮肤紫外线敏感以及因此的光致癌性的影响。与矿物油最相关的出版物来自Kligman和Kligman。后者的研究仅仅在小鼠中进行,规模有限,人类的相关性尚未确定。尽管动物研究不能被忽视,但他们作为一种风险评估工具,仍然是不充分的。使用的无毛小鼠是一种突变小鼠,对皮肤肿瘤的发展高度敏感,几十年来,长期使用润肤霜与肿瘤的发展没有任何关系,证明了这些小鼠模型缺乏相关性。然而,这些研究是在公共领域进行的。同样地,他们在因矿物油的急性应用而提升紫外线引起的伤害方面是矛盾的,但长期应用实际上提供了紫外线防护。人体研究显示含有10%矿物油或甘油的典型润肤霜将紫外辐射皮肤最小红斑用量(MED)减少了5-7.6%(也就是说,它们使皮肤对紫外线更加敏感)。然而,联系上下文,剃须或使用去角质的方法,如海绵或化妆品α-羟基酸的使用被报道降低MED 大约12-13.2%。尽管这听起来很有戏剧性,应当意识到在1月到4月之间的平均MED增长是14%。然而,Schleider等报道了矿物油仅仅有很小的影响(5-13%MED减少量),花生油和玉米油没有影响,而矿脂实际上是有效的。同样地,Hudson-Peacock等发现了矿物油减少MED达16%。相反地,Behrens-Williams等发现一份含有35%矿物油,30%棕榈醇和凡士林的乳液对紫外线引起的红斑没有影响,Otman等发现一些含矿物油的乳液减少了紫外线的敏感性,但是应该意识到这些配方中也含有柔软的石蜡。


The consensus of evidence of the effects of UV irradiation and mineral oil in humans is that mineral oil has a slight, reducing effect on the MED of skin of an order similar to that of glycerol because of its refractive index. Its long-term usage suggests that any detrimental effect on skin is probably minor and only as severe as the changes in sun sensitivity that occurs between the seasons.

紫外线辐射和矿物油对人体影响证据的共识是矿物油对皮肤MED有轻微的、减少的影响,由于其和甘油类似的折射率。它的长期使用表明,对皮肤的任何有害影响都可能是轻微的,而且和只有在季节间发生的太阳敏感性的变化一样严重。


Conclusion

结论


Mineral oil is a complex mixture of highly refined saturated branched-chain and napthenic hydrocarbons. Poly aromatic hydrocarbons (PAHs) that are known carcinogens are not present in mineral oil. The different grades are classified by their viscosities because of their complex compositions. They are used in many industrial, mechanical, medicinal, food and cosmetic applications. 

矿物油是一种复杂的混合物,有高度精炼的饱和长链烃和环烷烃。已知的致癌物聚芳烃(PAHs)不存在于矿物油中。由于它们复杂的组分,不同的等级按黏度分类。它们用于许多工业,机械,医药,食品和化妆品的应用。


Mineral oil is an efficacious skin moisturizer providing occlusivity and emolliency. Its occlusive effects lead to increases in stratum corneum water content by reducing transepidermal water loss. Through this mechanism, mineral oil is used to treat dry skin conditions in both leave-on and wash-off applications. It has been shown to improve skin softness better than wax esters, triglycerides and fatty acids. Its effect is largely confined to the epidermal layers, and as a result of its limited penetration, it is considered to be a very safe ingredient for cosmetic use.

矿物油提供封闭性和滋润性,是一种有效的皮肤保湿剂。它的封闭效果通过减少表皮水分流失,导致了角质层中水含量的增长。凭借这种机理,矿物油在免洗型和冲洗型的应用中被用来治疗干性皮肤状况。它在改善皮肤柔软度方面已经显现出优于蜡酯,甘油三酯和脂肪酸。其作用主要限于表皮层,并且因为它有限的渗透性,它被认为是化妆品使用中一种非常安全的成分。


Early animal studies suggested that mineral oil was comedogenic, but the evidence (using more recent human models) and consensus of opinion is now the opposite. However, because of its high refractive index, it actually improves the optical behaviour of skin, and as more light can now enter the skin, it has a slight reducing effect on skin MED. This effect, however, is no more than that of other cosmetic treatments and no different to seasonal effects on lowering MED. Recent animal studies have suggested that emollients including mineral oil may contribute to UV-induced photocarcinogenesis. However, these studies were of a very limited size and conducted in a mutant mouse that is highly sensitive to UV. Nevertheless, the relevance of these studies to human use of mineral oil is limited as there is no evidence to tumour development.

早期的动物研究认为矿物油是致粉刺成分,。然而,由于它的高折射率,它实质上的改善了皮肤的光学行为,因此现在更多的光纤可以进入皮肤,它对皮肤MED有轻微的降低作用。然而,这种效果并不比其他化妆品处理多,和季节性影响降低MED没有什么不同。最近的动物研究认为包括矿物油在内的润肤剂可能会促使紫外线诱导的的光致癌发生。然而,这些研究规模十分有限,并且是在对紫外线高度敏感的突变小鼠身上进行的。虽然如此,这些研究对人类使用矿物油的相关性是有限的,因为没有证据表明肿瘤的发展。


Comparisons with vegetable oils have been made wherever possible throughout this report. The main difference between vegetable oils and mineral oil is the wide variety of chemistry that may be present in vegetable oils (such as unsaturated, aromatic groups), whereas mineral oil contains mainly straight-chain hydrocarbons. As a consequence, the reasons for using vegetable oils and mineral oil are very different. Vegetable oils are used in cosmetics in relatively small amounts to obtain a specific effect of a specific ingredient with, for instance, a specific receptor in the skin. A very precisely defined chemical structure is necessary to achieve such a specific effect. Mineral oil is typically used in much higher concentrations for its emolliency, the soft skin feel that it provides to a formulation. This is a physical effect and not a biological effect. Another reason for using mineral oil is its occlusivity, which again is a physical effect and not a biological effect, although this does result in a biological effect: skin moisturization and a dampening of inflammatory responses.

在本报告中,尽可能的与植物油作出了比较。植物油和矿物油间的主要区别在于植物油中可能含有广泛的化学物质种类(比如不饱和键、芳烃基),而矿物油主要含有直链烃。因此,使用植物油和矿物油的原因是非常不同的。化妆品中使用的植物油是相对少量的,为了获得特定成分的特定效果,比如皮肤中的特定受体。要达到这种特定的效果,必须有一个非常精确的化学结构。矿物油通常因为滋润性而使用高得多的浓度,它提供给配方一个柔软的皮肤感觉。这是一种物理影响而不是生物影响。另外一个使用矿物油的原因是它的封闭性,又是一种物理影响而不是生物影响,尽管这确实导致了一种生物影响:保湿和抑制炎症反应。


Reference: omitted

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