DE102006034026A1 - Cosmetic pen - Google Patents

Abstract

A stick cosmetic formulation comprising a) a combination of one or more natural waxes, one or more microcrystalline waxes, one or more synthetic waxes, the total amount of all waxes in the formulation being 9 to 15% by weight, based on the total weight of the wax Preparation, is, b) several oils, c) one or more lipids having a melting point of 30-40 ° C in a total amount of 5-15 wt .-%, based on the total weight of the preparation.

Description

The The present invention relates to a cosmetic stick.

Of the Wish, nice and looking attractive has been in humans for thousands of years rooted. Even if the ideal of beauty has undergone changes over time, so is the pursuit of a flawless appearance, always the goal of the people since a sympathetic appearance their self-esteem and the attraction to their fellow human beings increased. The concept of decorative Cosmetics derives from the Latin "decoratio" - the Highlight the beauty - from. Most of time with the help of dyes individual body parts, especially in the face, highlighted and color inconsistencies mitigated.

To The most widely used decorative cosmetics include lipstick. More than 50% of women in Germany use it. Mostly serves In addition to the color emphasis of the lips, he also used lip care. In addition to the classic lipstick are also lip gloss and contour pencils used. Lip Gloss gives the lips a strong decorative Gloss, contour pins serve to emphasize the lips edges.

lipsticks usually consist of a wax matrix, in which lower Concentration liquid and semi-solid oils as well as pigments and fillers are incorporated. They are in solid pen form.

Lip gloss contains mostly liquid oils that Leave a damp "oil film" on the skin Lip-Gloss is in liquid at room temperature or viscous form in front.

The decorative most effective effects in the lip area can be especially by a combination of colored lipstick and achieve lip-gloss. The color emphasizes the mouth area, the moist-glossy lip gloss gives the lips a healthy lush appearance, because lip-gloss lets the Lips fuller (more voluminous) Act.

At the Make-up is usually female user decorative Lip cosmetics then usually pretend that first with the help of a lipstick the lips dyed and subsequently It is "painted" with lip gloss So it is a two-stage make-up process in which two different cosmetics (dyed Lipstick and lip gloss) are used.

adversely The state of the art is the fact that it has not been successful is Moisturizing Lip Gloss Lipsticks to develop. Used in conventional Lipsticks the oil content elevated, The pins lose strength quickly and they do not develop viscous malleable masses. Elevated in Lip Gloss formulations, the wax content, lose the preparations very fast on shine before ever the desired Achieve pen consistency.

Around the largest possible decorative effect (the combination of colored and moist-shiny Lip), so it is necessary according to the prior art 2 different products (lipstick and gloss) in succession to use. Besides the disadvantage that in this application form in the users like a "pebble" of the "kit" lost or premature comes to a halt, especially when it comes to products of different Manufacturer is the problem that the individual parts (pin and Gloss) of the "construction kit" with each other only limited tolerable are.

Though There has been no lack of attempts in the past, lipsticks to develop where the gloss effect using pearlescent pigments is to be imitated, but one reaches with these pearlescent pigments rather an undesirable one Glitter effect and not the Glosstypischen wet shine ("wet-look" in the jargon called the beautician).

• a) eine Kombination aus einem oder mehreren natürlichen Wachsen, einem oder mehreren mikrokristallinen Wachsen, einem oder mehreren synthetischen Wachsen, wobei die Gesamtmenge aller Wachse in der Zubereitung 9 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung beträgt,
• b) mehreren Ölen
• c) einem oder mehreren Lipiden mit einem Schmelzpunkt von 30–40 °C in einer Gesamtmenge von 5–15 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.

It was therefore surprising and unforeseeable for a person skilled in the art that the disadvantages of the prior art are overcome by containing a cosmetic preparation in stick form

• a) a combination of one or more natural waxes, one or more microcrystalline waxes, one or more synthetic waxes, the total amount of all waxes in the preparation being 9 to 15% by weight, based on the total weight of the preparation,
• b) several oils
• c) one or more lipids having a melting point of 30-40 ° C in a total amount of 5-15 wt .-%, based on the total weight of the preparation.

The preparations according to the invention are characterized by a high pin strength, a slight abrasion when applied to the lips and an exceptionally high wet shine.

By "stick-shaped preparation" according to the invention is a preparation understood that at room temperature (20 ° C) the consistency of a conventional Lipstick has. In particular, it is on the one hand firm and dimensionally stable, on the other hand easy to pass on the lips.

The melting points according to the invention and melting areas can according to DIN 51803 be determined.

It is preferred according to the invention, if the total amount of all waxes in the preparation is 10 to 12% by weight, based on the total weight of the preparation.

Further is it preferred according to the invention, if one or more lipids with a melting point of 30-40 ° C in one Total of up to 8-12 Wt .-%, based on the total weight of the preparation in this are included.

advantageous embodiments The present invention is characterized in that the preparation Pigments in an amount of 0.05-8 wt .-%, based on the Total weight of the preparation contains. It is preferred according to the invention when the preparation of the invention Pigments in an amount of up to 1-5% by weight or 2-4% by weight, based on the total weight of the preparation.

there it was surprising and for The person skilled in the art can not foresee that the color of the preparation will change the more intense the application to the skin, the smaller the Pigment particle size in the Preparation is. Furthermore, it was for the expert does not foresee that the wet gloss (wet look) the bigger is ever the pigment concentration is smaller.

It is preferred according to the invention, when the preparation of the invention in stick form, characterized in that the pigments have a average size of 2 up to 5 μm exhibit.

The average size of the particles can be determined as follows: Measuring instrument: Grindometer; Measuring range: 0-25 μm; The sample gets into the lower end (at 25 μm) of the grindometer filled with air bubbles. Subsequently, will with a scraper evenly until the other end of the sample Grindometers passed. After streaking the sample, the Particle size through consider the surface of the Grindometers set against the light. At the depth where the particles Traces on the surface leave the grindometer, the value is read.

Inventive pigments can be organic and inorganic origin, such as azo-type organic, indigoids, triphenylmethane-like, anthraquinones, and xanthine dyes known as D & C and FD & C blues, browns, greens, oranges, reds, yellows are known. inorganic Pigments are insoluble Salts of certified dyes, called lakes or iron oxides be designated. For example, barium lakes, calcium lakes, aluminum lakes, titanium dioxide, mica and iron oxides Find. For example, Al 3 salts include Red 3 Aluminum Lake, Red 21 Aluminum Lake, Red 27 Aluminum Lake, Red 28 Aluminum Lake, Red 33 Aluminum Lake, Yellow 5 Aluminum Lake, Yellow 6 Aluminum Lake, Yellow 10 Aluminum Lake, Orange 5 Aluminum Lake, Blue 1 Aluminum Lake and Combinations used.

When Iron oxides or oxide hydrates are e.g. cosmetic yellow oxides C22-8073 (Sunchemical) cosmetic yellow oxide C33-1700 (Sun Chemical), cosmetic brown oxide C33-115 (Sun Chemical), cosmetic iron oxide red C33-2199 (Sunchemical), cosmetic russet oxide C33-8075 (Sunchemical), cosmetic iron oxide black C33-5000 (Sunchemical), as titanium dioxides e.g. Kronos 1171 (Kronos), C47-051 Cosmetic White (Sunchemical) is known and if necessary advantageous.

It is likewise preferred if these preparations have a content of inorganic pigments selected from the group of metal oxides and / or other sparingly water-soluble or insoluble metal compounds, preferably oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides and the sulfate of barium (BaSO ₄ ).

The inorganic pigments can advantageous in the context of the present invention also in the form of a commercial available oily or aqueous predispersions come into use. These predispersions may advantageously dispersants and / or solubilization promoters may be added.

The Pigments can According to the invention advantageous superficial be treated ("coated"), for example a hydrophilic, amphiphilic or hydrophobic character formed should be or should be preserved. This surface treatment can consist of that the Pigments according to known methods with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer be provided. The different surface coatings can be used in the According to the present invention also contain water.

Inorganic surface coatings for the purposes of the present invention may consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ or aluminum oxide hydrate (also: Alumina, CAS No .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings may be present alone, in combination and / or in combination with organic coating materials.

organic surface coatings For the purposes of the present invention may consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. These organic surface coatings can alone, in combination and / or in combination with inorganic Coating materials occur.

Also according to the invention the method of incorporation of color pigments in the preparations according to the invention. The color pigments are first predispersed in a cosmetic oil, before this dispersion is incorporated into the formulation. According to the invention, advantageous oils for the production The dispersion of the dyes are especially polar oils, in particular castor oil, Coconut glycerides, octyldodecanol, diisostearyl fumarate. According to the invention advantageous it is for the preparation of the dispersion to use a bead mill, wherein the Pigments, the cosmetic oil and the grinding pearls together in the grinding basket exposed to a circulation become. This preserves after a very short time excellent dispersing results and a very narrow particle size spectrum. The mean particle size is while around 2-5 microns.

pigments In particular, inorganic pigments, can also act as a light filter and so the lips from injury protected by UV radiation.

The cosmetic according to the invention Preparation is characterized in that the preparation according to the order on the skin a gloss value of greater than or equal to 10 after one Time of 5 minutes generated. According to the invention, preparations are preferred the a gloss value of greater than 12 after generate a time of 5 minutes. Particularly preferred are Preparations having a gloss value greater than 14 after a period of Create 5 minutes.

Of the gloss value according to the invention is determined by the following method: To determine the Skin gloss becomes a reflectance spectrometer (meter: tenth Gloss meter ZGM 1020 60 °) used. With a light control technology and a special measuring head becomes white Light at an entrance angle of 60 ° placed on the skin surface. The reflected or mirrored at the exit angle of also 60 ° Light is supplied to the detector and quantified. Characteristic: gloss value according to DIN EN ISO 2813 Measurement takes place on the untreated area, as well as after 5 minutes and 15 minutes Application.

According to the invention advantageous contains the preparation according to the invention 0-5% by weight Pearlescent.

• – „Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und
• – „Perlmutt" (vermahlene Muschelschalen),

monokristalline Perlglanzpigmente wie z.B. Bismuthoxychlorid (BiOCl), Schicht-Substrat Pigmente: z.B. Glimmer/MetalloxidThese include natural pearlescent pigments, such as

• - "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and
• - "mother-of-pearl" (ground mussel shells),

monocrystalline pearlescent pigments such as bismuth oxychloride (BiOCl), layer substrate pigments: eg mica / metal oxide

Also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide: group Coating / colour Silver-white pearlescent pigments TiO2: 40-60 nm silver interference pigments TiO2: 60-80 nm yellow TiO ₂ : 80-100 nm red TiO ₂ : 100-140 nm blue TiO ₂ : 120-160 nm green Color Luster Pigments Fe ₂ O ₃ bronze Fe ₂ O ₃ copper Fe ₂ O ₃ red Fe ₂ O ₃ rotviolett Fe ₂ O ₃ Red Green Fe ₂ O ₃ black combination pigments TiO ₂ / Fe ₂ O ₃ golds TiO ₂ / Cr ₂ O ₃ green TiO ₂ / Berlin Blue deep blue TiO ₂ / Carmine red

When particularly preferred are the pigments of the companies Costenoble (cloisonne type, Flamenco guy, low Luster type), Merck (Colorona types, Microna type, Timiron type, Colorona, Ronasphere), Les Colornats Wacker (Covapure, Vert oxyde de Chrome), Cadre (Colorona, Sicopearl), BASF (Sicopearl, Sicovit), Rona (Colorona) known.

It may also be advantageous to completely dispense with a substrate such as mica. Particular preference is given to pearlescent pigments which are prepared using SiO ₂ , for example those obtainable from Merck under the name Xirona. Such pigments, which may also have additional gonichromatic effects, are available, for example, under the trade name Sicopearl Fantastico from BASF.

Advantageous can Synthetic mica based pigments (Synthetic Fluorophlogopite) the company Sunchemical. These are available under the name SunShine.

Farther can be advantageous Pigments of Engelhard / Mearl based on calcium sodium Borosilicate, which are coated with titanium dioxide, can be used. These are available under the name Reflecks. They point through their Particle size of 40-180 μm in addition to the color of a glittering effect.

Farther can be advantageous Pigments of Merck based on calcium aluminum borosilicate, the coated with titanium dioxide are used. These are available under the name Ronastar.

It is advantageous according to the invention if the weight ratio from microcrystalline wax to synthetic wax is 45:55 or the proportion of microcrystalline wax is greater. According to the invention preferred is this weight ratio: 50:50.

It is advantageous according to the invention when the microcrystalline invention Waxes have a melting range of 60-90 ° C. According to the invention preferred show a melting range of 80 to 90 ° C.

It is advantageous according to the invention when the synthetic Waxes have a melting range of 60-90 ° C. According to the invention preferred show a melting range of 70-85 ° C.

According to the invention, "natural waxes" are understood to mean compounds which fall under the term "natural waxes" according to the standard works (eg Römpp-Chemie-Lexikon). In addition, also fall hy Dried waxes of natural origin (ie a natural wax which has been hydrogenated) are included in this definition.

According to the invention preferred it is there, if the natural Waxes chosen are from the group of compounds candelilla wax, carnauba wax, Beeswax, shellac wax, berry wax, hydrogenated jojoba wax, Wool wax, sugar cane wax, rice germ wax. Here is the use of natural waxes Candelilla wax, carnauba wax and shellac wax according to the invention particularly prefers.

According to the invention under "microcrystalline Waxes "compounds understood, according to the standard works (e.g., Römpp Chemie Lexikon) under "microcrystalline Waxes "fall.

According to the invention preferred it is there when the microcrystalline waxes are chosen from the group of products Micro-La, Paracera, Micro Care of the company Paramelt, Kahlwachs / Microwax, special wax from Kahl Permulgin the company Koster Keunen and / or Microcrystalline Wax type SP of the Company Strahl & Pitch, which are freely available in the trade are.

According to the invention under "synthetic Waxes "compounds understood, according to the standard works (e.g., Römpp Chemie Lexikon) under "synthetic Waxes "fall.

According to the invention preferred It is when the synthetic waxes are chosen from the group of Compounds of straight-chain polyethylene waxes, Fischer-Tropsch waxes, Fatty alcohols (C30-50) which have a melting point of 60-90 ° C. Here is the use synthetic waxes polyethylene waxes, Fischer-Tropsch waxes particularly according to the invention prefers.

According to the invention Under "lipid" compounds understood, according to standard works (e.g. Römpp-Chemie-Lexikon) fall under "lipids", except of the compounds to count to the waxes or oils.

According to the invention preferred It is when the lipids are selected with a melting point of 30-40 ° C. from the group of compounds Shea butter, myristyl lactate.

According to the invention under oils Compounds understood in accordance with the standard works (e.g., Römpp Chemie Lexikon) fall under "oils".

• – Polyisobuten und/oder hydriertes Polyisobuten, hydriertes Polydecen in einer Menge von 10–25 Gew.-%,
• – Pentaerytritylester, Diisostearylmalat, Caprylic/Capric Triglyceride, Isododecylstearylstearat in einer Menge von 10–25 Gew.-%,
• – Octyldodecanol in einer Menge von 5–15 Gew.-%,
• – Rizinusöl, Jojoba, Avocado, Lanolin, Kokosglyceride in einer Menge von 5–25 Gew.-%, eingesetzt wird, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Zubereitung beziehen.

It is inventively preferred if as oils, a mixture of the components

• Polyisobutene and / or hydrogenated polyisobutene, hydrogenated polydecene in an amount of 10-25% by weight,
• Pentaerytrityl ester, diisostearyl malate, caprylic / capric triglyceride, isododecylstearyl stearate in an amount of 10-25% by weight,
• Octyldodecanol in an amount of 5-15% by weight,
• - Castor oil, jojoba, avocado, lanolin, coconut glycerides in an amount of 5-25 wt .-%, is used, wherein the weights are based on the total weight of the preparation.

The inventive preparation can be advantageous according to the invention contain further ingredients. So it is preferred according to the invention when the preparation of the invention as further constituents one or more compounds selected from the group of preservatives, UV protection filters, dyes, Film former, vitamin A palmitate, vitamin E acetate, allantoin, panthenol, α-bisabolol, Lecithin, ceramides, collagene contains.

there is it preferred according to the invention if as preservatives parabens and in particular propylparabens be used.

The inventive preparation contains the preservatives of the invention advantageous in a total concentration of 0.01 to 0.5 % By weight, based on the total weight of the preparation.

It is preferred according to the invention, when used as the UV light protection filter, the following compounds butyl methoxybenzoylmethane, octyl methoxycinnamate, bis-ethylhexyloxyphenol Methoxyphenyl triazines.

The preparation according to the invention contains the UV light protection filter according to the invention thereby advantageous in a total concentration of 0.1 to 3% by weight, based on the total weight of the preparation.

It is preferred according to the invention, if the following compounds are used as the film former: VP / eicosene copolymer, PVP hexadecenes copolymer, sucrose acetates Isobutyrate.

The inventive preparation contains the film formers according to the invention advantageous in a total concentration of 0.5 to 5% by weight, based on the total weight of the preparation.

The active ingredients according to the invention Vitamin A palmitate, vitamin E acetate, allantoin, panthenol, α-bisabolol, Lecithin, ceramides, collagens can According to the invention advantageous in a single concentration of 0.01 to 5% by weight to be included in the total weight of the preparation in this.

Also according to the invention the method for producing a cosmetic preparation analog the example recipes.

Also according to the invention a lipstick case containing the preparation according to the invention.

According to the invention Use of the preparation according to the invention as a lipstick.

gloss measurement

to Determination of skin gloss becomes a reflection spectrometer (measuring instrument: Tenth gloss meter ZGM 1020 60 °) used. With a light control technology and a special measuring head becomes white Light at an entrance angle of 60 ° placed on the skin surface.

The at the exit angle of 60 ° also reflected or mirrored Light is supplied to the detector and quantified. Characteristic: gloss value according to DIN EN ISO 2813 Measurement takes place on the untreated area, as well as after 5 minutes and 15 minutes Application. For results see example formulations.

Examples

The following examples are intended to illustrate the present invention without limiting it. Unless indicated otherwise, all amounts, proportions and percentages are based on the weight and the total amount or on the total weight of the preparations. example recipes Gloss readings example 1 > 13 Phase A Synthetic Wax 5 Microcrystalline wax 5 Euphorbia cerifera (candelilla) wax 5 Butyrospermum Parkii (Shea Butter) 3 Myristyl lactate 7 Polyisobutene 25 Ricinus Communis (Castor) Seed Oil 19.6 octyldodecanol 10 Pentaerythrityl tetraisostearate 15 Red 7 Lake 4 Propylparaben 0.2 Phase B Tocopheryl acetate 1 Perfume 0.2 100 Example 2 > 14 Phase A Synthetic Wax 3 Microcrystalline wax 3 Euphorbia cerifera (candelilla) wax 6 Butyrospermum Parkii (Shea Butter) 3 Myristyl lactate 7 Polyisobutene 25 Ricinus Communis (Castor) Seed Oil 19.1 octyldodecanol 10 Pentaerythrityl tetraisostearate 15 Red 7 Lake 4 Propylparaben 0.2 Butyl methoxybenzoylmethane 0.5 Octyl Methoxycinnamate 3 Phase B Tocopheryl acetate 1 Perfume 0.2 100 Example 3 > 10 Synthetic Wax 3 Microcrystalline wax 3 Euphorbia cerifera (candelilla) wax 6 Butyrospermum Parkii (Shea Butter) 3 Myristyl lactate 7 Polyisobutene 16.2 Phase A Ricinus Communis (Castor) Seed Oil 14.3 octyldodecanol 15 Pentaerythrityl tetraisostearate 15 Red 7 Lake 3 Propylparaben 0.2 avocado oil 5 Sucrose acetate isobutyrate 3 Lanolin oil 5 Phase B Tocopheryl acetate 1 Perfume 0.3 100 Example 4 > 12 Synthetic Wax 2 Microcrystalline wax 3 Euphorbia cerifera (candelilla) wax 7 Butyrospermum Parkii (Shea Butter) 3 Myristyl lactate 7 Polyisobutene 21.5 Phase A Ricinus Communis (Castor) Seed Oil 14.0 octyldodecanol 15 Pentaerythrityl tetraisostearate 15 Red 7 Lake 3 Propylparaben 0.2 Sucrose acetate isobutyrate 3 Lanolin oil 5 Phase B Tocopheryl acetate 1 Perfume 0.3 100

Also according to the invention the process for the preparation of a cosmetic preparation which thereby characterized in that phase A is melted with constant stirring at 90 ° C. After complete melting from Phase A Phase B is added and mixed. The cosmetic preparation is poured into a suitable mold, chilled and demoulded.

Claims (11)

Containing cosmetic preparation in stick form a) a combination of one or more natural To grow, one or more microcrystalline waxes, one or more synthetic waxes, the total amount all waxes in the preparation 9 to 15 wt .-%, based on the Total weight of the preparation is, b) several oils c) one or more lipids with a melting point of 30-40 ° C in one Total amount of 5-15% by weight, based on the total weight of the preparation. Cosmetic preparation in stick form according to claim 1, characterized in that it contains pigments in an amount of 0.05-8 Wt .-%, based on the total weight of the preparation contains. Cosmetic preparation in stick form after one of the previous claims, characterized in that the preparation after the order the skin has a gloss value of greater or greater equal to 10 generated. Cosmetic preparation in stick form after one of the previous claims, characterized in that the weight ratio of microcrystalline Wax to synthetic wax is 45:55 or the proportion of microcrystalline Wax is bigger. Cosmetic preparation in stick form according to one of the preceding claims, characterized gekenn records that the natural waxes are selected from the group of the compounds candelilla wax, carnauba wax, beeswax, shellac wax, berry wax, hydrogenated jojoba wax, wool wax, sugarcane wax, rice germ wax. Cosmetic preparation in stick form after one of the previous claims, characterized in that the microcrystalline waxes are chosen from the group of microcrystalline waxes, which have a melting range of 60-90 ° C have. Cosmetic preparation in stick form after one of the previous claims, characterized in that the synthetic waxes are chosen from the group of compounds of straight-chain polyethylene waxes, Fischer-Tropsch waxes, Fatty alcohols (C30-50) which have a melting point of 60-90 ° C. Cosmetic preparation in stick form after one of the previous claims, characterized in that the lipids have a melting point of 30-40 ° C can be selected from the group of compounds Shea butter, myristyl lactate. Cosmetic preparation in stick form after one of the previous claims, characterized in that as oils a mixture of the components - polyisobutene and / or hydrogenated polyisobutene, hydrogenated polydecene in one Quantity of 10-25 Wt .-%, - pentaerytritylester, Diisostearyl Malate, Caprylic / Capric Triglyceride, Isododecyl Stearyl Stearates in an amount of 10-25 Wt .-%, - Octyl dodecanol in an amount of 5-15 Wt .-%, - castor oil, jojoba, Avocado, lanolin, cocoglycerides in an amount of 5-25% by weight, is formed, wherein the weights are based on the total weight refer to the preparation. Cosmetic preparation in stick form after one of the preceding claims, characterized in that they as further constituents one or selected several connections from the group of preservatives, UV protection filters (which?), Dyes, film formers, vitamin A palmitate, vitamin E acetate, allantoin, Panthenol, α-bisabolol, Lecithin, ceramides, collagen included. Cosmetic preparation in stick form after one the claims 2 to 11, characterized in that the pigments have an average Size of 2 up to 5 μm exhibit.