Patent Application
20230181435
The subject of the present disclosure is a pigment suspension comprising a pigment and a carrier medium. Another article is a cosmetic agent prepared using the pigment suspension and an organosilicon compound.
Pigments are frequently used in coatings, paints, printing inks, powder coatings, cosmetics or plastics for coloration. Paints, varnishes, printing inks, cosmetics and powder coatings are liquid or powder coating materials that are applied to surfaces to obtain both improved or altered optical and physical properties.
The change in shape and color of keratin fibers, especially hair, is an important area of modem cosmetics. To change the hair color, the expert knows various coloring systems depending on coloring requirements. Oxidation dyes are usually used for permanent, intensive dyeing with good fastness properties and good grey coverage. Such dyes usually contain oxidation dye precursors, so-called developer components and coupler components, which form the actual dyes with one another under the influence of oxidizing agents, such as hydrogen peroxide. Oxidation dyes are exemplified by very long-lasting dyeing results.
When direct dyes are used, ready-made dyes diffuse from the colorant into the hair fiber. Compared to oxidative hair dyeing, the dyeing obtained with direct dyes have a shorter shelf life and quicker wash ability. Dyes with direct dyes usually remain on the hair for a period of between 5 and 20 washes.
The use of color pigments is known for short-term color changes on the hair and/or skin. Color pigments are generally understood to be insoluble, coloring substances. These are present undissolved in the dye formulation in the form of small particles and are only deposited from the outside on the hair fibers and/or the skin surface. Therefore, they can usually be removed without residue by a few washes with surfactant-comprising cleaning agents. Various products of this type are available on the market under the name hair mascara.
Metallic luster pigments or metallic effect pigments are widely used in many fields of technology. They are used, for example, to color coatings, printing inks, inks, plastics, glasses, ceramic products and preparations for decorative cosmetics such as nail polish. They are exemplified above all by their attractive angle-dependent color impression (goniochromism) and their metallic-looking luster.
Hair with a metallic finish or metallic highlights are in trend. The metallic tone makes the hair look thicker and shinier.
For applications in the cosmetic field, for example in the color modification of keratinic fibers with pigments, it is important that the pigments are provided to the user in a storage-stable and dosage-capable form. This can be done in particular in the form of a storage-stable pigment suspension.
This disclosure provides a pigment suspension comprising a) at least one coloring compound that is a pigment and b) an ester of glycerol with an aliphatic C2-C6 carboxylic acid.
The following detailed description is merely exemplary in nature and is not intended to limit the disclosure or the application and uses of the subject matter as described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description. It is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited.
Ground pigment powders and water are usually used for the production of inorganic pigment suspensions. If necessary, organic or inorganic dispersing aids must be added in small quantities.
Some pigments, for example so-called metal effect pigments, have only limited stability in an aqueous medium. For example, aluminum-based metal effect pigments decompose comparatively rapidly in water to form hydrogen and aluminum hydroxide. To prevent this, the metallic pigment surfaces are conventionally protected by phosphating, chromating, salinizing or other coatings, for example of synthetic resin.
These coated metal effect pigments are therefore more expensive than non-coated metal effect pigments.
It is the task of the present disclosure to provide pigment suspensions that can be prepared easily and inexpensively and are stable in storage. In particular, the pigments in the pigment suspension should be stable against decomposition and/or corrosion. For this purpose, it would be desirable if different types of pigments could be used in the pigment suspension.
It has been found that pigment suspensions which contain an ester of glycerol with an aliphatic C2-C6-carboxylic acid as carrier medium meet these requirements.
Accordingly, a first subject matter of the disclosure is a comprising a) at least one coloring compound selected from the group of pigments and b) an ester of glycerol with a C2-C6 aliphatic carboxylic acid.
As the first ingredient essential to the present disclosure, the pigment suspensions contain at least one colorant compound from the group of pigments.
Pigments within the meaning of the present disclosure are coloring compounds which have a solubility in water at 25° C. of less than 0.5 g/L, preferably less than 0.1 g/L, even more preferably less than 0.05 g/L. Water solubility can be determined, for example, by the method described below: 0.5 g of the pigment are weighed in a beaker. A beaker glass is added. Then one litre of distilled water is added. This mixture is heated to 25° C. for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g/L. If the pigment-water mixture cannot be assessed visually due to the high intensity of the possibly finely dispersed pigment, the mixture is filtered. If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g/L.
Suitable pigments can be of inorganic and/or organic origin.
The at least one pigment preferably has a substrate platelet.
In principle, the substrate platelet can be made of any material that can be formed into a platelet shape.
They can be of natural origin, but also synthetically produced. Materials from which the substrate platelets can be constructed include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, and plastics. Preferably, the substrate platelets are composed of a metal or alloy or a mica. The mica can be of natural or synthetic origin.
Accordingly, it may be preferred that the pigment comprises a substrate platelet, wherein the substrate platelet comprises a metal, metal alloy, natural mica or synthetic mica. In particular, the substrate plate is preferably made of a metal, a metal alloy, a natural mica or a synthetic mica.
Any metal suitable for pigments can be used. Such metals include iron and steel, as well as all air- and water-resistant (semi)metals such as platinum, tin, zinc, chromium, molybdenum and silicon, as well as their alloys such as aluminum bronzes and brass. Preferred metals are aluminum, copper, silver and gold.
In a particularly preferred embodiment, the pigment comprises a substrate platelet of a metal, wherein the metal is selected from the group of aluminum, copper, silver and gold, with substrate platelets of aluminum being particularly preferred.
Substrate platelets made of aluminum can be produced, among other things, by punching out of aluminum foil or according to common milling and atomization techniques. For example, aluminum platelets are available from the reverberation process, a wet milling process.
In another preferred embodiment, the pigment has a metal alloy substrate plate, wherein the metal alloy comprises brass.
In a particularly preferred embodiment, the pigment comprises a substrate platelet of a mica, wherein a substrate platelet of synthetic mica (INCI: Synthetic Fluorophlogopite) is particularly preferred.
A substrate platelet made of metal or a metal alloy preferably has an average thickness of at most 150 nm, preferably less than 50 nm, more preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for substrate platelets thickness are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm, and 10 to 20 nm. Preferably, each substrate plate has a thickness that is as uniform as possible.
A substrate platelet of mica preferably has an average thickness of 50 to 1500 nm and more preferably 90 to 1000 nm.
The size of the substrate platelet can be tailored to the specific application, for example the desired effect on a keratinous material. Typically, the substrate platelets made of metal or a metal alloy have an average largest diameter of about 2 to 200 µm, especially about 5 to 100 µm. Typically, the substrate platelets of a mica have an average largest diameter of about 1 to 200 µm, particularly about 5 to 100 µm, and even more preferably about 5 to 25 µm.
In a preferred embodiment, the shape factor (aspect ratio), expressed by the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750. The average size of the uncoated substrate platelets is the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with quixel wet dispersion. To prepare the sample, the sample to be analyzed was pre-dispersed in isopropanol for 3 minutes.
The substrate plates can have different shapes. For example, lamellar or lenticular metal platelets or so-called vacuum metallized pigments (VMP) can be used as substrate platelets. Lamellar substrate platelets are exemplified by an irregularly structured edge and are also referred to as “cornflakes” due to their appearance. Lenticular substrate platelets have an essentially regular round edge and are also referred to as “silverdollars” due to their appearance.
The metal or metal alloy substrate plates can be passivated, for example by anodizing (oxide layer) or chromating.
A coating can change the surface properties and/or optical properties of the pigment and increase the mechanical and chemical resistance of the pigments. For example, only the upper and/or lower side of the substrate platelets may be coated, with the side surfaces being recessed. Preferably, the entire surface of the optionally passivated substrate platelets, including the side surfaces, is covered by the layer. The substrate platelets are preferably completely encased by the coating.
The coating may include or consist of one or more layers. In a preferred embodiment, the coating has only layer A. In a likewise preferred embodiment, the coating has a total of at least two, preferably two or three, layers. It may be preferred to have the coating have two layers A and B, with layer B being different from layer A. Preferably, layer A is located between layer B and the surface of the substrate plate. In yet another preferred embodiment, the coating has three layers A, B and C. In this embodiment, layer A is located between layer B and the surface of the substrate platelets and layer C is located on top of layer B, which is different from the layer B below.
Suitable materials for layers A and, if necessary, B and C are all substances that can be permanently applied to the substrate platelets. The materials should preferably be applicable in film form. Preferably, the entire surface of the optionally passivated substrate platelets, including the side surfaces, is enveloped by layer A or by layers A and B or by layers A, B and C.
In particular, the layers may each contain at least one metal oxide (hydrate).
It is preferred that the metal oxide (hydrate) is selected from the group of silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.
In the case of pigments with a substrate platelet made of metal or a metal alloy, layer A preferably comprises at least one low-refractive metal oxide and/or metal oxide hydrate. Low refractive index materials have a refractive index of 1.8 or less, preferably 1.6 or less.
Low refractive index metal oxide (hydrate) suitable for Layer A include, for example, silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, and mixtures thereof, with silicon dioxide being preferred. Layer A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, especially preferably 5 to 20 nm.
Layer B, if present, is distinct from layer A and, in the case of pigments having a substrate platelet of metal or metal alloy, may contain at least one highly refractive metal oxide (hydrate). Highly refractive materials have a refractive index of at least 1.9, preferably at least 2.0, and more preferably at least 2.4. Preferably, layer B comprises at least 95 wt.%, more preferably at least 99 wt.%, of high refractive index metal oxide(s).
If the layer B comprises a (highly refractive) metal oxide, it preferably has a thickness of at least 50 nm. Preferably, the thickness of layer B is no more than 400 nm, more preferably no more than 300 nm.
Highly refractive metal oxides suitable for layer B are, for example, selectively light-absorbing (i.e. colored) metal oxides, such as iron(III) oxide (α- and γ—Fe2O3, red), cobalt(II) oxide (blue), chromium(III) oxide (green),titanium(III) oxide (blue, usually present in admixture with titanium oxynitrides and titanium nitrides), and vanadium(V) oxide (orange), as well as mixtures thereof. Colorless high-index oxides such as titanium dioxide and/or zirconium oxide are also suitable.
Layer B can contain a selectively absorbing dye in addition to a highly refractive metal oxide, preferably 0.001 to 5 wt.%, particularly preferably 0.01 to 1 wt.%, in each case based on the total amount of layer B. Suitable dyes are organic and inorganic dyes that can be stably incorporated into a metal oxide coating. Dyes in the sense of the present disclosure have a solubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and are therefore not to be regarded as pigments.
As an alternative to a metal oxide, layer B in the case of pigments with a substrate platelet made of metal or a metal alloy may comprise a metal particle support layer with metal particles deposited on the surface of the metal particle support layer. In a preferred embodiment, the metal particles directly cover a portion of the metal particle carrier layer. In this embodiment, the effect pigment has areas in which there are no metal particles, i.e. areas which are not covered with the metal particles.
The metal particle carrier layer comprises a metal layer and / or a metal oxide layer.
If the metal particle carrier layer comprises a metal layer and a metal oxide layer, the arrangement of these layers is not limited.
It is preferred that the metal particle support layer at least comprises a metal layer. It is further preferred that the metal layer comprises an element selected from tin (Sn), palladium (Pd), platinum (Pt) and gold (Au).
The metal layer can be formed, for example, by adding alkali to a metal salt solution comprising the metal.
If the metal particle carrier layer comprises a metal oxide layer, this preferably does not comprise silicon dioxide. The metal oxide layer preferably comprises an oxide of at least one element selected from the group of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr (zirconium), Ti (titanium) and Ce (cerium). Particularly preferably, the metal particle support layer iii) in the form of a metal oxide layer comprises a metal oxide of Sn, Zn, Ti and Ce.
The metal particle support layer in the form of a metal oxide layer can be produced, for example, by hydrolysis of an alkoxide of a metal forming the metal of the metal oxide in a sol-gel process.
The thickness of the metal layer is preferably not more than 30 nm.
The metal particles may comprise at least one element selected from the group of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof. It is particularly preferred that the metal particles comprise at least one element selected from copper (Cu), nickel (Ni) and silver (Ag).
The average particle diameter of the metal particles is preferably not more than 50 nm, more preferably not more than 30 nm. The distance between the metal particles is preferably not more than 10 nm.
Suitable methods for forming the metal particles include vacuum evaporation, sputtering, chemical vapor deposition (CVD), electro less plating, or the like. Of these processes, electro less plating is particularly preferred.
According to a preferred embodiment, the pigments with a substrate platelet made of metal or a metal alloy have a further layer C comprising a metal oxide (hydrate), which is different from the layer B underneath. Suitable metal oxides include silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide, and chromium (III) oxide. Silicon dioxide is preferred.
In the case of pigments with a substrate platelet made of metal or a metal alloy, layer C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm.
Suitable pigments based on a substrate platelet made of a metal or metal alloy are, for example, the pigments Alegrace® Marvelous, Alegrace© Gorgeous or Alegrace® Aurous from Schlenk Metallic Pigments.
In the case of pigments with a substrate platelet of mica, in particular synthetic mica, layer A comprises a metal oxide (hydrate) selected from the group of titanium dioxide (TiO2), iron oxide (Fe2O3 and/or Fe3O4) and mixtures thereof. In a very preferred embodiment, layer A comprises titanium dioxide (TiO2) and/or iron oxide (Fe2O3). In a highly preferred embodiment, layer A comprises titanium dioxide (TiO2).
Layer B, if present, is also different from the first metal oxide (hydrate) layer in the case of pigments with a substrate platelet of mica.
Metal oxide (hydrate)s suitable for layer B are tin oxide (SnO2), silicon oxide (SiO2), aluminum oxide (Al2O3) and/or iron oxide (Fe2O3 and/or Fe3O4). Accordingly, it is preferred that layer B comprises a metal oxide (hydrate) selected from the group of tin oxide (SnO2), silicon oxide (SiO2), aluminum oxide (Al2O3), iron oxide (Fe2O3 and/or Fe3O4), and mixtures thereof. It is particularly preferred that layer B comprises tin oxide (SnO2) in the case of pigments with a substrate platelet of mica, preferably synthetic mica.
Layer B may further comprise a selectively absorbing dye or pigment. Suitable dyes and/or pigments include, for example, carmine, ferric hexacyanidoferrate(II/III), and chromium oxide green (Cr2O3).
The pigments with a substrate platelet of mica may have another layer C, which acts as a protective layer and comprises a metal oxide (hydrate) or a polymer, for example a synthetic resin. Suitable metal oxide (hydrates)s include silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide, and chromium (III) oxide. Silicon dioxide is preferred.
It is particularly preferred that a pigment with a substrate platelet of synthetic mica (INCI: Synthetic Fluorophlogopite) has a layer A comprising titanium dioxide (TiO2).
It is also preferred that a pigment with a substrate platelet of synthetic mica (INCI: Synthetic Fluorophlogopite) has a layer A comprising iron(III) oxide (Fe2O3).
It is also preferred that a pigment with a substrate platelet of synthetic mica (INCI: Synthetic Fluorophlogopite) has a layer A comprising titanium dioxide (TiO2) and iron(III) oxide (Fe2O3), and a layer B comprising tin dioxide (SnO2).
It is highly preferred that a pigment with a substrate platelet of synthetic mica (INCI: Synthetic Fluorophlogopite) has a layer A comprising titanium dioxide (TiO2) and a layer B comprising tin dioxide (SnO2).
A preferred pigment with a substrate platelet of synthetic mica is available, for example, under the name Timiron SynWhite Satin from Merck.
It is also particularly preferred that the pigment comprises at least one pigment of organic origin.
The organic pigments are correspondingly insoluble organic dyes or colorants which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine and/or triarylmethane compounds.
Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.
Highly preferred pigment suspensions are correspondingly exemplifiedwherein the pigment comprises at least one organic pigment selected from the group of carmine, quinacridone, phthalocyanine, Sorgho, blue pigments with the color index numbers Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 and mixtures thereof.
The amount of pigment in the pigment suspension depends in particular on the type of pigment(s) and its intended use. Preferably, the amount of pigment is between 1 and 90 wt.%, more preferably between 5 and 80 wt.% and most preferably between 10 and 70 wt.%, in each case based on the total weight of the pigment suspension.
In addition to the above-mentioned, particularly preferred pigments with substrate platelets made of metal, a metal alloy or mica, as well as the organic pigments, further color-imparting compounds can be included in the pigment suspension. The further colorant compounds may comprise, for example, further inorganic pigments and/or direct-acting dyes.
As a second ingredient essential to the present disclosure, the pigment suspension comprises an ester of glycerol with an aliphatic C2-C6-carboxylic acid.
The aliphatic C2-C6 carboxylic acids are preferably saturated carboxylic acids.
Suitable aliphatic C2-C6 carboxylic acids include in particular acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and mixtures thereof. Particular preference is given to the aliphatic C2-C6-carboxylic acid selected from the group of acetic acid, propionic acid, butyric acid and mixtures thereof. Very particular preference is given to the aliphatic C2-C6-carboxylic acid comprising acetic acid.
Accordingly, in a preferred embodiment, a pigment suspension is exemplified wherein it comprises as carrier medium at least one ester of glycerol with a C2-C6 aliphatic carboxylic acid (b) selected from the group of acetic acid glycerol esters, propionic acid glycerol esters, butyric acid glycerol esters, valeric acid glycerol esters, caproic acid glycerol esters and mixtures thereof. Preferably, the carrier medium of the pigment suspension comprises an acetic acid glycerol ester.
In the case of glycerol esters, a distinction is made between monoesters, diesters and triesters, depending on the number of acid molecules esterified with the glycerol molecule.
In another preferred embodiment, the pigment suspension is exemplified wherein it comprises at least one ester of glycerol with a C2-C6 aliphatic carboxylic acid selected from the group of monoesters, diesters and triesters of glycerol with a C2-C6 aliphatic carboxylic acid and mixtures thereof.
The pigment suspension may comprise, for example, monoacetin, diacetin and/or triacetin, or monopropionin, dipropionin and/or tripropionin, or monobutyrin, dibutyrin and/or tributyrin, and any mixtures thereof.
In a more preferred embodiment, the pigment suspension is exemplified wherein it comprises at least one triester of glycerol with an aliphatic C2-C6 carboxylic acid selected from the group of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid.
In a highly preferred embodiment, the pigment suspension is exemplified by comprising at least one ester of glycerol with a 2-C6 aliphatic carboxylic acid comprising triacetin (triacetic acid glycerol ester).
Preferably, the amount of the ester of glycerol with an aliphatic C2-C6 carboxylic acid is between 10 and 99% by weight, more preferably between 20 and 95% by weight and very particularly preferably between 30 and 90% by weight, in each case based on the total weight of the pigment suspension.
Correspondingly, in an extremely preferred embodiment, the pigment suspension is exemplified wherein it comprises at least one ester of glycerol with an aliphatic C2-C6-carboxylic acid comprising triacetin (triacetic acid glycerol ester) in an amount of between 10 and 99% by weight, more preferably between 20 and 95% by weight and very particularly preferably between 30 and 90% by weight, in each case based on the total weight of the pigment suspension.
It has been shown that the pigments, especially those with substrate platelets of metal, metal alloy, natural mica or synthetic mica, are protected from decomposition and can be accurately metered. In particular, pigments with substrate platelets made of metal or a metal alloy are protected against corrosion.
It has also been found that organic pigments can also be stably incorporated into a pigment suspension comprising esters of glycerol with an aliphatic C2-C6-carboxylic acid as carrier medium.
The present disclosure also relates to a cosmetic composition. This was prepared by combining a pigment suspension according to the present disclosure with one or more organic C1-C6 alkoxysilanes and/or their condensation products. In this way, cosmetic agents can be provided that contain all the desired components beneficial to the cosmetic agent, with the pigments protected from decomposition and the C1-C6 alkoxysilanes protected from hydrolysis.
Such cosmetic agents can be used, for example, in processes for coloring keratinous material, especially human hair.
The cosmetic agent is exemplified wherein it comprises one or more organic C1-C6 alkoxysilanes and/or their condensation products.
The organic C1-C6 alkoxysilane(s) are organic, non-polymeric silicon compounds, preferably selected from the group of silanes having one, two or three silicon atoms
Organic silicon compounds, alternatively called organosilicon compounds, are compounds which either have a direct silicon-carbon bond (Si-C) or in which the carbon is bonded to the silicon atom via an oxygen, nitrogen or sulfur atom. The organic silicon compounds of the present disclosure are preferably compounds comprising one to three silicon atoms. Organic silicon compounds preferably contain one or two silicon atoms.
According to IUPAC rules, the term silane stands for a group of chemical compounds based on a silicon basic framework and hydrogen. In organic silanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl groups and/or alkoxy groups.
A characteristic feature of the C1-C6 alkoxysilanes as contemplated herein is that at least one C1-C6 alkoxy group is directly bonded to a silicon atom. The C1-C6 alkoxysilanes as contemplated herein thus comprise at least one structural unit R′R″R‴Si-O-(C1-C6 alkyl) where the radicals R′, R″ and R‴ represent the three remaining bond valencies of the silicon atom.
The C1-C6 alkoxy group or groups bonded to the silicon atom are very reactive and are hydrolyzed at high rates in the presence of water, the reaction rate depending, among other things, on the number of hydrolysable groups per molecule. If the hydrolysable C1-C6 alkoxy group is an ethoxy group, the organic silicon compound preferably comprises a structural unit R′R″R‴Si-O-CH2-CH3. The radicals R′, R″ and R‴ again represent the three remaining free valences of the silicon atom.
Even the addition of small amounts of water leads first to hydrolysis and then to a condensation reaction between the organic alkoxysilanes. For this reason, both the organic alkoxysilanes and their condensation products may be present in the composition.
A condensation product is understood to be a product formed by the reaction of at least two organic C1-C6 alkoxysilanes with elimination of water and/or with elimination of a C1-C6 alkanol.
The condensation products can, for example, be dimers, or even trimers or oligomers, where in the condensation products are always in balance with the monomers.
Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from monomeric C1-C6 alkoxysilane to condensation product.
In a very particularly preferred embodiment, a cosmetic agent is exemplified wherein the cosmetic agent comprises one or more organic C1-C6 alkoxysilanes selected from silanes having one, two or three silicon atoms, the organic silicon compound further comprising one or more basic chemical functions.
This basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably connected to a silicon atom via a linker. Preferably, the basic group is an amino group, a C1-C6 alkylamino group or a di(C1-C6)alkylamino group.
A very particularly preferred agent is exemplified wherein the cosmetic agent comprises one or more organic C1-C6 alkoxysilanes selected from the group of silanes having one, two or three silicon atoms, and wherein the C1-C6 alkoxysilanes further comprise one or more basic chemical functions.
Particularly good results were obtained when C1-C6 alkoxysilanes of the formula (SI) and/or (S-II) and/or (S-IV) were used in the cosmetic agent. Since, as previously described, hydrolysis/condensation already starts at traces of moisture, the condensation products of the C1-C6 alkoxysilanes of formula (S-I) and/or (S-II) and/or (S-IV) are also included in this embodiment.
In another very particularly preferred embodiment, a process as contemplated herein is exemplified wherein the cosmetic agent comprises one or more organic C1-C6 alkoxysilanes of the formula (S-I) and/or (S-II),
where
where
The substituents R1, R2, R3, R4, R5, R5′, R5″, R6, R6′, R6″, R7, R8, L, A, A′, A″, A‴ and A⁗ in the compounds of formula (S- I) and (S- II) are explained below as examples: Examples of a C1-C6 alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a C2-C6 alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C2-C6 alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy C1-C6 alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred. Examples of an amino C1-C6 alkyl group are the aminomethyl group, the 2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred. Examples of a linear bivalent C1-C20 alkylene group include the methylene group (—CH2—), the ethylene group (—CH2—CH2—), the propylene group (—CH2—CH2—CH2—), and the butylene group (—CH2—CH2—CH2—CH2—). The propylene group (—CH2—CH2—CH2—) is particularly preferred. From a chain length of 3 C atoms, bivalent alkylene groups can also be branched. Examples of branched divalent, bivalent C3-C20 alkylene groups are (—CH2—CH(CH3)—) and (—CH2—CH(CH3)—CH2—).
In the organic silicon compounds of the formula (S-I)
the radicals R1 and R2 independently of one another represent a hydrogen atom or a C1-C6 alkyl group. Very preferably, R1 and R2 both represent a hydrogen atom.
In the middle part of the organic silicon compound is the structural unit or the linker -L- which stands for a linear or branched, divalent C1-C20 alkylene group. The divalent C1-C20 alkylene group may alternatively be referred to as a divalent or divalent C1-C20 alkylene group, by which is meant that each - L grouping may form - two bonds.
Preferably -L- stands for a linear, bivalent C1-C20 alkylene group. Further preferably -L- stands for a linear bivalent C1-C6 alkylene group. Particularly preferred -L stands for a methylene group (CH2—), an ethylene group (—CH2—CH2—), propylene group (—CH2—CH2—CH2—) or butylene (—CH2—CH2—CH2—CH2—). In particular, L stands for a propylene group (—CH2—CH2—CH2—)
The alkoxysilanes of the formula (S-I)
one end of each carries the silicon-comprising group —Si(OR3)a(R4)b
In the terminal structural unit —Si(OR3)a(R4)b radicals R3 and R4 independently represent a C1-C6 alkyl group, and particularly preferably R3 and R4 independently represent a methyl group or an ethyl group.
Here a stands for an integer from 1 to 3, and b stands for the integer 3 - a. If a stands for the number 3, then b is equal to 0. If a stands for the number 2, then b is equal to 1. If a stands for the number 1, then b is equal to 2.
Cosmetic agents with particularly good coloring properties for keratinous materials could be prepared if the agent comprises at least one organic C1-C6 alkoxysilane of the formula (S-I) in which the radicals R3, R4 independently of one another represent a methyl group or an ethyl group.
Furthermore, colorations with the best wash fastness could be obtained if the cosmetic agent comprises at least one organic C1-C6 alkoxysilane of the formula (S-I) in which the radical a represents the number 3. In this case the radical b stands for the number 0.
In another preferred embodiment, a cosmeceutical agent is exemplified wherein it comprises one or more organic C1-C6 alkoxysilanes of formula (S-I), where
In a further preferred embodiment, a process as contemplated herein is exemplified wherein the composition (A) comprises at least one or more organic C1-C6 alkoxysilanes of the formula (S-I),
where
Particularly well suited organic silicon compounds of formula (I) are (3-Aminopropyl)triethoxysilane
(3-Aminopropyl)trimethoxysilane
(2-Aminoethyl)triethoxysilane
(2-Aminoethyl)trimethoxysilane
(3-Dimethylaminopropyl)triethoxysilane
(3-Dimethylaminopropyl)trimethoxysilane
(2-Dimethylaminoethyl)triethoxysilane.
(2-Dimethylaminoethyl)trimethoxysilane and/or
In a further preferred embodiment, a process as contemplated herein is exemplified wherein the first composition (A) comprises at least one organic C1-C6 alkoxysilane of formula (S-I) selected from the group of
The aforementioned organic silicon compound of formula (I) is commercially available.
aminopropyl)trimethoxysilane, for example, can be purchased from Sigma-Aldrich. Also aminopropyl)triethoxysilane is commercially available from Sigma-Aldrich.
In a further embodiment of the process as contemplated herein, composition (A) may also comprise one or more organic C1-C6 alkoxysilanes of formula (S-II),
The alkoxysilanes of the formula (S-II) carry at both ends the silicon-comprising groups (R5O)c(R6)dSi— and —Si(R6′)d′(OR5′)c′.
In the central part of the molecule of formula (S- II) there are the groups —(A)e— and —[NR7—(A′)]f—and —[O—(A″)]g— and —[NR8—(A′”)]h-. Here, each of the radicals e, f, g and h can independently of one another stand for the number 0 or 1, with the proviso that at least one of the radicals e, f, g and h is different from 0. In other words, a preferred alkoxysilane of formula (II) comprises at least one moiety selected from the group of -(A)- and —[NR7—(A′)]— and —[O—(A″)]— and —[NR8—(A′”)]—.
In the two terminal structural units (R5O)c(R6)dSi— and — Si(R6′)d′(OR5′)c′, the radicals R5, R5′, R5″ independently represent a C1-C6 alkyl group. The radicals R6, R6′ and R6″ independently represent a C1-C6 alkyl group.
Here c stands for an integer from 1 to 3, and d stands for the integer 3 - c. If c stands for the number 3, then d is equal to 0. If c stands for the number 2, then d is equal to 1. If c stands for the number 1, then d is equal to 2.
Analogously c′ stands for a whole number from 1 to 3, and d′ stands for the whole number 3 - c′. If c′ stands for the number 3, then d′ is 0. If c′ stands for the number 2, then d′ is 1. If c′ stands for the number 1, then d′ is 2.
Dyeings with the best wash fastness values could be obtained if the radicals c and c′ both stand for the number 3. In this case d and d′ both stand for the number 0.
In another preferred embodiment, a cosmetic agent is exemplified wherein it comprises one or more organic C1-C6 alkoxysilanes of the formula (S-II),
where
When c and c′ are both 3 and d and d′ are both 0, the organic silicon compounds as contemplated herein correspond to the formula (S-IIa)
The radicals e, f, g and h can independently stand for the number 0 or 1, whereby at least one radical from e, f, g and h is different from zero. The abbreviations e, f, g and h thus define which of the groupings —(A)e— and —[NR7—(A′)]f— and —[O—(A″)]g— and —[NR8—(A′″)]h- are located in the middle part of the organic silicon compound of formula (II).
In this context, the presence of certain groupings has proven to be particularly advantageous in terms of achieving wash fast dyeing results. Particularly good results could be obtained if at least two of the radicals e, f, g and h stand for the number 1. Especially preferred e and f both stand for the number 1. Furthermore, g and h both stand for the number 0.
When e and f are both 1 and g and h are both 0, the organic silicon compounds as contemplated herein are represented by the formula (S-IIb)
The radicals A, A′, A″, A‴ and A⁗ independently represent a linear or divalent, bivalent C1-C20 alkylene group. Preferably the radicals A, A′, A″, A‴ and A⁗ independently of one another represent a linear, bivalent C1-C20 alkylene group. Further preferably the radicals A, A′, A″, A‴ and A⁗ independently represent a linear bivalent C1-C6 alkylene group.
The divalent C1-C20 alkylene group may alternatively be referred to as a divalent or divalent C1-C20 alkylene group, by which is meant that each grouping A, A′, A″, A‴ and A⁗ may form two bonds.
In particular, the radicals A, A′, A″, A‴ and A⁗ independently of one another represent a methylene group (—CH2—), an ethylene group (—CH2—CH2—), a propylene group (—CH2—CH2—CH2—) or a butylene group (—CH2—CH2—CH2—CH2—). Very preferably, the radicals A, A′, A″, A‴ and A⁗ represent a propylene group (—CH2—CH2—CH2—).
If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein comprises a structural grouping —[NR7—(A′)]—.
If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein comprises a structural grouping —[NR8—(A‴)]—.
Wherein R7 and Rs independently represent a hydrogen atom, a C1-C6 alkyl group, a hydroxy-C1-C6 alkyl group, a C2-C6 alkenyl group, an amino-C1-C6 alkyl group or a group of the formula (S- III)
Very preferably the radicals R7 and R8 independently of one another represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (S- III).
When the radical f represents the number 1 and the radical h represents the number 0, the organic silicon compound as contemplated herein comprises the grouping [NR7-(A′)] but not the grouping —[NR8—(A″)]. If the radical R7 now stands for a grouping of the formula (III), the organic silicon compound comprises 3 reactive silane groups.
In another preferred embodiment, a cosmetic agent is exemplified wherein the cosmetic agent comprises one or more organic C1-C6 alkoxysilanes of the formula (S-II)
where
In a further preferred embodiment, a process as contemplated herein is exemplified wherein the composition (A) comprises one or more organic C1-C6 alkoxysilanes of the formula (S-II), wherein
Well-suited organic silicon compounds of the formula (S-II) are 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamine
N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
2-[Bis[3-(triethoxysilyl)propyl]amino] ethanol
3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-l-propanamine
N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,
N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,
N,N-Bis[3-(trimethoxysilyl)propyl]-2-propene-1-amine
N,N-Bis[3-(triethoxysilyl)propyl]-2-propene-1-amine
The aforementioned organic silicon compounds of formula (S-II) are commercially available.
In another preferred embodiment, a cosmetic agent is exemplified wherein the cosmetic agent comprises one or more organic C1-C6 alkoxysilanes of formula (S-II) selected from the group of
In dyeing tests, it has also been found to be particularly advantageous if the cosmetic agent comprises at least one organic C1-C6 alkoxysilane of the formula (S-IV)
The compounds of formula (S-IV) are organic silicon compounds selected from silanes having one, two or three silicon atoms, wherein the organic silicon compound comprises one or more hydrolysable groups per molecule.
The organic silicon compound(s) of formula (S-IV) may also be referred to as silanes of the alkyl-C1-C6 alkoxysilane type,
where
In a further embodiment, a particularly preferred cosmetic agent is exemplified wherein it comprises one or more organic C1-C6 alkoxysilanes of the formula (S-IV),
where
In the organic C1-C6 alkoxysilanes of formula (S-IV), the radical R9 represents a C1-C12 alkyl group. This C1-C12 alkyl group is saturated and can be linear or branched. Preferably, R9 represents a linear C1-C8 alkyl group. Preferably R9 stands for a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group or an n-dodecyl group. Particularly preferred, R9 stands for a methyl group, an ethyl group or an n-octyl group.
In the alkoxysilanes of formula (S-IV), the radical R10 represents a C1-C6 alkyl group. Highly preferred R10 stands for a methyl group or an ethyl group.
In the alkoxysilanes of formula (S-IV), the radical R11 represents a C1-C6 alkyl group. Particularly preferably, R11 represents a methyl group or an ethyl group.
Furthermore k stands for a whole number from 1 to 3, and m stands for the whole number 3 - k. If k stands for the number 3, then m is equal to 0. If k stands for the number 2, then m is equal to 1. If k stands for the number 1, then m is equal to 2.
Colorations with the best wash fastness could be obtained when the cosmetic agentcomprises at least one organic C1-C6 alkoxysilane of formula (S-IV), in which the radical k represents the number 3. In this case the radical m stands for the number 0.
Particularly suitable organic silicon compounds of the formula (S-IV) are Methyltrimethoxysilane
Methyltriethoxysilane
Ethyltrimethoxysilane
Ethyltriethoxysilane
n-Propyltrimethoxysilane (also known as propyltrimethoxysilane)
n-Propyltriethoxysilane (also known as propyltriethoxysilane)
n-Hexyltrimethoxysilane (also known as hexyltrimethoxysilane)
n-Hexyltriethoxysilane (also known as hexyltriethoxysilane)
n-Octyltrimethoxysilane (also known as octyltrimethoxysilane)
n-Octyltriethoxysilane (also known as octyltriethoxysilane)
n-Dodecyltrimethoxysilane (also known as dodecyltrimethoxysilane) and/or
n-Dodecyltriethoxysilanes (also known as dodecyltriethoxysilane)
and n-octadecyltrimethoxysilane and/or n-octadecyltriethoxysilane.
In another preferred embodiment, a cosmetic agent is exemplified wherein it comprises at least one organic C1-C6 alkoxysilane of the formula (S-IV) selected from the group of
It has been found that, with regard to staining keratinous material, it is particularly preferable if the cosmetic agent comprises two structurally different alkoxysilanes.
In a preferred embodiment, a cosmetic agent is exemplified wherein it comprises at least one alkoxysilane of the formula (S-I) and at least one alkoxysilane of the formula (S-IV).
The corresponding hydrolysis or condensation products are, for example, the following compounds:
Hydrolysis of C1-C6 alkoxysilane of formula (S-I) with water (reaction scheme using 3-aminopropyltriethoxysilane as an example):
Depending on the amount of water used, the hydrolysis reaction can also take place several times per C1-C6 alkoxysilane used:
Hydrolysis of C1-C6 alkoxysilane of the formula (S-IV) with water (reaction scheme using methyltrimethoxysilane as an example):
Depending on the amount of water used, the hydrolysis reaction can also take place several times per C1-C6 alkoxysilane used:
or
Possible condensation reactions include (shown using the mixture (3-aminopropyl)triethoxysilane and methyltrimethoxysilane):
and/or
and/or
and/or
and/or
and/or
and/or
In the above exemplary reaction schemes the condensation to a dimer is shown in each case, but further condensations to oligomers with several silane atoms are also possible and also preferred.
Both partially hydrolyzed and fully hydrolyzed C1-C6 alkoxysilanes of the formula (S-I) can participate in these condensation reactions, which undergo condensation with as yet unreacted, partially or also fully hydrolyzed C1-C6 alkoxysilanes of the formula (S-I). In this case, the C1-C6 alkoxysilanes of formula (S-I) react with themselves.
Furthermore, both partially hydrolyzed and fully hydrolyzed C1-C6-alkoxysilanes of the formula (S-I) can also participate in the condensation reactions, which undergo condensation with not yet reacted, partially or also fully hydrolyzed C1-C6-alkoxysilanes of the formula (S-IV). In this case, the C1-C6 alkoxysilanes of formula (S-I) react with the C1-C6 alkoxysilanes of formula (S-IV).
Furthermore, both partially hydrolyzed and fully hydrolyzed C1-C6-alkoxysilanes of the formula (S-IV) can also participate in the condensation reactions, which undergo condensation with not yet reacted, partially or also fully hydrolyzed C1-C6-alkoxysilanes of the formula (S-IV). In this case, the C1-C6 alkoxysilanes of formula (S- IV) react with themselves.
The cosmetic agent may contain one or more organic C1-C6 alkoxysilanes in various proportions. This is determined by the specialist depending on the desired application. In the case of coloring keratinous material, for example, the amount may depend on the thickness of the silane coating on the keratinous material and the amount of keratinous material to be treated.
Particularly storage-stable cosmetic agents with very good coloring results when applied to keratinous material could be obtained when the cosmetic agent comprises - based on its total weight - one or more organic C1-C6 alkoxysilanes and/or the condensation products thereof in a total amount of from 30 to 85 wt.%, preferably from 35 to 80 wt.%, more preferably from 40 to 75 wt.%, still more preferably from 45 to 70 wt.% and very particularly preferably from 50 to 65 wt.%.
It may be preferred that the cosmetic agent ready for use comprises further ingredients, in particular water, in addition to the pigment suspension as contemplated herein and the organic C1-C6 alkoxysilane(s).
The cosmetic agent comprises alkoxysilanes, a class of highly reactive compounds that can undergo hydrolysis or oligomerization and/or polymerization when applied.
To avoid premature oligomerization or polymerization, it may be of significant advantage to the user to prepare the ready-to-use cosmetic agent just prior to application.
To increase user convenience, the user is preferably provided with all the necessary agents in the form of a multi-component packaging unit (kit-of-parts).
Thus, a third object of the present disclosure is a multi-component packaging unit (kit-of-parts) comprising, separately assembled from each other
In this embodiment, the cosmetic agent (a) is prepared by mixing the agent (a′) and the agent (a″).
With regard to further preferred embodiments of the cosmetic agent and/or the multicomponent packaging unit (kit-of-parts), what has been said about the pigment suspensions applies mutatis mutandis.
The following formulations have been produced (unless otherwise indicated, all figures are in wt. %)
A cosmetic agent (a) was prepared by mixing 5 g of the agent (a′) and 5 g of an agent (a″) (E1 or E2).
While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the various embodiments in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment as contemplated herein. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the various embodiments as set forth in the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2020 203 100.2 | Mar 2020 | DE | national |
This application is a U.S. National-Stage entry under 35 U.S.C. § 371 based on International Application No. PCT/EP2021/050081, filed Jan. 5, 2021, which was published under PCT Article 21(2) and which claims priority to German Application No. 102020203100.2, filed Mar. 11, 2020, which are all hereby incorporated in their entirety by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/050081 | 1/5/2021 | WO |
