WO2012150238A1

WO2012150238A1 - Containers for cosmetic and dermatological products

Info

Publication number: WO2012150238A1
Application number: PCT/EP2012/057983
Authority: WO
Inventors: Oliver Sperber
Original assignee: Beiersdorf Ag
Priority date: 2011-05-05
Filing date: 2012-05-02
Publication date: 2012-11-08
Also published as: DE102011100635A1; EP2704960A1

Abstract

The invention relates to containers and applicators for cosmetic and dermatological products, of which the swelling properties have been modified by surface treatment.

Description

Beiersdorf AG

Containers for cosmetic and dermatological products

description

The invention relates to containers, functional and system packaging and applicators for cosmetic and dermatological products, their stability, functionality or visual impression through interaction with the product or the constituents (raw materials) contained therein due to migration of the same into and through the packaging materials used ( eg plastic). The swelling property of precisely these product / packaging systems has been modified by surface treatment.

Cosmetic and dermatological preparations are becoming increasingly complicated. Whereas the basics of cosmetic and dermatological preparations used to be simple emulsion systems, nowadays a whole range of cosmetic and dermatological active substances and auxiliaries are incorporated into the preparations. The emulsion bases are based on increasingly complex

Emulsifier systems that make a decisive contribution to product performance.

The previously used forms of application as a cream or lotion have been expanded in recent decades by new forms of application such as pump sprays and roll-on. The packaging used for this purpose is no longer the classic glass bottle or tin can, but usually plastic containers and applicators.

Glass is still an ideal container material for modern cosmetic and dermatological preparations, as it only interacts with the ingredients in very rare cases and there is no diffusion of ingredients into the glass.

Due to the limited design options and the susceptibility to breakage and the high weight of glass, the use is declining and it is used on modern materials such as plastics. However, the plastics used for cost reasons for mass products have the disadvantage that relatively frequent interactions occur with the preparations. In addition to the reaction of the plastic with the contents, the diffusion of constituents into and through the plastic is the most common problem.

If preparation constituents diffuse through the container wall, the preparation changes in its mixing ratio, which in the worst case can lead to spoilage of the preparation. The storage stability is thus limited and can lead to sales difficulties. In order to solve this problem, multi-layered containers such as laminate tubes or multi-layered bottles are used in special cases. These represent a satisfactory but expensive solution.

When constituents of the formulation diffuse into the plastic, this is generally accompanied by a swelling, which means an increase in the volume of the plastic as the polymer network expands. If swelling occurs on mechanically stressed parts, this can lead to failure of the mechanism, since, for example, the mechanical load capacity is reduced or fitting inaccuracies prevent it from functioning. Especially with lotion / spray pumps or roll-on applicators swelling inevitably leads to uselessness. Also in applicator systems for spreadable preparations, such as mascara or nail polish, a swelling of the applicator leads to a change in the order result.

EP 1722962 describes the difficulties of synthetic packaging materials for cosmetic and pharmaceutical products. In particular, it presents individual disadvantages of polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP) or polybutene (PB) packaging materials, through which various oils can migrate. As a solution to problems, attention is drawn to the coating of the packaging materials with resistant materials, such as acrylonitriles or polychlorotrifluoroethylene.

EP 1722962, however, discloses as solution films for packaging liquid products or the like, the film comprising a first polyolefin layer, a tie layer formed from copolymer of a polyolefin and glycidyl methacrylate, and a layer of polychlorotrifluoroethylene (PCTFE).

DE 102008034957 discloses another approach to avoid oil migration through a polyolefinic packaging by adding oil migration inhibitors to the emulsion preparation. These inhibitors reduce or prevent the migration of various oils into or through the polyolefinic packaging. As the statements in DE 102008034957 on polyolefin packaging show, the chemical resistance is good in all polyolefins, but for example, the diffusion of gases and of aromatics and ethereal substances by PE relatively high. Likewise, a swelling in PE packaging is observed when in contact with aliphatic or aromatic hydrocarbons.

It also shows that there are problems with the packaging of lipid-containing cosmetic preparations in polyolefin packaging.

For example, cosmetic deodorants or antiperspirants in the form of microemulsions are not compatible with polyolefinic packaging, especially polypropylene packaging. That is, the lipid component of dicaprylyl ether contained in these exemplary deo / AT preparations will diffuse through the PP packaging over time, causing oiling of the outer surface of the packaging and delamination of labels.

The disadvantage is that certain migration inhibitors must be added to the preparation of the solution to the migration problem according to DE 102008034957. This in turn restricts the freedom from formulation or requires a complicated adaptation of the preparation to these migration inhibitors.

It is therefore desirable to carry together packaging materials of different materials and preparations of different content without the described swelling or migration problems occurring.

The aim and object of the invention is to provide low-cost containers, functional and system packaging and applicators available whose

Diffusion barierreeigenschaften and in particular their swelling properties allow use for cosmetic or dermatological preparations.

This object is achieved by the use of surface-treated containers, functional and system packages and applicators for the provision and application of cosmetic and / or dermatological preparations, wherein the surface treatment produces a functional layer at least on the preparation-contacting surfaces. A surface treatment in the sense of the use according to the invention is the coating of the corresponding surface with insoluble inert inorganic substances, such as, for example, silicon oxide and / or insoluble metal oxides. Such a coating is referred to as glass in the context of the invention.

Glass, that is a layer of silicon oxide and / or insoluble metal oxides, is an inert, hydrophobic, optically transparent, biocompatible, polymeric coating material with a wide range of industrial applications.

The coating of the substrate is carried out by plasma polymerization.

In plasma polymerization, vaporous organic precursor compounds (precursor monomers) in the process chamber are first activated by a plasma. Activation generates ionized molecules and first fragments of the molecule form in the gas phase in the form of clusters or chains. The subsequent condensation of these fragments on the substrate surface then causes under the influence of substrate temperature, electron and ion bombardment the polymerization and thus the formation of a closed layer.

In this case, virtually any substrate material such. B. _^ plastics, especially PET, PP, PE, PLA, SAN and ABS, as well as glass, ceramic and silicones with glass coatable. The gaseous deposition from the plasma and structures are reached and coated, which are not coatable by deposition from liquids such. As sharp edges and points or undercuts

The precursors used are gaseous or vacuum-volatile substances which form the glass by means of microwave discharge, plasma-activated variant of chemical vapor deposition (PE-CVD). For the construction of the inventive glasses of silicon oxide particularly well hexamethyldisiloxane (HMDSO) and / or hexamethyldisilazane are (HMDSN) in a doped with oxygen atmosphere, which results in a SiO _x layer is deposited and formed as by-products C0 ₂ and H ₂ 0 and NO _Y ,

The reaction looks like this (non-stoichiometric representation):

Si (CH ₃ ) 3-0-Si (CH ₃ ) 3 + O ₂ -> SiO _x + C0 ₂ + H ₂ 0

Si (CH ₃ ) 3-N-Si (CH ₃ ) 3 + O ₂ -> SiO _x + C0 ₂ + NO _y + H ₂ 0 In fact, HMDSO and / or HMDSN, two liquid siloxane oils which are individually or individually sprayed with a mixture of O and or argon into a highly evacuated hollow body (eg a bottle) via a gas lance, are vacuum decomposed by means of a microwave discharge. The microwave discharge gives rise to a plasma which leads to this decomposition reaction. The bonding of the SiO _x layer is not only by physical layer structure, but also by real, covalent bonds which enters the activated polymer surface with the SiO _x .

Glass has good barrier properties and surface properties. As a result, glass coatings are mainly used in two areas, for the coating of glasses (lenses or windshields & fiber discs) to achieve special, water-repellent effects and glass panels against salting out and hydrolysis less susceptible and the inner coating of plastic beverage bottles (usually PET), here for an increased gas and

Aroma barrier to worry.

Glass coatings according to the invention are a hydrophobic, chemically resistant coating with very good barrier action against inorganic and organic media (eg oils), strong acids, alkalis, gases and water vapor. As a thin and transparent coating, it is suitable for complex substrates, even on edges. As a biostable and biocompatible coating, they can be approved, for example by the FDA.

The functional thin films, which are built far below 1 micron, do not affect the normal material properties such as strength, color and elasticity, but lead to significantly improved diffusion barrier properties and swelling behavior.

Particularly advantageous are layers with a thickness of 10 to 250 nm, since at higher layer thicknesses, the brittleness increases greatly. Layer thicknesses of 30 to 50 nm are particularly advantageous, since here the barrier effect is optimal in terms of mechanical stability.

The modification of plastic surfaces by silica or metal oxide coating is known per se from the food industry (WO 1995/21948). The aim of these conventional modifications is to facilitate the desorption of packaging material components into the food and the absorption of food components in food to prevent or reduce the packaging walls. Such treatment is therefore carried out only on the surfaces coming into contact with food.

The surfaces to be coated are automatically cleaned in the coating process by the plasma treatment, so that no special pretreatment is necessary.

For the purposes of the inventive use, it is therefore useful, surface-treated containers, functional and system packaging and applicators made of polyethylene (PE, especially HDPE), polypropylene (PP) and polyethylene terephthalate (PET) and styrene polymers such as PS, SAN or ABS in conjunction with cosmetic and / or dermatological preparations.

According to the invention preferably hollow body with a certain stiffness, such as tube bottles (so-called Totties), bottles and crucibles are coated.

It is particularly advantageous to use the coated materials in conjunction with cosmetic or dermatological preparations which contain at least one substance from group A, since these lead to swelling particularly frequently.

Group (A) includes: 1,3,6,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentagamma-2-benzopyran 2,6-dimethyl-7-octene -2-ol, 2-acetone-pentone-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl, 2-isobutyl-4-hydroxy-4-methyltetrahydropyran, 2 tert-pentylcyclohexyl acetate, 3,7-dimethyl-2,6-octadien-1-ol, 3-methyl-5-phenyl-1-pentanol, 7-acetyl-1,1,1,4,4,6-hexamethyltetralin , Adipic diester, alpha-amylcinnamaldehyde, alpha-isomethylionone, alpha-methylionone, amyl C butylphenylmethylpropionalcinnamal, amylcinnamyl alcohol, amyl salicylate, anisalcohol, benzoin, benzyl acetate, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl salicylate, bergamot oil, bitter orange oil, butylphenylmethylpropioal, C12-C15 alkyl benzoate, Caprylic / capric triglycerides,

Cardamom oil, cedrol, cetearyl isonononoate, cinnamal, cinnamyl alcohol, citral,

Citronellol, citronellylmethyl crotonate, citron oil, coco-caprylate / caprate, coumarin, cyclopentasiloxane (cyclomethicone), decyl oleate, diethylhexyl carbonate, dicapryl carbonate, diethyl succinate, d-limonene, ethylenebasylate, ethylhexyl cocoate, ethylhexyl salicylate, ethyllinalool, eugenol, Evernia furfuracea extract, Evernia prunastri extract, farnesol , Geraniol, guaiac wood oil, heliotropin, hexylcinnamal, hexyl salicylate, hydroxycitronellal, hydroxyisohexyl 3-cyclohexene carboxaldehydes, isoeugenol, isopropyl palmitate,

Isopropyl stearate, lavender oil, lemone oil, limonene, linalool, linalyl acetate, tangerine oil, Menthyl PCA, methyl 2-octynoate, methyl benzoate, BHT, methyl cedryl ketones,

Methyldihydrojasmonates, methylheptenone, nutmeg oil, p-t-butyl-alpha-methyldihydrocinnamic aldehyde, rosemary oil, sweet orange oil, terpineol,

Tonka bean oil, triethyl citrate, vanillin.

In particular, caprylic / capric triglycerides, C12-C15 alkyl benzoate, diethylhexyl carbonate, cetearyl isonononoate, isopropyl palmitate, isopropyl stearate, dicapryl carbonate,

Ethylhexyl salicylate, ethylhexyl cocoate, decyl oleate, cyclopentasiloxane (cyclomethicone), coco-caprylate / caprate, isoparaffin, phenoxyethanol, glycerol, dioctyl carbonate,

Dicapryl ether, paraffin oil, dimethicone, cetyl alcohol.

Especially caprylic / capric triglycerides, C12-C15 alkyl benzoate,

Diethylhexyl carbonate, cetearyl isonononoate, isopropyl palmitate, isopropyl stearate,

Dicapryl carbonate, ethylhexyl salicylate, ethylhexyl cocoate, decyl oleate, cyclopentasiloxane (cyclomethicone), coco-caprylate / caprate.

The invention also relates to a combination product comprising a packaging material containing a cosmetic and / or dermatological preparation comprising one or more lipids, characterized in that the packaging material is coated with glass on the contact surfaces with the preparation.

The cosmetic or dermatological preparations according to the invention comprise one or more lipids. Lipid is a collective term for all fatty substances, such as oils and waxes and lipophilic emulsifiers, UV filters, spreaders and also include fatty substances of natural origin, which are made for example of petroleum. Fats protect the skin from drying out and damaging environmental influences. They moisturize and smooth the skin structure. Lipids have a positive effect on the care properties of the cosmetic or dermatological product. They improve the

Spreadability, richness and create a smooth and supple skin feeling. The appearance is also positively influenced by the proportion of lipids: the higher the proportion, the whiter, richer and glossier, for example, an emulsion looks like.

Due to these advantages, a simple waiver of lipid components in the cosmetic preparation to prevent the problem of packaging migration is not possible. The preparations according to the invention may comprise cosmetic adjuvants conventionally used in such preparations, for example preservatives, bactericides, UV filters, antioxidants, water-soluble vitamins, minerals, suspended solid particles, substances for preventing foaming, dyes, pigments having a coloring effect have, thickeners, moistening and / or moisturizing substances or other conventional ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers or silicone derivatives.

In addition to other excipients and additives customary in cosmetics, the preparations according to the invention may of course also include plant extracts, in particular also those on a lipophilic carrier matrix. Such extracts may e.g. by pressing pulp or seeds, or by the use of additional extractive or carrier agents on parts of the corresponding plant or their fruit.

Preferably, the packaging means are constructed of polyolefins or at least they include polyolefins (PE, PP). But also other packaging materials such as plastics (including their blends) such as styrene polymers (PS, SAN, ABS, etc.), PET, PMMA, PC, the family of PHA's, PHB's, PLA, cellulose, derivatives - but also glass may be part of packaging according to the invention. Roll-on packaging whose ball and / or fitment are made of PE or PP are also to be understood as polyolefinic packaging materials according to the invention.

Likewise, polyolefin packaging means all those packaging materials which consist entirely of polyolefins or comprise only parts of polyolefins, in particular polypropylene, which may be in contact with the formulations.

For example, since a packaging material may also constitute a bag-in-can system by storing a preparation in an additional bag contained in the packaging material, according to the invention both the inner bag and the outer packaging means are to be understood as packaging means.

Likewise according to the invention, a coating of the packaging with glass is only necessary at the points at which the packaging can come into contact with the preparations contained. For example, the bag-in can would contain the surrounding packaging material only at the dispensing opening at which the preparation meets the bag. to coat with glass. This allows a resource-saving use of the glass coating according to the invention.

In particular, tubes, bottles, such as roll-ons and other stable small hollow bodies, crucibles, sticks, lotion and atomizer pumps and pump components, lids, applicators, aerosol headers (spray heads), risers, sachets and suitable foils or composite materials are considered as packaging means ,

Comparative tests to untreated polymer samples have shown that in all cases the swelling can be reduced to less than one-tenth.

In a comparative experiment, the swelling behavior of HDPE bottles was investigated.

Various bottles (150 ml, 250 ml and 400 ml) and crucibles (50 ml) consisting of PE, PP, PET and SAN were subjected to an SiO x coating. As a precursor for the PE-CVD process was a mixture of hexamethyldisiloxane (HMDSO) and

Hexamethyldisilazane (HMDSN) used.

The BIF (Barrier Improvement Factor) of the coated bottles compared to the uncoated bottles averaged 86.9. The BIF is the quotient of permeability of oxygen without coating and permeability of oxygen with coating.

The BIF describes the improvement of the barrier effect against oxygen diffusion. A BIF means no barrier enhancement, a BIF above 1 means an increase of the barrier effect.

Oxygen Transmission Rate (OTR) was measured at a pressure of 0.21 bar and normalized to surface area and diffusion time.

In the containers were recipes, which z.T. the ingredients described contained and filled individual ingredients and each stored at room temperature and 40 ° for a total of 6 months.

During a subsequent assessment, the geometric and haptic and organoleptic changes of the container on the one hand and changes in the contents on the other hand were examined. It could be shown that untreated (uncoated) containers have already undergone significant negative changes. Visible were, for example, strong bottle deformation, label peel effects and migrated raw materials in Shape of a smear layer on the outer wall of the container. The SiO _x coated containers did not show these defects.

It thus turned out that with the glass layer a very good barrier against the filling material contained therein is achieved.

This was surprising for the person skilled in the art, since previous tests with other coating methods, for example with acetylene, have had little or no effect.

Claims

claims

1. Use of surface-treated containers, functional and system packaging and applicators for the provision and application of cosmetic and / or dermatological preparations, characterized in that the surface treatment a functional layer of silicon oxide and / or insoluble metal oxide (glass) at least on the preparation touch the surfaces was created.

2. Use according to claim 1, characterized in that the provided or applied cosmetic and / or dermatological preparation contains at least one substance from group A, wherein the group A comprises:

C12-C15 alkyl benzoate, aromatic fatty acid esters, 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran, cetyl alcohol,

Dicapryl ether, dioctyl carbonate, 2,6-dimethyl-7-octene-2-ol, 2-acetone-pentone-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl, 2-isobutyl-4-hydroxy-4-methyltetrahydropyran, 2-tert-pentylcyclohexylacetate, 3,7-dimethyl-2,6-octadien-1-ol, 3-methyl-5-phenyl-1-pentanol, 7-acetyl 1, 1, 3,4,4,6-hexamethyltetralin,

Adipic diester, alpha-amylcinnamaldehyde, alpha-isomethylionone, alpha-methylionone, amyl C butylphenylmethylpropionalcinnamal, amylcinnamyl alcohol, amyl salicylate, anisalcohol, benzoin, benzylacetate, benzyl alcohol, benzyl benzoate, benzyl cinnamate, benzyl salicylate, bergamot oil, bitter orange oil,

Butylphenyl methylpropioal, cardamom oil, cedrol, cinnamal, cinnamyl alcohol, citral, citronellol, citronellylmethyl crotonate, citrus oil, coumarin, diethyl succinate, dimethicones, d-limonene, ethylene brassylate, ethyllinalool, eugenol, Evernia furfuracea extract, Evernia prunastri extract, farnesol, geraniol, glycerol,

Guaiac wood oil, heliotropin, hexylcinnamal, hexyl salicylate, hydroxycitronellal, hydroxyisohexyl 3-cyclohexene carboxaldehydes, isoeugenol, isoparaffin, lavender oil, lemone oil, limonene, linalool, linalyl acetate, mandarin oil, menthyl PCA, methyl-2-octynoate, methyl benzoate, BHT, methyl cedryl ketones, methyl dihydrojasmonates, methyl heptenone, nutmeg oil , p-butyl-alpha-methyldihydrocinnamic aldehyde, Rosemary oil, sweet orange oil, paraffin oil, phenoxyethanol, silicone oil, terpineol, tonka bean oil, triethyl citrate, vanillin.

3. Use according to claim at least one of the preceding claims, characterized in that the provided or applied cosmetic and / or dermatological preparation contains at least one substance from group B, wherein the group B comprises:

Caprylic / capric triglycerides, C12-C15 alkyl benzoate, diethylhexyl carbonate, cetearyl isonononoate, isopropyl palmitate, isopropyl stearate, dicapryl carbonate,

Ethylhexyl salicylate, ethylhexyl cocoate, decyl oleate, cyclopentasiloxane

(Cyclomethicone), coco-caprylate / caprate.

4. Containers for cosmetic and / or dermatological preparations, characterized in that the containers have a modified at least partially by glass coating surface.

5. Containers according to claim 4, characterized in that the preparation-contacting surface portions, in particular the inner wall, are coated with glass.

6. Applicators for cosmetic and / or dermatological preparations, characterized in that the applicators have an at least partially modified by coating with glass surface.

7. An applicator according to claim 6, characterized in that the applicator is a lotion pump, a spray pump, a roll-on applicator, a brush, a brush, a sponge or a Päd.

8. An applicator according to claim 7, characterized in that the slidingly contacting components have at least on their sliding surfaces a modified surface, in particular pistons and cylinders in pumps and order ball and fitment in roll-on applicators.

9. Applicators or containers according to one of claims 4 to 8, characterized in that the glass layer has a thickness of 10 to 250 nanometers, in particular 30 to 50 nm.

10. Combination product comprising a packaging containing a cosmetic

and / or dermatological preparation, wherein the preparation comprises one or more lipids, characterized in that the packaging material is at least partially coated with glass at the contact surfaces with the preparation.