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EP1509193A1 - Dispersions aqueuses haute concentration renfermant des particules d'oxyde metallique hydrophiles microfines et un agent dispersant - Google Patents

Dispersions aqueuses haute concentration renfermant des particules d'oxyde metallique hydrophiles microfines et un agent dispersant

Info

Publication number
EP1509193A1
EP1509193A1 EP03730067A EP03730067A EP1509193A1 EP 1509193 A1 EP1509193 A1 EP 1509193A1 EP 03730067 A EP03730067 A EP 03730067A EP 03730067 A EP03730067 A EP 03730067A EP 1509193 A1 EP1509193 A1 EP 1509193A1
Authority
EP
European Patent Office
Prior art keywords
aqueous dispersions
microfine
oxide particles
metal oxide
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03730067A
Other languages
German (de)
English (en)
Inventor
Christoph Batz-Sohn
Petra Brandt
Thomas Dietz
Steffen Hasenzahl
Klaus Jenni
Kathrin Lehmann
Ralf Mathiak
Angela Ruettgerodt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Goldschmidt GmbH
Evonik Operations GmbH
Original Assignee
Degussa GmbH
TH Goldschmidt AG
Goldschmidt GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH, TH Goldschmidt AG, Goldschmidt GmbH filed Critical Degussa GmbH
Publication of EP1509193A1 publication Critical patent/EP1509193A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/044—Suspensions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines

Definitions

  • the invention relates to aqueous dispersions containing hydrophilic microfine metal oxide particles and maleic anhydride / maleate-acrylate copolymers as dispersants and the use of these dispersions for the production of cosmetic formulations, in particular sunscreen formulations.
  • UV filters such as creams or lotions
  • UV filters they contain one or more organic compounds that absorb in the wavelength range between 290 and 400 nm: UVB- (290 to 320 nm); UVA radiation (320 to 400 nm).
  • the high-energy UVB radiation causes the typical sunburn symptoms and is also responsible for suppressing the immune system, while the UVA radiation penetrating deeper into the skin layers causes the premature aging of the skin. Since the interaction of the two types of radiation should promote the development of light-related skin cancer such as skin cancer, the search for ways to significantly improve the UV protection that was already achieved began early on. It has been found that microfine (ultra-fine) pigments based on metal oxides can also scatter, reflect and absorb UV radiation. Therefore, their highly dispersed formulations represent an effective addition to the organic UV filters in sunscreens.
  • Microfine titanium dioxide is used in a variety of ways in cosmetic formulations because it is chemically inert and toxicologically harmless and does not lead to skin irritation or sensitization. It is currently the most frequently used and most important mineral sunscreen. In addition to titanium dioxide, microfine zinc oxide is increasingly being used.
  • the average primary particle size for the micropigments is generally well below 200 nm, usually in the range from 10 to 100 nm, generally below 50 nm.
  • the coarse-particle pigment (0.2 to 0.5 ⁇ m) absorbs or reflects broadly and relatively uniformly over the entire UV range and the range of visible light, while the fine-particle material significantly increases the effectiveness in the UV range with simultaneous loss of effectiveness in long-wave UV -A and especially in the visible area. Since only a little visible light is reflected, preparations based on this active ingredient are therefore largely transparent.
  • the microfine Ti0 2 particles are photoactive and able to generate reactive species (e.g. hydroxyl radicals).
  • reactive species e.g. hydroxyl radicals
  • These substances can adhere to the surface chemisorptively or physisorptively (lattice doping / coating). This leads to qualities that are suitable for cosmetic light stabilizers.
  • WO-A-90/06103 proposes the tendency to clump (tendency towards reagglomeration of titanium dioxide particles with grain sizes ⁇ 100 nm) by coatings from phospholipids.
  • aqueous dispersions do not contain sufficiently high levels of microfine Ti0 2 , sediment during storage and / or the photoactivity is still too high.
  • Another major disadvantage is that they are not stable in the pH range of approximately 5 to 7 (pH of the skin surface) which is particularly preferred for cosmetic formulations.
  • the object of the present invention was therefore to overcome the existing disadvantages and to produce stable, highly concentrated aqueous dispersions of microfine metal oxide particles, in particular microfine titanium dioxide, with comparatively low viscosities, which are stable even in the acidic physiologically favorable pH range.
  • the object is achieved by using uncoated or hydrophilically coated microfine metal oxide particles and
  • the invention therefore relates to aqueous dispersions comprising:
  • Another object of the invention is the use of the aqueous dispersions according to claim 1 for the production of cosmetic formulations.
  • These products are used in amounts of 0.5 to 40% by weight, preferably in amounts of 1 to 35% by weight, based on the aqueous dispersion.
  • microfine metal oxide particles all metal oxides customary in the respective fields of application can be used as microfine metal oxide particles.
  • microfine or “ultra-fine” refers to particle sizes of on average ⁇ approximately 250 nm, preferably approximately 100 nm and below.
  • the selection is naturally limited to the compounds which are harmless from a toxicological and dermatological point of view, such as preferably cerium oxide, zinc oxide, iron oxide and in particular titanium dioxide.
  • Titanium dioxide P-25 has proven to be particularly advantageous here
  • Titanium dioxide P-25 consists of about 80% anatase and about 20% rutile and has an average primary particle size of about 21 nm. It is characterized by high cosmetic acceptance and very good water resistance.
  • auxiliaries and additives known in this field can be used if required, such as ethanol, propanol, butanol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, alkoxilates, glycol ethers, glycols, polyethylene glycols, polypropylene glycols, polybutylene glycols, Glycerol ester ethoxylates, glycerol, polyglycerol, sorbitol, sucrose, fructose, galactose, mannose, polysorbate, starch, xanthan gum, carrageenan gum, cellulose
  • alginates alginates, glycol esters, sorbitan esters, opacifiers, solubilizers, ethoxylated fatty alcohols, sodium chloride, sodium sulfate, magnesium sulfate, buffer systems, cholesterol, pantothenic acid, ascorbic acid, polyacrylic acids, carbomers.
  • the dispersions obtained are notable for high fineness of the dispersed solid, long-term storage stability and low viscosity.
  • the viscosity is measured using a Brookfield RVT, spindle 5, according to the manufacturer's instructions and is between 10 and 40,000 mPas at room temperature at 10 revolutions per minute (rpm).
  • the zeta potential can be used as a feature for the electrostatic stabilization of a dispersion.
  • the beta potential is the outwardly effective potential of the particles and represents a measure of the electrostatic interaction between individual particles. It plays a role in the stabilization of suspensions and in particular of dispersions with dispersed microfine particles. With a zeta potential value of ⁇ -20 mV or> + 20 mV there is a strong repulsion between the particles, the dispersions remain stable. At values within this range, the rejection becomes so low that the van der Waal's forces allow the formation of agglomerates and lead to undesired sedimentation of the particles. Measurements of the aqueous dispersions according to the invention have a significantly lower zeta in the pH range from about 3 to about 10
  • the dispersions according to the invention can be prepared by the processes which are generally known in this field, dispensers with toothed disks, bead mills, rotor-stator systems or the Scandex shaker being used as mixing devices.
  • the dispersing additives and any polyols which may be used are advantageously placed in the water and the pigment is sprinkled in with appropriate stirring. The pre-dispersion thus obtained is then finely dispersed.
  • the aqueous dispersions contain:
  • Glycerin, propylene glycol, butylene glycol and higher glycols, polyglycerols, sorbitol and comparable sugar alcohols and 0.1 to 0.5% water-soluble or water-dispersible preservatives can also be used as auxiliaries and additives.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne des dispersions aqueuses renfermant des particules d'oxyde métallique microfines et un agent dispersant. Ces dispersions sont caractérisées en ce que l'agent dispersant utilisé est un des composés de formules générales (I), dans lesquelles M représente hydrogène, un cation métallique monovalent ou bivalent, un ion ammonium, un radical amine organique, a vaut 1 ou, si M est un cation métallique bivalent, ? X représente -OMa ou -O- (CpH2pO) q - R1 avec R1 = H, un radical hydrocarbure aliphatique à 1-20 atomes de C, un radical hydrocarbure cycloaliphatique à 5-8 atomes de C, un radical alkyle éventuellement substitué à 6-14 atomes de C, p = 2 à 4, q = 0 à 100, -NHR2 et/ou -NR2 2 avec R2 = R1 ou -CO-NH2 Y représente O, NR2 A1 représente un radical éthylène, propylène, iso-propylène, butylène, m vaut de 10 à 30, n vaut de 0 à 50, k vaut de 10 à 30, la somme m + k étant située entre 20 et 60, de préférence entre 20 et 40.
EP03730067A 2002-06-06 2003-05-17 Dispersions aqueuses haute concentration renfermant des particules d'oxyde metallique hydrophiles microfines et un agent dispersant Withdrawn EP1509193A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225123 2002-06-06
DE10225123A DE10225123A1 (de) 2002-06-06 2002-06-06 Hochkonzentrierte wässrige Dispersion enthaltend hydrophile mikrofeine Metalloxidpartikel und Dispergierhilfsmittel
PCT/EP2003/005203 WO2003103619A1 (fr) 2002-06-06 2003-05-17 Dispersions aqueuses haute concentration renfermant des particules d'oxyde metallique hydrophiles microfines et un agent dispersant

Publications (1)

Publication Number Publication Date
EP1509193A1 true EP1509193A1 (fr) 2005-03-02

Family

ID=29557587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03730067A Withdrawn EP1509193A1 (fr) 2002-06-06 2003-05-17 Dispersions aqueuses haute concentration renfermant des particules d'oxyde metallique hydrophiles microfines et un agent dispersant

Country Status (8)

Country Link
US (1) US7399487B2 (fr)
EP (1) EP1509193A1 (fr)
JP (1) JP2005529939A (fr)
AU (1) AU2003240671B2 (fr)
CA (1) CA2484783A1 (fr)
DE (1) DE10225123A1 (fr)
PL (1) PL372066A1 (fr)
WO (1) WO2003103619A1 (fr)

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JP2008506662A (ja) * 2004-07-13 2008-03-06 ロレアル 親水性金属酸化物ナノ顔料と低分子量のポリアルキレングリコールとを含む水性光保護組成物；その使用
DE102004037045A1 (de) 2004-07-29 2006-04-27 Degussa Ag Wässrige Silan-Nanokomposite
DE102004037044A1 (de) 2004-07-29 2006-03-23 Degussa Ag Mittel zur Ausstattung von auf Cellulose und/oder Stärke basierenden Substraten mit Wasser abweisenden und gleichzeitig pilz-, bakterien-, insekten- sowie algenwidrigen Eigenschaften
DE102004049427A1 (de) 2004-10-08 2006-04-13 Degussa Ag Polyetherfunktionelle Siloxane, polyethersiloxanhaltige Zusammensetzungen, Verfahren zu deren Herstellung und deren Verwendung
DE102005004872A1 (de) * 2005-02-03 2006-08-10 Degussa Ag Wässrige Emulsionen von funktionellen Alkoxysilanen und deren kondensierten Oligomeren, deren Herstellung und Verwendung zur Oberflächenbehandlung
DE102005032427A1 (de) * 2005-07-12 2007-01-18 Degussa Ag Aluminiumoxid-Dispersion
DE102006006656A1 (de) * 2005-08-26 2007-03-01 Degussa Ag Silan enthaltendes Bindemittel für Verbundwerkstoffe
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Also Published As

Publication number Publication date
PL372066A1 (en) 2005-07-11
JP2005529939A (ja) 2005-10-06
US20030229172A1 (en) 2003-12-11
WO2003103619A1 (fr) 2003-12-18
AU2003240671A1 (en) 2003-12-22
AU2003240671B2 (en) 2007-10-11
CA2484783A1 (fr) 2003-12-18
DE10225123A1 (de) 2003-12-18
US7399487B2 (en) 2008-07-15

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