WO2023196410A1 - Modified natural and green particles for cosmetic application - Google Patents

Modified natural and green particles for cosmetic application Download PDF

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Publication number
WO2023196410A1
WO2023196410A1 PCT/US2023/017603 US2023017603W WO2023196410A1 WO 2023196410 A1 WO2023196410 A1 WO 2023196410A1 US 2023017603 W US2023017603 W US 2023017603W WO 2023196410 A1 WO2023196410 A1 WO 2023196410A1
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WO
WIPO (PCT)
Prior art keywords
particles
acid
groups
modification
modified
Prior art date
Application number
PCT/US2023/017603
Other languages
French (fr)
Inventor
Laxmi Samantara
Amar PAWAR
Thorsten FELDER
Raghu N
Roland Wagner
Christian WENSKE
Benjamin Falk
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Momentive Performance Materials Inc.
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.)
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Application filed by Momentive Performance Materials Inc. filed Critical Momentive Performance Materials Inc.
Publication of WO2023196410A1 publication Critical patent/WO2023196410A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/027—Fibers; Fibrils
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • 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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives 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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/12—Face or body powders for grooming, adorning or absorbing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/612—By organic compounds

Definitions

  • the present invention relates to modified natural and green particles which are particularly useful for personal care and cosmetic applications, the use of such particles in personal care products, and personal care products comprising the same.
  • Sub-micron particles as well as particles in the micron range are used to improve the line blurring, soft focus properties on the skin.
  • US 20180078484 describes microfibri Hated celluloses having a length of 0.1 to 50 microns and a diameter from 0.001 to 0.5 microns, in particular, modified microfibrillated cellulose (MFC) with fibril length from 100 nm to 50 pm, fibril diameter from 1 nm to 500 nm as an anti -wrinkle-agent.
  • MFC modified microfibrillated cellulose
  • US9962565 describes the use of different particles including mica particles as the light scattering materials.
  • US10137064B2 describes use of different fillers including inorganic fillers, polyolefin particle, cellulose and bamboo in the personal care compositions.
  • US9446265B2 describes starch particles of particle size of 5 to 30 microns as optical materials to improve the soft-focus effect.
  • micronized particles of cellulose and bamboo with particle size ⁇ 50 microns and their modification for personal care applications is not studied.
  • EP 3081209 Al is directed at microfibrillated cellulose, which is modified by various means including silylation and condensation with glycidyl derivatives, whereas neither esterification nor physisorption modifications of the cellulose particles are addressed.
  • CN104358152 discloses cellulose particles that are modified by quaternary ammonium compounds. Therein, the modification takes place by reacting the hydroxyl groups of the cellulose fibers with the epoxy groups of a small molecule quaternary ammonium salt cation modifier or epoxy groups of a high molecular quaternary cation modifier, while modification by physisorption of such compounds is not disclosed, and both the small molecule quaternary ammonium molecules and the high molecular quaternary cation modifiers are different from the C4 to C29 alkyl derived quaternary ammonium compounds applied for the modification of particles by physisorption in the present invention.
  • CN109674751 B discloses the modification of small particle size starch particles by esterification by using octenyl succinic anhydride, while modifications of cellulose particles or other fibrous natural particles as defined herein are not addressed.
  • WO 2019/151936 Al discloses quinoa starch particles modified by esterification with octenyl succinic anhydride, while modifications of particles different from starch- based particles are not addressed.
  • CN103898630 a modified bamboo charcoal polyester fiber, which is prepared with bamboo charcoal powder, PET slices and, inter alia, chitosan, is disclosed, while there is no disclosure of a modification of the material by esterification or physisorption of quaternary ammonium compounds or metal carboxylates in the document.
  • CN 109486160 is directed at a green tea powder prepared by pulverizing and grinding green tea leaves, further modified with a surface modifier which is an organopoly siloxane modified by an alkyl group. Therein, there is no indication of an esterification of the tea leaf particles.
  • This invention is intended to replace synthetic microplastics (e.g. Tospearls) and focuses on the modification of micronized cellulose and micronized natural fibers in the size range of 1 to 50 microns.
  • the unmodified micronized cellulose samples are either obtained from commercial sources, i.e. the VIVAPUR CS and VITACEL CS series (J. Rettenmaier & Sohne GmbH), alternatively larger natural fibers, in particular bamboo fibers, are grinded into particles in the 1 to 50 micron range for the intended soft focus application and modified afterwards.
  • the modification of these micron sized particles is done by an either chemical or physical treatment, resulting in chemical modifications such as esterification and silication, or in the physisorption of quaternary ammonium compounds, amines or metal carboxylates.
  • the preferred chemical modifications are esterifications, such as acetylation, long fatty acid esterification, and parallel modification by acylation, such as acetylation, and silication.
  • Preferred reagents for the modifications are acetic acid anhydride, fatty acid chlorides and silicate esters of carboxylic acids, such as tetraacetoxysilane Si(OAc)4.
  • the preferred method for the physical modification of the particles is the treatment with quaternary ammonium compounds.
  • commercial ester quats and poly fatty acid based quats as outlined in WO 2004/093834 and WO 2021/123904 are the most preferred reagents.
  • the modification of the particles allows to control and steer the water- and solvent absorbance properties of the particles, to control the hydrophilicity /hydrophobicity properties of the particles and to adjust the sensory properties of the particles and the properties imparted to personal care and cosmetic compositions.
  • the present invention relates to modified particles, wherein
  • said particles are selected from cellulose-based particles,
  • said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
  • metal carboxylates of divalent metals or trivalent metals preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and
  • TAA triethanol amine
  • the invention further relates to the use of such modified particles for the manufacture of personal care products, and personal care products comprising such modified particles.
  • said particles are selected from cellulose-based particles,
  • said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
  • metal carboxylates of divalent metals or trivalent metals preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and
  • said particles being optionally modified by one or more secondary modifications selected from the group consisting of: modification by physisorption of primary, secondary and tertiary amines, preferably of triethanol amine (TEA), modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides (quats), preferably of quatemized guar gums, and modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides
  • a modified particle is any particle selected from the group (A) that has been submitted to one or more primary modifications selected from the group (B) and optionally one or more secondary modifications selected from the group (C).
  • a particle is a portion of matter defined by its size and the type of matter it consists of.
  • the scope of the invention described herein is limited to particles having an average particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20 pm, each as determined by Scanning Electron Microscope (SEM) analysis. It is also preferred that the average particle size is in the range of 2 to 50, more preferably 4 to 40, even more preferably 7 to 30, and still more preferably 10 to 20 pm, as determined by SEM Analysis. It is clarified at this point that the average particle size cited as being according to the invention refers to the size of the particles selected from the group (A) before they are submitted to any primary modification or secondary modification.
  • SEM Scanning Electron Microscope
  • the particle size is preferably determined by Scanning Electron Microscopy (SEM) according to the ASTM Fl 877- 16 Standard Practice for Characterization of Particles. The average particle size is evaluated by Scanning Electron Microscopy.
  • Zeiss EVO-18 Scanning Electron Microscope is used, with test condition SEM: HV, 15 kV Voltage, WD: 8.5-9.5 mm, Probe Current: 100 pa, Detector: SE and BSD. Samples were prepared by smearing the powder on carbon adhesive tape and blowing air to remove excess particles. Samples were sputter coated with gold at 10mA for 90 sec. Smart SEM software from Carl Zeiss software is used for determining the particle size. The particle size range was determined by SEM and the values were reported for particles that were in the average range of 80%.
  • the particle size may also be determined by Laser Diffraction Spectrometry Analysis. (Reference: https://www.govinfo.gov/content/pkg/GOVPUB-C13- 765c83e30d67c74a880858fcd261b43e/pdf/GOVPUB-C13- 765c83e30d67c74a880858fcd261b43e.pdf as retrieved on November 15, 2021).
  • average particle size refers to having such D50 particle size distribution value.
  • D50 particle size distribution value means that 50% (per volume) of the particles have a particle size above or below the defined D50 value expressed in pm.
  • the particles selected from the group (A) before they are submitted to any primary modification or secondary modification have a D50 value in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20 pm, and it is also preferred that the D50 value of the particles is in the range of 2 to 50, more preferably 4 to 40, even more preferably 7 to 30, and still more preferably 10 to 20 pm, as determined by Laser Diffraction Analysis.
  • PSD particle size distribution
  • Measuring device e.g. LS 13 320 Laser Diffraction Particle Size Analyzer of Beckmann Coulter, Beckman Coulter International S.A. Switzerland
  • Sample module Vacuum pressure dispersion system, e.g. Dry Powder System (Tornado), Beckman Coulter International S. A. Switzerland
  • Measurement Apply the specified vacuum to transfer the sample and determine the cumulative volume distribution using a laser light diffraction instrument in accordance with the instruction manual. The parameters may be adjusted so that the test dispersion is representative, homogeneous and well dispersed.
  • Evaluation/assessment Determine the particle sizes at the undersize values of 10%, 50% and 90% (dlO, d50, d90), and additional values in question, from the cumulative volume distribution.
  • the average particle size is determined by SEM, as described above first.
  • the particles according to the invention are selected from
  • cellulose-based particles in general refers to particles comprising at least 90 percent by weight of cellulose, preferably at least 92 percent by weight, more preferably 93 or more percent by weight and most preferably 95 percent by weight.
  • Natural materials containing cellulose include plants, algae and bacteria. While plant-derived cellulose is usually found in a mixture with hemicellulose, lignin, pectin and other substances, bacterial cellulose is of higher purity. Due to the structure of cellulose, cellulose-based particles are characterized by the presence of hydroxyl groups on the surface of the particles, which enable further functionalization by chemical modification, for example by esterification or silication of the hydroxyl groups.
  • cellulose-based particles are commercially available microcrystalline cellulose powders produced from wood pulp or cotton linters, as obtainable from many commercial suppliers, such as Sigma Aldrich, J. Rettenmaier & Sbhne GmbH + Co. KG and many more. Specific examples are the materials of the VIVAPUR CS and VITACEL CS series (J. Rettenmaier & Sohne GmbH + Co. KG; https://www.jrs.eu/jrs_en/life-science/cosmetics/skin-care/ as retrieved on November 1 1, 2021).
  • the cellulose particles may be submitted to any procedure suitable for micronization, for example milling, grinding and/or sieving.
  • natural fiber particles in general refers to fibers that are produced from plants, in contrast to non-natural fibers made from materials obtained synthetically from chemical processes.
  • plant fiber particles are a preferred group of natural fiber particles, generally comprising any particles of seed fiber, leaf fiber, bast fiber, fruit fiber and stalk fiber.
  • natural fiber particles are particles of bamboo fiber, coconut fiber, cotton fiber, flax fiber, hemp fiber, jute fiber, kenaf fiber, sisal fiber and wood fiber, in particular bamboo fiber, Lac fiber and hemp fiber.
  • natural fibers may be submitted to a pretreatment for micronization such as grinding, milling and/or sieving in order to obtain natural fiber particles displaying an average particle size as determined by SEM Analysis of up to 50 pm, preferably 1 to 50 pm.
  • starch-based particles in general refers to particles comprising at least 90 percent by weight of starch, preferably at least 92 percent by weight, more preferably 93 or more percent by weight and most preferably 95 percent by weight.
  • Specific examples of starch-based particles are commercially available starch powders, such as corn starch, potato starch, wheat starch, rice starch or manioc starch.
  • starch powders are extracted and refined starches, wherein the term “starch powders” according to the invention also comprises unrefined starch powders.
  • the starch-based particles according to the invention also comprise particles obtained by drying and/or grinding plant parts which are rich in starch, such as for example potato flour, sweet potato flour, corn flour or rice flour.
  • the starch-based particles may be submitted to grinding, milling and/or sieving in order to obtain starch-based particles displaying an average particle size as determined by Scanning Electron Microscopy (SEM) Analysis of up to 50 pm, preferably 1 to 50 pm.
  • SEM Scanning Electron Microscopy
  • the particles described here are plant derived particles not included by the above definition of natural fiber particles.
  • said particles comprise in particular particles obtained by grinding or milling dry or dried plant parts, for example dried leaves, seeds, blossoms, fruits, branches, twigs and roots.
  • plant-based particles are green tea leave powder, orange peel powder, and bamboo particles obtained from processed bamboo pole.
  • particles may fall under more than one of the above-cited typed of particles from which the particles according to the invention are selected.
  • many plant fiber particles may also be considered to be cellulose-based particles, as they typically have a high content of cellulose.
  • the modified particles according to the invention are obtained when the particles as described above have been submitted to one or more primary modifications (B) selected from the group consisting of esterification, esterification and silication, physisorption of C4 to C29 alkyl derived quaternary 7 ammonium compounds (quats), physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate
  • the term “primary modification” in general refers to the mandatory modification step or steps to which the particles are submitted, whereas the secondary modificati on steps (C) are optional and may be applied for further modification of the particles.
  • the primary and secondary modification steps are performed at the same time, for example in one reaction set-up.
  • An example in which more than one modification of one type of the primary modifications (B) is performed is the case when several esterification reactions using different esterification reagents are performed by simultaneous or sequential reaction of the particles with two or more acyl donor reagents, for example with a long-chained, i.e. CIO or more, acyl chloride and a short-chained, i.e. C2-C5, acyl chloride.
  • acyl donor reagents for example with a long-chained, i.e. CIO or more, acyl chloride and a short-chained, i.e. C2-C5, acyl chloride.
  • a part of or all of the free hydroxyl groups of the particles are esterified by a reaction with an acyl donor reagent.
  • the invention comprises esterification reactions using any type of organic compound having one, two, three or more carboxylic acid groups or derivatives thereof, such as the corresponding acyl halides, anhydrides or esters.
  • any type of organic compound having one, two, three or more carboxylic acid groups or derivatives thereof such as the corresponding acyl halides, anhydrides or esters.
  • esterification using monocarboxylic acids or derivatives thereof as acyl donor reagents and to compounds having two, three or more carboxylic acid groups or derivatives thereof, which are referred to as di- and higher carboxylic acids and derivatives thereof.
  • the acyl donor reagents applied in the esterification of the particles are not restricted in any way and may be selected from carboxylic acid anhydrides, acyl chlorides, carboxylic acids, carboxylic acid esters, and carboxylic acid thioesters, or carboxylic acid amides, wherein carboxylic acid anhydrides and acyl chlorides are preferred due to their high reactivity.
  • the acyl donor reagents for esterification are preferably selected from C2-C18 n-alkyl monocarboxylic acid chlorides and non-mixed C2-C18 n-alkyl monocarboxylic acid anhydrides, as well as fZ)-9-Octadecenoic acid chloride or (Zj-9-Octadecenoic acid anhydride, more preferably from C2, C4, C6, CIO, C12, C14, C16 and C18 n-alkyl monocarboxylic acid chlorides and non-mixed C2, C4, C6, CIO, C12, C14, C16 and C18 n-alkyl monocarboxylic acid anhydrides, as well as (ZJ- 9-Octadecenoic acid chloride or fZl-9-Octadecenoic acid anhydride.
  • acyl donor reagents derived from monocarboxylic acids according to the invention are selected from C2 to C18 monocarboxylic acid anhydrides and oleic acid anhydride, preferably C6 to C18 monocarboxylic acid anhydrides and oleic acid anhydrides, more preferably C6 to C12 monocarboxylic acid anhydrides and oleic acid anhydride.
  • the acyl donor reagents derived from monocarboxylic acids are selected from acetic anhydride, hexanoyl chloride, vinyl acetate, isopropenyl acetate, acetic acid and palmitoyl chloride.
  • esterification specifically refers to a reaction of a part of or all of the free hydroxyl groups of the particles with a di- or higher carboxylic acid or a corresponding acyl donor reagent, for example, in the case of dicarboxylic acids, the corresponding dicarboxylic halides, e.g. diacylchlorides.
  • Esterification using dicarboxylic acids, higher carboxylic acids or acyl donor reagents corresponding thereto enables cross-linking of the particles by an esterification reaction of a dicarboxylic acid or higher carboxylic acid with hydroxyl groups of two or more particles.
  • esterification reactions may be used as a further option for tuning the hydrophilicity /hydrophobicity properties of the particles, and also allows to aggregate the particles (A) in a controlled manner, preferably in addition to further modification steps.
  • the carboxylate groups of the di- and higher carboxylic acids or the analogous ester, anhydride or acyl halide groups of the corresponding acylating reagents are linked by a single bond, aliphatic or aromatic groups.
  • the two carboxylic groups or the analogous acyl donor functional groups of dicarboxylic acids and acyl donor reagents derived thereof are preferably linked by a single bond, Cl -Cl 8 alkylene groups, C2-C18 alkenylene groups, C4-C18 aromatic or heteroaromatic groups, even more preferably a single bond, linear unbranched Cl -Cl 8 alkylene groups, C2-C18 alkenylene groups, in particular monounsaturated C2-C18 alkenylene groups, phenylene groups, benzylene groups, xylylene groups, or naphtalenyl groups.
  • the group of C 1 -C 12 linear unbranched alkylene groups and C2-C 12 monounsaturated alkenylene groups is particularly preferred as linker group.
  • Examples of preferred dicarboxylic acids selected from the group of linear saturated dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanoic acid, preferred dicarboxylic acids selected from monounsaturated alkenylene dicarboxylic acids are maleic acid, fumaric acid, glutaconic acid, citraconic acid, mesaconic acid and itaconic acid.
  • acyl chlorides, mono- and diesters formed with C1-C6 alcohols, internal anhydrides and mixed anhydrides formed with C1-C6 monocarboxylic acids thereof are likewise preferred.
  • Preferred higher carboxylic acids are citric acid, isocitric acid, aconitic acid, propane-1, 2, 3 -tricarboxylic acid, agaric acid, trimesic acid, pyromellitic acid, and compounds having three or more terminal carboxylic acid groups formally obtained by the esterification of polyols having three or more hydroxyl groups with dicarboxylic acids.
  • Preferred conditions for modification by esterification is the suspension of the particles in a solvent and the addition of one or more acyl chlorides and/or carboxylic acid anhydrides, and of a tertiary amine, for example triethyl amine or 4- (dimethylamino)pyridine.
  • the reaction may also be performed neat in an excess of the acylation reagent if it is a liquid at reaction temperature or may be used as a melt.
  • Further preferred conditions for esterification are Lewis- or Bronsted-acid catalyzed esterification, which are achieved by the conversion of the particles in the presence of a carboxylic acid or carboxylic acid ester acting as the acyl donor reagent, preferably added in excess, and a Lewis acid or Brbnsted acid acting as catalyst.
  • Esterification may also be achieved under mild conditions using mono-, di- or higher carboxylic acids or the corresponding carboxylic acid esters as acylation reagents in the presence of enzymes effecting esterification and transesterification reactions, in particular of hydrolases, for example lipases and esterases.
  • acyl donors and the reaction conditions may be chosen by the skilled artisan in view of the technical, environmental and economical requirements of the production of the modified particles according to the invention.
  • the hydroxyl groups on the surface of the particles are completely or partially converted to groups of the structure OC(O)R 1 , wherein R 1 is independently selected from C1-C17 alkyl and alkylene groups. Specific examples of R 1 are methyl, pentyl, tetradecyl.
  • R 1 ’ are methyl, propyl, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl and (Z)-heptadec-8-enyl.
  • the particles in a step of primary modification can be modified by esterification and simultaneous silication.
  • Preferred reagents for this type of primary modification are acylated silanes, preferred acetoxysilanes, i.e tetraacetoxy si lane and methyltriacetoxysilane.
  • acylated silanes are used as reagent, the free hydroxyl groups of the particles are esterified by reaction with the acyl group, i.e. acetyl group in case of acetoxy silanes.
  • the siloxy portion of the silanes by condensation forms a silicate polymer within the particles or on their surface.
  • the basic reaction mechanism is outlined in US2014/0127523 and M. Pries et. al., Wood Sci. Technol. 47, 2013, 685 to 699.
  • the particles are contacted with one or more quaternary ammonium compounds (quats) in such way that an amount of the one or more quaternary ammonium compound is adsorbed on the particles acting as adsorbent by intermol ecular forces which do not involve a significant change in the electronic orbital patterns of the species involved, i.e. without the formation of chemical bonds or ionic structures.
  • Physisorption thus refers to the accumulation of molecules or ions on the surface of a material, creating a film of the adsorbate, i.e. the molecules or ions being accumulated on the adsorbent's surface.
  • C4 to C29 alkyl derived means that the quat structures contain CHs and CH2 based moieties of the chain length C4 to C29, as for example typically found in fatty acids and fatty alcohols as hydrophobic moieties. It is within the scope of the invention that the hydrophobic chains in the quats used for the primary modification contain more than one of these C4 to C29 alkyl derived moieties. Therein, while it is mandatory that the quats comprise at least one, more preferably two or more CH3 and CH2 based moieties of the chain length C4 to C29, the quats may also contain CH?, and CH2 based moieties consisting of or comprising shorter alkyl and alkylene groups , i.e. C1-C3 alkyl and alkylene groups, and also moieties comprising 30 or more carbon atoms.
  • This definition explicitly includes quats containing poly fatty acid-based estolide moieties.
  • fatty acids and alcohols bearing these C4 to C29 alkyl derived moieties are the C5 to C30 fatty acids, such as hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecenoic acid, octadecanoic acid, behenic acid, oleic acid, ricinoleic acid, lesquerolic acid and 1 -ethylhexanoic acid and the respective alcohols.
  • a C4 to C29 alkyl derived quaternary ammonium compound is a quaternary ammonium compound comprising one or more C4 to C29 alkyl or alkylene groups.
  • the physisorption of the one or more quaternary ammonium compounds used may be effected in the absence or in the presence of a solvent.
  • one or more quaternary ammonium compounds are contacted with the particles selected from the group of (A) in a suspension of the particles, wherein the quaternary ammonium compound may be added to the suspension, or the suspension of the particles may be prepared in a solution or suspension containing the quaternary ammonium compound.
  • the load of the material adsorbed on the modified particles submitted to physisorption as modification treatment can be determined by quantitative FTIR, wherein the modified particles are submitted to an extraction protocol, and the content of material in the solution of the adsorbed material can be determined by comparison to a standard solution of the respective material.
  • the load is indicated by the weight ratio of the weight of the adsorbed material on the modified particles, for example the quaternary ammonium compound, to the total weight of the modified particles including any compounds adsorbed thereon.
  • the load “1” may be indicated as the ratio obtained following the equation
  • the load of said carboxylates can be determined by determination of the metal ion content of a sample by inductively coupled plasma optical emission spectrometry (ICP-OES) upon digestion of the sample.
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • the load of quaternary ammonium salts on the modified particles is in the range of from 0.01 to 10 weight-%, preferably from 0.05 to 5 weight-%, more preferably from 0.1 to 2 weight-% and most preferably from 0.5 to 1 weight-%.
  • the first group of these preferred quat compounds are quats containing poly fatty acid-based estolide moieties, i.e. compounds as described in WO2021/123904 Al, having the general formula
  • R 1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups
  • R 2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from O -, -NH -,
  • R 3 , R 4 , R 5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)--, -C(S)--, tertiary amino groups
  • quaternary ammonium groups can be substituted with one or more groups selected from OH groups and halide groups, wherein R 3 , R 4 , R 5 each bind with a carbon atom to the nitrogen atom, and preferably R 3 , R 4 , R 5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R 1 , R 2 , R 3 , R 4 , R 5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV ): ( ⁇ X-C(O)-R 6 )m-X--C(O)- (III) or
  • X is O or NR 11 , and
  • R 11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from
  • R 1 , R 3 , R 4 , R 5 do not bind through OCH2CH2 to the nitrogen atom of the group
  • these quat compounds are characterized by containing at least one estolide group, i.e. a poly carboxylic acid group formed by the condensation of at least two hydroxy or amino carboxylic acid units.
  • Estolide groups containing quats having the specific structures outlined in examples 6, 7, 8, 9, 10, 11, Ha, l ib, 11c, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29b, 29c, Synthesis Example 30, Synthesis Example 30a, Synthesis Example 30b, Synthesis Example 32, Synthesis Example 32a, Synthesis Example 32b, 33, Synthesis Example 33a, Synthesis Example 33b, 34, Synthesis Example 34a, Synthesis Example 34b, 35, Synthesis Example 35a, Synthesis Example 35b, 36b, 37b of WO 2021/123904 are particularly preferred.
  • These specific structures of the Examples of WO2021/123904 are hereby incorporated by reference as being particularly preferred C4 to C29 alkyl derived quaternary ammonium compounds for physisorption on the particles as a primary modification according to the present invention.
  • C4 to C29 alkyl derived quats are C4 to C29 alkyl derived ester quats.
  • Ester quats according to the invention are characterized by containing an ester group in at least one of the organyl substituents of one or more quaternary ammonium moieties of the quats.
  • cationic saturated or unsaturated fatty acid based mono-ester and di-ester quats having 7 to 21, preferred 7 to 17 carbon atoms in each of the fatty acid- derived alkyl chains, in particular monoester compounds, such as dimethylethanolamine-, methyldiethanolamine- and triethanolamine-derived C8-C18 saturated and unsaturated mono-ester quats, for example wherein each R is a C7-C17 saturated or unsaturated hydrocarbyl group, preferably a linear C7-C17 alkenyl or alkyl group, more preferably a C7 or C17 alkyl group, ethoxylated C8-C18 saturated and unsaturated mono-ester quats, such as cocoyl pentaethoxy methyl ammonium metho-sulfate (Rewoquat® CPEM), triethanolamine-derived C8-C18, preferably C16 - Cl 8 saturated and unsaturated di -ester quat
  • monoester compounds
  • each R independently is a C7-C17, preferably a C7 or C17 alkyl or alkenyl group, N, N-dimethyl-3 -aminopropane- 1 ,2-diol derived C8-C18, preferred C16 - C18 saturated and unsaturated ester quats, for example
  • N-dimethyl -diisopropanolamine derived C16 - C18 saturated and unsaturated ester quats for exampl e wherein each R independently is a C7-C17 alkyl or alkenyl group, and A' is a Cl', Br‘ or CHs-O-SCh" counter ion, such as dioleoylisopropyl dimethylammonium methosulfate, dioleoylisopropyl dimethylammonium chloride, dipalmitoylisopropyl dimethylammonium methosulfate, dipalmitoylisopropyl dimethylammonium chloride, bis-(isostearoyl/oleoyl isopropyl) dimethylammonium methosulfate, bis- (isostearoyl/oleoyl isopropyl) dimethylammonium chloride.
  • ester-containing di-quatemary ammonium compounds i.e. ester-containing di-quatemary compounds, containing at least one, preferred at least two C7-C29, more preferred C7-C21, even more preferred C7-C17 alkyl groups, for example head group-bridged di-quatemary compounds, such as ester brigded, preferably C4-C29 ether and ester bridges containing di-quatemary compounds, such as
  • ester-containing tri-quaternary ammonium compounds for example tri-quaternary compounds containing at least one, preferred at least two C10- C29, more preferred three C10-C22, even more preferred C10-C18 alkyl groups, in particular derived from
  • octadecaval ent preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from alkyl halogenides having more than one, preferred more than two carbon atoms such as alkyl chlorides, bromides, iodides, e.g.
  • octadecavalent preferably divalent to octadecavalent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetraval ent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from esters of halogenated carboxylic acids, preferred, chloro carboxylic acids, in total (ester) having more than two, preferred more than three carbon atoms such as esters of chloroacetic acid, 3- chloropropionic acid, 4-chlorobutanoic acid or the respective bromo carboxylic acids, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2, -propanediol, 1,3-propanediol, 1,3-
  • polyethylene glycols like diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol
  • polypropylene glycols like dipropylene glycol (e.g, derived from 2,2'-oxydi-l -propanol, l,l'-oxy di -2-propanol, and 2-(2-hydroxypropoxy)-l -propanol), tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide) and (butylene oxide)-based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copoly ethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers,
  • octadecaval ent preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from ethers or esters of epoxy compounds, in total having more than three, preferred more than four carbon atoms, preferred glycidyl ethers, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2, -propanediol, 1,3-propanediol, 1,3- butanediol, 1 ,4-butanediol, 1,2 hexanediol, 1,6-hexanediol,
  • polyethylene glycols like di ethylene glycol, tri ethylene glycol, tetraethylene glycol, and pentaethylene glycol
  • polypropylene glycols like di propylene glycol (e.g, derived from 2,2'-oxydi-l -propanol, l,l'-oxy di -2-propanol, and 2-(2-hydroxypropoxy)-l -propanol), tri propylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide)- and (butylene oxide)- based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copolyethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers, or preferred glycidyl esters, with acids, in particular neodecanoic acid,
  • octadecaval ent preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, formed from esters of halogenated carboxylic acids, preferred chloro carboxylic acids, in total having more than two, preferably more than three carbon atoms, such as chloroacetic acid, 3 -chloropropionic acid, 4-chlorobutanoic acid or the respective bromo carboxylic acids, with ethers or esters of epoxy compounds, preferred glycidyl ethers, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2-propaned
  • -propanol tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide)- and (butylene oxide)- based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copoly ethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers, or preferred glycidyl esters, with acids, in particular neodecanoic acid,
  • - monovalent to octadecavalent preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent, optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, formed from ethers of epoxy compounds, in total having more than seven, preferred more than eight carbon atoms, preferred glycidyl ethers, with di- to hexavalent carboxylic acids, in particular maleic acid, succinic acid, adipic acid, sebacic acid, itaconic acid, tartaric acid, trimellitic acid, fatty dimer acids, carboxyl (-C(O)OH) functionalized polyesters, in particular preferably formed by the condensation of di- to hexavalent carboxylic acids, e g.
  • fatty dimer acids with di- to hexavalent alcohols as outlined above or alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and compounds comprising at least one glycidoxy group, such as glycidol, diglycidyl ether, glycerol digly cidyl ether, glycerol triglycidyl ether and oligomeric glycerol glycidyl ethers, butanediol diglycidylether, in particular the condensation products of succinic acid, maleic acid and tartaric acid, fatty dimer acids with glycerol diglycidyl ether, polyesters, in particular preferably derived from oligomerized hydroxycarboxylic acids, in particular oligomerized lactic acid, 12- hydroxy stearic acid,
  • octadecaval ent preferably divalent to octadecavalent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent, optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from esters of halogenated carboxylic acids, preferably chloro carboxylic acids, in total having more than five, preferred more than six carbon atoms such as esters of chloroacetic acid, 3 -chloropropionic acid, 4- chlorobutanoic acid or the respective bromo carboxylic acids, with OH functionalized polyesters, in particular preferably formed by the condensation of di- to hexavalent carboxylic acids, e.g.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide
  • compounds comprising at least one glycidoxy group such as glycidol
  • the particles (A) are contacted with metal carboxylates of divalent and trivalent metals, in particular of Mg and Al, in such way that an amount of the one or more metal carboxylates of divalent and trivalent metals is adsorbed on the particular adsorbent by intermolecular forces which do not involve a significant change in the electronic orbital patterns of the species involved, i.e. without the formation of chemical bonds or ionic structures.
  • the term physisorption is thus understood in the same way as described above for the physisorption of quats.
  • the divalent metal cations are preferably selected from the group of the alkaline earth metal cations, in particular from magnesium and calcium.
  • the trivalent metals cations are preferably Al cations.
  • the carboxylate anions are preferably derived from fatty acids, more preferably from C12-C18 saturated or unsaturated unbranched aliphatic monocarboxylic acids, in particular C12, C14, C16 and C18 saturated or unsaturated unbranched aliphatic monocarboxylic acids.
  • the carboxylate anions are derived from capric acid, lauric acid, myristic acid, palmitic acid and stearic acid , specifically from stearic acid.
  • a preferred example of divalent metal carboxylates is thus Mg stearate, a preferred example of trivalent metal carboxylates is thus Al stearate.
  • the carboxylate anions are derived from linear, branched or dendritic poly fatty acids as outlined in WO 2021/123904 and WO 2021/123911, which in the sense of this invention are compounds characterized by at least one ester or amide linkage, more preferably ester linkage, of a fatty acid acyl structure to the alkyl or alkenyl backbone of another fatty acid compound or fragment.
  • the poly fatty acid-derived carboxylate anions comprise estolide structures formed by carboxylic acids as described above, preferably from the fatty acid compounds typically obtainable by hydrolysis of natural oils and fats.
  • estolide structure is identified by the secondary ester linkage of one fatty acyl molecule to the hydrocarbyl backbone of another fatty acid fragment.
  • fatty acid and “fatty acyl molecule” seem to imply that the individual residue needs to be derived from a component of a fat, which is not the case.
  • fatty acid herein generally refers to carboxylic acids with chain-shaped organyl groups, in particular unbranched aliphatic monocarboxylic acids. Fatty acids differ from each other by their number of carbon atoms (chain length) and, when referring to unsaturated fatty acids, the number and position of double bonds. Fatty acids may be classified as short chain fatty acids with up to 7 carbons atoms, middle chain fatty acids with 8 to 12 carbon atoms, long chain fatty acids with 13 to 21 carbon atoms, and very long chain fatty acids with more than 22 carbon atoms.
  • Poly fatty acids are obtained by condensation of the carboxyl group of one carboxylic acid molecule with a hydroxyl group or amino group, more preferably a hydroxyl group, of another carboxylic acid molecule. If such condensation is performed once, a carboxylic acid dimer is obtained, repeating the condensation reaction sequentially results in the formation of trimers, tetramers, pentamers and so on.
  • the poly fatty acid structure may comprise several types of carboxylic acids, and the properties of the poly fatty acids may be controlled by the number, type and sequence order of the carboxylic acids and hydroxyl -substituted carboxylic acids constituting the poly fatty acid structure.
  • poly fatty acid anions of the poly fatty acid metal carboxylates are preferably selected from the group consisting of anions of the formulae (V), (VII), and (X): formula (V):
  • R 7 in formula (V) is selected from a p-valent, optionally substituted hydrocarbon radical and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-,
  • X can be the same or different and is selected from -O-, or -NR 10 -, wherein R 10 is selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-,
  • R 10 may form a bond to R 7 to form a cyclic structure
  • G can be the same or different and is selected from optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1005 carbon atoms, which optionally contain one or more groups selected from
  • R 9 cannot contain a combination of a -C(O)- group and a -O- group or a combination of a — C(O)— group and a -NH- or tertiary amino group, and with the proviso that in at least one moiety of the formula (VI) R 9 has at least 2, preferably at least 6 carbon atoms, and that in the same moiety of the formula (VI) at least one R 8 has at least 6, preferably at least 8 carbon atoms, with the proviso, that at least one of R 7 and G comprises one or more carboxylate anion (-COO”) groups,
  • R 9 * is independently selected from optionally substituted branched or dendrimeric hydrocarbon radicals which have 1 to 1000 carbon atoms, optionally containing one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • T is a monovalent straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radical optionally substituted with carboxyl, hydroxyl, or halide groups with up to 36 carbon atoms, with the proviso that in at least one moiety of the formula (VI*) R 9 * is terminated by one or more groups T having at least 2, preferably at least 6 carbon atoms, and in the same moiety of the formula (VI*) at least one R 8 has at least 6, preferably at least 8 carbon atoms, and with the proviso, that at least one of R 7 and G in formula (V) comprises one or more carboxylate anion (-COO”) groups, formula (VII):
  • Y can be the same or different and is selected from optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1005 carbon atoms, which optionally contain one or more groups selected from
  • the poly fatty acid-based carboxylate anions of the poly fatty acid metal carboxylates are selected from a group consisting of polymeric fatty acid carboxylates of the type R 7 [(-C(O)-X-R 8 ) m +i-C(O)-X-R 9 ]q or R 7 [(X-C(O)-R 8 )m+i-X-C(O)-R 9 ] P , wherein X, R 7 , R 8 ,R 9 , m, p and q are as defined above for the formulas (V), (VI), (VII) and (VIII) and wherein either R 7 or at least one of R 9 , or both R 7 and at least one of R 9 bear
  • R 7 [(-C(O)-X- R 8 )m+i-C(O)-X-R 9 C(O)O'] q or COC(O)) q -i-R 7 -(C(O)-X- R 8 )m+i-C(O)-X-R 9 C(O)O‘ are preferably mono- to pentacontavalent, more preferably mono- to decavalent, even more preferably mono- to pentavalent, most preferably pentavalent, tetravalent, trivalent, divalent or monovalent anions.
  • At least one group R 9 radical is selected from linear alkyl groups and linear alkenyl groups, in particular from linear C6-C24 alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylene, nonadecyl, eicosyl, henicosyl, doicosyl, tricosyl, and tetraicosyl, or linear C6-C24 alkenyl groups such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, te
  • linear C6-C24 alkenyl groups such as hexenyl,
  • At least one R 9 represents the alkyl or alkenyl chain of a carboxylic acid or hydroxyl carboxylic acid obtained by abstraction of the carboxylate group, and wherein preferably the carboxylic acid is selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, linoleic acid, a-linolenic acid, y-linolenic acid, oleic acid, nonadecylic acid, arachidic acid, mead’s acid, arachidonic acid, heneicosanoic acid, docosanoic acid, tricosylic acid and lignoceric acid, from hydroxyl carboxylic acid
  • R 8 is independently selected from optionally hydroxyl -substituted hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, henicosylene, doicosylene, tricosylene, and tetraicosylene, or hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene,
  • R 9 is independently selected from optionally hydroxyl -substituted hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, doicosyl, tricosyl, and tetraicosyl, or hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,
  • the poly fatty acid-based carboxylate anions have the structure as outlined in WO 2021/123904 pages 13 line 34 to page 19 line 2.
  • poly fatty acid-based carboxylate anions of the divalent or trivalent metal salts are polymeric fatty acid carboxylates of the type R 1 [(-C(O)-X-R 6 )m-C(O)-X-R 7 ] x or
  • R 6 (-C(O)-X-R 6 ) m -i-C(O)-X-R 7 , wherein in the two latter types the R 7 group bears at least one anionic carboxylate group, or of the type
  • R 1 [(-C(O)-X-R 6 )m-C(O)O']x , such as
  • R 7 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, optionally containing one or more groups selected from -O-, -NH-, -C(O)-,
  • R 7 cannot contain an internal carboxy group or amide, i.e. R 7 cannot contain a combination of a -C(O)- group and a -O- group or a combination of a -C(O)- group and a -NH- or tertiary amino group.
  • carboxylate metal salts used in the primary modification method of physisorption of metal carboxylates of divalent metals or trivalent metals are magnesium stearate and aluminum stearate.
  • the physisorption of the metal carboxylates of divalent metals used may be effected in the absence or presence of a solvent.
  • one or more metal carboxylates of divalent metals are contacted with the particles selected from the group of (A) in a suspension of the particles, wherein the metal carboxylates of divalent metals may be added to the suspension, or the suspension of the particles may be prepared in a solution or suspension containing the metal carboxylates of divalent metals.
  • the load of metal carboxylate salts on the modified particles is in the range of from 0.1 to 10 weight-%, preferably from 0.5 to 5 weight-%, more preferably from 1 to 3 weight-% and most preferably from 1 to 2 weight-%.
  • TAA triethanol amine
  • quaternary ammonium compounds derived from mono-, oligo- and polysaccharides (quats), preferably of quaternized guar gums,
  • the particles are submitted to at least one primary modification selected from physisorption of quaternary compounds as mentioned under (B), and at least one secondary modification as mentioned under (C).
  • the modification of the particles by the physisorption of primary, secondary and tertiary amines is effected by contacting the particles with such an amine in the presence or absence of a solvent. By such treatment, the amine is adsorbed on the particle.
  • the amine is selected from the following groups of organic amines:
  • Preferred primary amines are C12-C18 fatty amines e.g. stearyl amines, oleyl amines; OH functionalized amines such as ethanol amine and glucosamine; preferred secondary amines are N-methyl C12-C18 fatty amines, OH functionalized amines, diethanol amine and N-methyl glucosamine, N-octyl glucosamine.
  • Preferred tertiary amines are: Cl to C18 with at least total C-number of 6.
  • C1-C18 herein refers to the number of carbon atoms of the amine substituents. In one preferred embodiment N,N dimethyl C8-C18 amines are used.
  • the C8-C18 tertiary amines are derived from amidation of C8-18 fatty acids with n,n dimethyl propylene diamine.
  • the tertiary amines are alkanol amines such as triethanol amine, ethyl diethanol amine and diethyl monoethanol amine.
  • One preferred commercially available example of tertiary amines is Schercodine-C supplied by Lubrizol, i.e. cocamidopropyl dimethylamine.
  • the amine is selected from of triethanol amine.
  • the secondary modification of the particles by an amine as described above improves the sensory properties of the particles and the formulations comprising the same, in particular the friction coefficient, the tackiness of the formulations as well as the hydrophobicity /hydrophilicity properties of the particles.
  • the modification of the particles by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides,, preferably of quaternized guar gums is effected by contacting the particles with the quaternary ammonium compounds (quats) derived from mono-, oligo- and polysaccharides in the presence or absence of a solvent as described above for the primary modification by physisorption of C4 to C29 alkyl derived quaternary ammonium compounds.
  • the saccharide derived quaternary ammonium compound is selected from cationic guar polymers, for example cationic and hydroxypropyl-modified guar polymers such as the Jaguar® guar polymers provided by Solvay, for example guar hydroxypropyltrimonium chloride.
  • the quaternary ammonium compounds used in the second modification are derived from mono-, oligo- and polysaccharides. Quaternized cellulose, quaternized crosslinked cellulose, quaternized hydroxyl ethyl celluloses and ethoxylated celluloses, quaternized guar gum, quaternized chitins, and quaternized chitosans represent a preferred group of quaternary ammonium compounds for the second modification by physisorption.
  • the quaternary ammonium compounds derived from polysaccharides are preferably based on cellulose, guar gum, chitin and chitosan, more preferably quaternized celluloses and crosslinked quatemized celluloses (hydrogels), such as quatemized cellulose according to the following structure or - H wherein the structure displays a repeating unit of the corresponding polymer, quatemized cel lulose of the following structure with n > 1, hydrogel of the following structure
  • n 1, or which displays the structure of a repeating unit of the corresponding polymer, i.e.quatemized hydroxy ethyl celluloses and ethoxylated celluloses, such as
  • guar gum based products such as guar hydroxypropyltrimonium chlorides, quaternized chitins, such as the products (1) and (2) as obtained in the reaction schemes displayed below, and quaternized chitosans, in particular N-quaternized chitosans, O-quaternized chitosans, N,O-quatemized chitosans, for example (N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride (HTCC), Q-chitosan or TMCTPCHT as obtained in the reaction schemes displayed below
  • HTCC N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride
  • TMCTPCHT TMCTPCHT
  • a particularly preferred group of quats are quaternary ammonium compounds derived from guar gums, so-called guar quats.
  • Guar polymers and “guar gums” may be used interchangeably with regard to the present invention.
  • Guar gum is a galactomannan polysaccharide extracted from guar beans composed of the sugars galactose and mannose.
  • the backbone is a linear chain of P-l,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches.
  • Cationic guar gum quats are cationic polymers obtained by quaternization of guar gum, i.e. by functionalization with residues comprising quaternary ammonium groups.
  • hydroxypropyl guar hydroxypropyltrimonium chloride is prepared by the etherification of free hydroxyl groups of the guar gum polysaccharide with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride under substitution of the chloro substituent.
  • Preferred cationic guar gums for the secondary modification (C) of the particles according to the invention are guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.
  • a further secondary modification of the particles according to the invention is modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides.
  • the aminosugars glucosamine, mannosamine and galactosamine may be used, or monosaccharides bearing primary, secondary and tertiary amino groups obtained from monosaccharides such as glucose, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose or sorbose by reaction with a compound bearing a primary, secondary or tertiary amino group.
  • Such compounds obtained from glucose, mannose, or fructose are particularly preferred.
  • the oligosaccharides and polysaccharides may either be saccharides comprising aminosugars as building blocks, such as for example chitosan, or oligo- and polysaccharides such as starch, cellulose, chitin, pectin, and guaran that have been modified to bear primary, secondary or tertiary amino groups.
  • the physisorption of the C4-C29 alkyl derived quats (primary modification) and mono-, oligo- and polysaccharide derived quats (secondary modification) can be carried out sequentially.
  • the C4-C29 alkyl derived quats and mono-, oligo- and polysaccharide derived quats are dissolved separately in water or water/organic solvent mixtures. Afterwards, the calculated quantities of the quat solutions are mixed with the particles in a sequential mode (primary modification first, secondary modification afterwards) yielding a sequential physisorption.
  • the physisorption of the C4-C29 alkyl derived quats (primary modification) and mono-, oligo- and polysaccharide derived quats (secondary modification) can be carried out simultaneously.
  • the C4-C29 alkyl derived quats and mono-, oligo- and polysaccharide derived quats are dissolved separately in water or water/organic solvent mixtures. Afterwards, the calculated quantities of both quat solutions are mixed with the particles yielding a simultaneous physisorption.
  • the particles may be modified by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent and trivalent metals, in particular of Mg stearate and Al stearate.
  • the secondary modification is performed by physisorption of fatty acid or poly fatty acid metal carboxylates of divalent and trivalent metals, in particular of Mg stearate and Al stearate.
  • a secondary modification (C) is required to be different from the primary modification or primary modifications (B) performed in order to modify the particles.
  • the acetylation of the particles (A) cannot be the only modification of the modified particles according to the invention.
  • the load of adsorbate or several adsorbates on the modified particles based on the total weight of the modified particles as defined above is in the range of 0.1 to 10 weight-%, more preferably 0.5 to 5 weight-%, even more preferably 0.7 to 3 weight-%, and most preferably 1 to 2 weight-%.
  • the modified particles according to the invention are selected from cellulose-based particles.
  • the cellulose-based particles in particular particles of pure microcrystalline cellulose, have an average particle size of 1 to 50, more preferably 2 to 40, most preferably 3 to 20 pm as determined by SEM Analysis as described above.
  • the average particle size may also be the D50 average particle size determined by Laser Diffraction Analysis as described above.
  • the cellulose-based particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, more preferably using a carboxylic acid anhydride or an acyl chloride reagent as primary modification.
  • at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, more preferably using a carboxylic acid anhydride or an acyl chloride reagent as primary modification.
  • Preferred acylation reagents for esterification of cellulose-based particles according to this embodiment are for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride, vinyl acetate, isopropenyl acetate and palmitoyl chloride.
  • the cellulose-based particles are modified by physisorption of quaternary ammonium compounds, wherein the quat compounds are preferably selected from the group consisting of poly fatty acidbased quats as described above, STEPANTEX® VK 90 as supplied by Stepan Company, i.e. ethyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate, or ester quats as described above, for example Tetranyl L 12-90
  • Methylsulfate and Evonik VARISOFT® EQ 100 i.e. bis-(isostearoyl/oleoyl isopropyl) dimonium methosulfate.
  • cellulose-based particles are modified by physisorption of quaternary ammonium compounds as primary modification, it is preferred that a secondary modification by physisorption of a quaternized guar gum is performed.
  • the load of the adsorbate or the adsorbates on the modified particle is in the range of 0.1 to 10 weight %, preferably 0.5 to 10 weight %, more preferably 0.7 to 3 weight % and most preferably 1 to 2 weight %.
  • the cellulose-based particles are modified by a primary step of physisorption of a C4-C29 alkyl derived quaternary ammonium compound, preferably being an ester quat, in particular having the structure as displayed above for the Tetranyl L12-90 quat, and it is even more preferred when the particles are additionally modified by the physisorption of a triorganoamine compound, most preferably by the physisorption of triethanol amine.
  • the cellulose particles are esterified, preferably acetylated, and modified by the additional physisorption of a C4- C29 alkyl derived quat, preferably an ester quat, more preferably of the Tetranyl type displayed above.
  • the modified particles according to the invention are selected from natural fiber particles.
  • Preferred natural fiber particles according to this embodiment in particular bamboo fiber particles, have an average particle size of 1 to 50 pm, more preferably 2 to 45 pm, most preferably 10 to 40 pm, preferably as determined by Scanning electron microscope (SEM) Analysis as described above.
  • the average particle size may also refer to the D50 value determined by Laser Diffraction Analysis as described above.
  • the natural fiber particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, as primary modification.
  • Preferred acylation reagents for esterification of cellulose-based particles are carboxylic acid anhydrides or acyl chloride reagent, for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride and palmitoyl chloride, or carboxylic acids, for example acetic acid, or carboxylic acid esters, such as vinyl acetate or isopropenyl acetate.
  • the natural fiber particles are modified by silication, wherein the silication is preferably achieved by the use of tetraacetoxy silane as silication reagent.
  • the modified particles according to the invention are selected from starch-based particles.
  • Preferred starch-based particles according to this embodiment for example potato starch and com starch particles, have an average particle size of 1 to 50, more preferably 2 to 40, most preferably 3 to 20 pm as determined by SEM Analysis.
  • the average particle size may also refer to the D50 average particle size as determined by Laser Diffraction analysis as described above.
  • the starch-based particles are modified by physisorption of quaternary ammonium compounds, wherein the quat compounds are preferably selected from the group consisting of poly fatty acid-based quats, or ester quats, for example STEPANTEX® VK 90 as supplied by Stepan company, i.e. ethyl bis[ethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate, and Evonik VARISOFT® EQ 100.
  • the quat compounds are preferably selected from the group consisting of poly fatty acid-based quats, or ester quats, for example STEPANTEX® VK 90 as supplied by Stepan company, i.e. ethyl bis[ethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate, and Evonik VARISOFT® EQ 100.
  • starch-based particles are modified by physisorption of quaternary ammonium compounds as primary modification, it is preferred that a secondary modification by physisorption of a divalent or trivalent metal carboxylate, even more preferably of a stearic acid salt, most preferably of Mg stearate or AL stearate is performed.
  • the starch- based particles are modified by a primary step of physisorption of a C4-C29 alkyl derived quaternary ammonium compound, preferably being an ester quat, in particular having the structure as displayed above for the Tetranyl L12-90 quat, and it is even more preferred when the starch-based particles are additionally modified by the physisorption of a triorganoamine compound, most preferably by the physisorption of triethanol amine.
  • the starch particles according to this embodiment are submitted to a primary modification step (B) of physisorption of a C4-C29 alkyl derived quat, preferably of an ester quat as described above, more preferably of an ester quat, and a secondary modification step (C) of physisorption of a quaternary ammonium compound derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, most preferably of guar hydroxypropyltrimonium chloride.
  • the load of the adsorbate or the adsorbates on the modified particle is in the range of 0.1 to 10 weight-% to , preferably 1 to 5 weight% , more preferably 0.5 to 3 weight-%, and most preferably 1 to 2 weight-%.
  • the modified particles according to the invention are selected from plant-based particles.
  • Preferred plant-based particles according to this embodiment are leaf powder particles, for example green tea leave powder.
  • the plant-based particles according to this embodiment have an average particle size as determined by SEM Analysis, of 1 to 50 pm , more preferably 12 to 40 pm, most preferably 3 to 20 pm.
  • the average particle size may also refer to the D50 average particle size as determined by Laser Diffraction analysis as described above.
  • the plant-based particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, as primary modification.
  • Preferred acylation reagents for esterification of the plant-based particles are carboxylic acid anhydrides or acyl chloride reagent, for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride, and palmitoyl chloride, or carboxylic acids, for example acetic acid, or carboxylic acid esters, such as vinyl acetate or isopropenyl acetate.
  • the plant-based particles are modified by silication.
  • the silication is achieved by the use of tetraacetoxy silane as silication reagent.
  • the modified particles according to the invention are plant-based particles which are selected from particles made from tea leaves.
  • the modified particles are based on green tea leaf powders.
  • the modified particles based on green tea leaf powders are submitted to a primary modification by esterification of a part or all OH groups present on the surface of the green tea leaf powder particles, most preferably by acetylation.
  • the modified particles according to the invention are cellulose-based particles which are selected from micronized cellulose particles, such as microcrystalline cellulose particles.
  • micronized cellulose particles are particles of cellulose which have been submitted to a process for the reduction of the average diameter, such as milling, grinding and sieving.
  • Microcrystalline cellulose is generally obtained from cellulose by the isolation of the crystalline regions from cellulose chain microfibrils. The isolation of microcrystalline cellulose may be effected by destroying the amorphous regions with appropriate reagents, leaving the crystalline domains termed microcrystalline cellulose.
  • the modified particles according to the invention are starch-based particles selected from natural starch particles, such as com starch particles or potato starch particles.
  • natural starch-based particles comprises particles obtained from grains and root vegetables rich in starch without further processing for extraction and/or refining the starch, or for chemical modifications.
  • Examples of such natural starch-based particles according to the invention are corn starch particles or potato starch particles obtained by drying and milling of the grains or tubers.
  • the modified particles according to the invention are natural fiber particles that are selected from bamboo fiber particles.
  • bamboo fiber particles are obtained from bamboo fiber, which is cellulose fiber extracted or fabricated from natural bamboo.
  • bamboo pole is cut into chips, the chips are dried, for example in a hot air oven, and then pulverized.
  • bamboo fiber particles having the average particle size as required by the invention are then obtained by sieving the bamboo fiber powder using a 25 um sieve three times.
  • the modified particles according to the invention are modified particles obtained by physisorption of quaternary ammonium compounds by the particles of any of the previ ous embodi m ents, and wherein preferably the weight ratio of the particles to said quaternary ammonium compounds is from 99.9 : 0. 1 to 90 : 10.
  • the load 1 of the quaternary ammonium compounds based on the total weight of the modified particles is preferably 0.1 weight-% to 10 weight-%, more preferably 0.5 weight-% to 8 weight-%, even more preferably 1.0 weight-% to 5 weight-%, further more preferably 1.5 weight-% to 4.5 weight-%, and most preferably 2.0 weight-% to 4 weight-%.
  • the weight ratio of the particles to said quaternary ammonium compounds refers to the ratio by weight, which is determined by quantitative IR analysis.
  • any type of the particles (A) may be submitted to the modification (B) of physisorption of C4 to C29 quaternary ammonium compounds.
  • any type of the particles (A) may be submitted to a primary modification (B) and in addition to the modification (C) of physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums.
  • the physisorption of quaternary ammonium compounds is achieved by contacting particles with the quaternary ammonium compounds in the presence of a solvent, more preferably the particles are dissolved or suspended in a solvent and the quaternary ammonium compounds or a solution thereof are added.
  • a solvent for the dissolution or suspension of the particles (A) preferably a solvent selected from water, alcohols, i.e. ethanol, propanol, iso propanol, C4 mono alcohols, ethylene glycols, propylene glycols, butylene glycols, ester alcohols i.e. propylene glycol mono acetic acid ester, ether alcohols i.e. propylene glycol mono butyl ether, or mixtures thereof, is used.
  • the modified particles according to the invention consist of the particles (A) and the quaternary ammonium compounds adsorbed by said particles.
  • the modified particles consist exclusively of particles (A) selected from cellulose-based particles,
  • the quaternary ammonium compound or compounds are absorbed physically to the particles (A), i.e. there are no covalent bonds linking the quaternary ammonium group-containing structures to the particles (A).
  • the weight to weight ratio (w/w) of primary articles (A) to quaternary ammonium compound absorbed thereon is in the range of 99.9 : 0.1 to 90 : 10, preferably 99.5: 0.5 to 95: 5, more preferably 99.3 : 0.7 to 92 : 3, even more preferably 99 : 1 to 98 : 2.
  • modified particles consisting of particles selected from (A) and a quaternary ammonium compound from a primary modification step (B) are further modified by a secondary modification (C) being the physisorption of a quaternary ammonium compound derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, in particular guar hydroxypropyltrimonium chloride.
  • the C4 to C29 alkyl derived quaternary ammonium compounds of the primary modification (B)contained in the modified particles according to the invention are selected from the group consisting of ester quats or poly fatty acid based quats.
  • the quats are selected from the group of Stepan VK-90, Tetranyl L12-90, Vari soft EQ 100, TEAQ, DEEDMAC, HEQ, more preferably Stepan VK-90, Tetranyl L12-90, and Vari soft EQ 100.
  • R 1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • ( ),and can be substituted by one or more groups selected from OH groups and halide groups, and F can be the same or different and is represented by the general formula (II) wherein the groups F bind to a carbon atom of R 1 , and n is independently 0 to 100,
  • R 3 , R 4 , R 5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • quaternary ammonium groups can be substituted with one or more groups selected from OH groups and halide groups, wherein R 3 , R 4 , R 5 each bind with a carbon atom to the nitrogen atom, and preferably R 3 , R 4 , R 5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R 1 , R 2 , R 3 , R 4 , R 5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV): (-X-C(O)-R 6 ) m -X-C(O)- (III) or
  • R 1 , R 3 , R 4 , R 5 do not bind through -OCH2CH2- to the nitrogen atom of the group
  • the quaternary ammonium compounds for the preparation of the modified particles according to any of the previous embodiments in the primary or secondary modification step are selected from the group consisting of the ester quats, Stepan VK-90, STEPANQUAT® Helia, Kao Tetranyl L 12, and Fentacare TEP 90, in particular Tetranyl LI 2, estolide-based quats, or guar-gum based quats, in particular Jaguar Excel.
  • Tetranyl L12 is an ester quat commercially available from the Kao company having the structure Structure
  • Methylsulfate a compound formally derived from triethanol amine by methylation of the amine group to obtain a quaternary ammonium compound, and R 1 and R 2 result from the esterification of two of the hydroxyl groups with the carboxylic acids selected from palmitic acid, stearic acid, myristic acid, oleic acid, palmitoleic acid, linoleic acid and linolenic acid, wherein oleic acid is found most frequently in the ester groups comprising R 1 and R 2 .
  • the anion of the structure may be selected from chloride, bromide, fluoride, and methosulfate, wherein methosulfate is preferred and also used in the commercially available product.
  • Stepan VK-90 is the commercially available ester quat methyl bis[ethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate, i.e. having the structure
  • STEPANQUAT®Helia is a commercially available naturally-derived cationic surfactant having the INCI name di sunfl oweroyl ethyl dimonium chloride (and) sunflower seed oil glycerides (and) lauryl lactyl lactate, and
  • Fentacare TEP 90 is an agent having the chemical nam Ethanaminium, 2-hydroxy-N,N- bis(2-hydroxyethyl)-N-methyl-, esters with Cl 6- 18 and C18-unsaturated fatty acids, methyl sulfates (salts), having the CAS-number 157905-74-3.
  • Jaguar® is a brand of cationic guar derivatives supplied by the Solvay company; the term Jaguar Excel refers to guar hydroxypropyltrimonium chloride, which may be used interchangeably according to the invention.
  • the number of repeating units in the galactomannan polysaccharide chain constituting the guar is not limited.
  • esterification agents listed above are used for the esterification of a part or all hydroxyl groups present on the particles selected from the group of (A).
  • acyl donor agents serving as esterification agents acyl halides and carboxylic acid anhydrides, are preferred due to their high reactivity.
  • the primary modification (B) by esterification for the production of the modified particles according to the previous embodiments of the invention is carried out with acetic acid, acetic acid anhydride, alkanoyl chlorides derived from C3-C28 saturated or unsaturated, linear or branched chain fatty acids which are monocarboxylic acids, preferably with an even number of carbon atoms of from 4 to 28, more preferably of from 6 to 24 carbon atoms, such as the acyl chlorides derived from hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid.
  • esterification agents derived from carboxylic acids having a higher number of carbon acids it is preferred to select esterification agents derived from carboxylic acids having a higher number of carbon acids.
  • C6-C28 acyl halides more preferably C10-C28 acyl halides, most preferably C14-C28 acyl halides are used for the esterification of the particles.
  • a primary modification (B) by esterification for the production of the modified particles according to the invention as described by any of the previous embodiments is carried out with at least one di- or higher carboxylic acid or a derivative thereof selected from a corresponding ester, acyl chloride or carboxylic acid anhydride, preferably with a dicarboxylic acid or a derivative thereof, even more preferably with a Cl -Cl 8 linear alkylene dicarboxylic acid or C2-C18 linear monounsaturated alkenylene dicarboxylic acids or derivatives thereof.
  • Esterification of the particles by di- and higher carboxylic acids enables crosslinking of the particles, which occurs when at least one acyl donor group of the agent reacts with an hydroxyl group of one particle and at least one acyl donor group of the agent reacts with an hydroxyl group of another particle.
  • the molecules of the di- and higher carboxylic acids and their derivatives bind to a single particle only at two or more sites, wherein either all available acyl donor groups bind to said particle, or one or more acyl donor groups, e.g. carboxylic acid groups, remain unreacted as terminal groups linked to the particle.
  • the ratio of di- and higher carboxylic acid compound molecules reacting with one or more hydroxyl groups of only one single particle and di- and higher carboxylic acid compound molecules reacting with one or more hydroxyl groups of two or more individual particles, resulting in the cross-linking of the particles can be controlled by the selection of the reaction conditions, in particular of the ratio of the amount of acylating agent to the amount of particles, and of the amount of solvent used in the esterification reaction.
  • the modified particles according to the invention are modified by a primary modification (B) of esterification and silication, wherein the silication is preferably carried out with alkanoyloxy silanes, such as tetraacetoxy silane or methy 1 tri acetoxy sil ane .
  • B primary modification
  • alkanoyloxy silanes such as tetraacetoxy silane or methy 1 tri acetoxy sil ane .
  • any actives well known in the context of personal care formulations can be added as well optionally.
  • buffer substances i.e. tertiary amine, such as fatty acid amino amide like SchercodineTM C amido-amine, antioxidants, or preservatives.
  • a further aspect of the present invention is the use of any of the modified particles as described above for the manufacture of personal care products, such as cosmetic compositions.
  • personal care products are products used in personal hygiene, personal grooming or for beautification
  • more specifically cosmetics are products intended to be applied to the human body for cleansing, beautifying, promoting attractiveness, or altering the appearance without affecting the body's structure or functions.
  • modified particles according to the invention has beneficial effects with regard to formulation stability, texture, spreadability, absorption, smoothness, soft- focus and brightness of various formulations.
  • the present invention further relates to personal care products comprising the modified particles as defined in any of the previous embodiments.
  • the personal care products comprising the particles according to the invention as described in one or more of the embodiments above comprise at least one additional cosmetic active ingredient.
  • a cosmetic ingredient is any compound which may be used in the formulation of products that are used to care for the face and body or to enhance or change the appearance of the face or body.
  • oils, waxes, thickeners, humectants, sunscreens, emollients, fats obtained from animals, or minerals, in particular metal oxides, organic compounds acting as colorants, fragrances or preservatives, pigments, natural products and mixtures thereof obtained by extraction of plants, processed plant parts or polymers, emulsifiers and surfactants are preferred.
  • the personal care products comprises 0.1 to 99 weight-% of the particles according to the invention.
  • the weight-% value indicates the ratio of the weight of the modified particles relative to the overall weight of the personal care product composition.
  • the personal care product comprises 0.2 to 50 weight-% of the particles, further preferred 0.5 to 30 weight-% of the modified particles, even more preferred 1.0 to 20 weight-% of the modified particles, even further preferred 2 to 15 weight-% of the modified particles, and most preferred 5 to 10 weight-% of the modified particles according to the previous embodiments.
  • the modified particles comprised by the personal care product according to the invention may fall under two or more of the embodiments as described above, unless this is impossible by mere logic. Further, the personal care product according to the invention may also comprise two or more different types of modified particles according to the invention, each displaying different features and adding different properties to the personal care product.
  • a personal care product can be any kind of product used in personal hygiene, personal grooming or for beautification.
  • the modified particles according to the invention can render personal care products more smooth, improve formulation stability, texture, spreadability, absorption, soft-focus and brightness of the formulations, or prevent undesired high tackiness.
  • the personal care products comprising the modified particles according to the previous embodiments are selected from: a. topical compositions to be applied to keratinous substrate such as skin, lip, hair, nail; b. antiperspirant and deodorant compositions in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, selffoaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories; c.
  • skin care compositions such as lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti-acne products, day-creams, night-cream, under eye-cream, face mask, face lotion, body lotion, after-shave lotions, cleaning milk, toners;
  • color cosmetic compositions such as lip-stick, pencils, lip-color, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer; e.
  • hair care compositions such as hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams;
  • sun care compositions such as sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products.
  • bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash.
  • a topical composition is defined as a composition that is applied directly to a part of the body, in this case to the keratinous substrates such as skin, lip, hair and nail.
  • a antiperspirant according to the invention is any kind of substance or composition that is put on the skin, especially under the arms, in order to prevent or to reduce sweating.
  • Such antiperspirant according to the invention may be any kind of composition comprising at least one of the volatile compounds according to the invention, however, it is preferably in the form of a spray, stick, multiphase stick, paste, powder, aerosol, cream, cream foam, lotion, self-foaming, foam-like, after-foaming or foamable emulsion, gel, roll-on preparation, foam or depilatories;
  • a deodorant according to the invention is defined as any kind of substance or composition that is applied to the body to prevent or mask body odor due to bacterial breakdown of perspiration in the armpits, groin, and feet, and according to the invention such deodorant may be any kind of composition comprising at least one of the volatile compounds according to the invention, and is preferably in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols
  • a skin care composition is defined any composition which may be applied to the skin in order to support skin integrity, enhance its appearance and relieve skin conditions.
  • such skin care composition may be any composition containing at least one of the volatile compounds according to the invention and are typically in the form of lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti -acne products, day-creams, night-cream, under eye-cream, face mask, face lotion, body lotion, after-shave lotions, cleaning milk, toners
  • a color cosmetic composition denotes any cosmetic composition, i.e. any composition intended to be placed in contact with the various external parts of the human body (epidermis, hair system, nails, lips and external genital organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them, perfuming them, changing their appearance and/or correcting body odors and/or protecting them or keeping them in good condition which is primarily directed at the aim of changing the appearance by the provision of color.
  • any cosmetic composition i.e. any composition intended to be placed in contact with the various external parts of the human body (epidermis, hair system, nails, lips and external genital organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them, perfuming them, changing their appearance and/or correcting body odors and/or protecting them or keeping them in good condition which is primarily directed at the aim of changing the appearance by the provision of color.
  • compositions according to the invention containing at least one of the volatile compounds according to the invention are in the form of lip-stick, pencils, lipcolor, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer.
  • a hair care composition is any cosmetic composition applied for care and treatment of hair, in particular on the head.
  • such hair care composition may be any composition containing at least one of the volatile compounds according to the invention and are typically in the form of hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams.
  • a sun care composition according to the invention is any kind of skin care, hair care product and nail care product directed at the protection against the effect of sunlight, wherein both the lowering of the amount of radiation interacting with the keratinous parts of the body and alteration of effects of the absorption of radiation, in particular the reduction of skin damage and skin aging, is included.
  • hair sun care composition may be any such composition containing at least one of the volatile compounds according to the invention and are typically in the form of sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products.
  • bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash are product which are applied to the skin for the removal of dirt, dust, grease and other undesired substances and particles adherent to the skin and/or hair, which are used either in a pure form, for example make up remover for the removal of make up residues, or in combination with water, for instance bathing soap or bath gel.
  • the personal care products according to the previous embodiments are aqueous compositions.
  • a personal care product comprising the modified particles of the invention is considered to be an aqueous composition when it contains at least 10 weight-% of water based on the total weight of the composition.
  • lotions, creams, emulsions are aqueous compositions.
  • water content of the personal care products as defined above is in the range of 10 to 80 weight-%, more preferably 15 to 70 weight-% of the composition, most preferably 20 to 60 weight-% based on the total weight of the composition.
  • the personal care product comprising the particles according to the embodiments according to the embodiment described above has a water content of less than 10 weight-%, preferably less than 8 weight-%, even more preferably less than 5 weight-% and most preferably less than 3 weight-% on the basis of the overall weight of the personal care product. This is the case when the personal care product is an application as a compact in powder form.
  • personal care products according to the invention comprise from 0.5 to 95 weight-% of one or more types of modified particles according to the invention as described above.
  • the composition comprises 0.1 to 90 weight-%, more preferably 2 to 80 weight-%, even more preferably 5 to 70 weight-%, and most preferably 10 to 60 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition.
  • the composition comprises 1 to 90 weight-%, more preferably 2 to 80 weight-%, even more preferably 3 to 70 weight-%, and most preferably 5 to 60 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition.
  • the composition comprises 0.01 to 99 weight-%, more preferably 0.5 to 95 weight-%, even more preferably 1 to 92 weight-%, and most preferably 2 to 90 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition.
  • said particles are selected from cellulose-based particles,
  • said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
  • metal carboxylates of divalent metals or trivalent metals preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in parti cular of Mg stearate, and
  • TAA triethanol amine
  • Modified particles according to embodiment 1 wherein the particles are selected from cellulose-based particles. Modified particles according to embodiment 1, wherein the particles are selected from natural fiber particles. Modified particles according to embodiment 1, wherein the particles are selected from starch-based particles. Modified particles according to embodiment 1, wherein the particles are selected from plant-based particles.
  • Modified particles according to the previous embodiment wherein the plant-based particles are selected from particles made from tea leaves, preferably green tea leaf powders.
  • Modified particles according to embodiments 1 or 2 wherein the cellulose-based particles are selected from micronized cellulose particles, such as microcrystalline cellulose particles.
  • Modified particles according to embodiments 1 or 4 wherein the starch particles are selected from natural starch particles, such as corn starch particles or potato starch particles.
  • Modified particles according to embodiments 1 or 3 wherein the natural fiber particles are selected from bamboo fiber particles.
  • Modified particles according to any of embodiments 1 to 10 wherein the modified particles are consisting of the particles and the quaternary ammonium compounds adsorbed by said particles.
  • Modified particles according to any of embodiments 1 to 12, wherein the particles are modified by the physisorption of C4 to C29 alkyl derived quaternary ammonium compounds selected from compounds of the general formula (I): R 1 (-F) X (I), wherein x is 1 to 50,
  • R 1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • ( ),and can be substituted by one or more groups selected from OH groups and halide groups, and
  • F can be the same or different and is represented by the general formula (II) wherein the groups F bind to a carbon atom of R 1 , and n is independently 0 to 100,
  • R 2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • R 3 , R 4 , R 5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • quaternary ammonium groups can be substituted with one or more groups selected from OH groups and halide groups, wherein R 3 , R 4 , R 5 each bind with a carbon atom to the nitrogen atom, and preferably R 3 , R 4 , R 5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R 1 , R 2 , R 3 , R 4 , R 5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV):
  • R 11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
  • R 1 , R 3 , R 4 , R 5 do not bind through -OCH2CH2- to the nitrogen atom of the group
  • Modified particles according to any of embodiments 1 to 13, wherein the quaternary ammonium compounds for the preparation of the modified particles according to any of the previous embodiments in the primary or secondary modification step are selected from the group consisting of the ester quats Stepan VK-90,
  • acetic acid acetic acid anhydride
  • alkanoyl chlorides derived from C3-C28 saturated or unsaturated linear or branched chain fatty acids which are monocarboxylic acids, more preferably with an even number of carbon atoms of from 4 to 28, even more preferably of from 6 to 24 carbon
  • Personal care products comprising the modified particles as defined in any of the previous embodiments 1 to 18, and at least one further additional cosmetic active ingredient.
  • Personal care products which are selected from: a. topical compositions to be applied to keratinous substrate such as skin, lip, hair, nail; b. antiperspirant and deodorant compositions in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, selffoaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories; c.
  • skin care compositions such as lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti-acne products, day- creams, night-cream, under eye-cream, face mask, face lotion, body lotion, aftershave lotions, cleaning milk, toners;
  • color cosmetic compositions such as lip-stick, pencils, lip-color, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer; e.
  • hair care compositions such as hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams;
  • sun care compositions such as sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products.
  • bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash.
  • the grinding protocols for natural fibers larger than covered by the invention are outlined in the experimental section. Further, chemical as well as physical modification protocols for the micronized particles are described in the example section. The example section also outlines the incorporation of these particles in personal care formulations and the determination of the overall likeabilitiy based on the sensory properties of the particles.
  • Vivapur ® CS 4 FM microcrystalline cellulose having average particle size of 4 pm as determined by laser diffraction method according to the supplier JRS
  • Vivapur ® CS 5 microcrystalline cellulose having an average particle size of 5 pm
  • Vivapur ® CS 12 microcrystalline cellulose having an average particle size of 12 pm
  • Vitacel ® CS8 Green Tea powders 0.16mol OH with M w 324.28 for cellobiose (particle size 8 pm)
  • Iodine was procured from TCI chemicals, India. All reagents were used as received.
  • Stepantex VK-90 was procured from the Stepan Company
  • Jaguar Excel was procured from Solvay
  • Tetranyl L12 was procured from Kao Industrial (Thailand) Co., Ltd.
  • Varisoft EQ100 was procured from Evonik Industries AG
  • Cellulobeads D- 10 was procured from Kobo Products, Inc.
  • Dendrocalamus stocksii species of bamboo was obtained from Institute of Wood Science and Technology (Parent Institution: Indian Council of Forestry Research and Education), Bengaluru, India. It contains cellulose (45 weight-%), hemicellulose (25 weight-%), lignin (23 weight-%), extractives (5 weight-%), ash content (2 weight-%).
  • bamboo pulverization and sieving was done at Institute of Wood Science and Technology, Bengaluru, India. The bamboo pole was converted into chips using a small scale wood chipper. The chips were dried in a hot air oven at 90 °C for 24 hours and then pulverized. The pulverized wood powder was further sieved using a gyrator sieve shaker and segregated into different particle size. The bamboo particles were further micronized using cryogrinding using Retsch Cryogrinder and sieved through 25 microns sieve.
  • Width of the particle was below 50 microns as per SEM image analysis.
  • 1% H2O2 solution mixture was prepared from 3% H2O2 peroxide solution (6.6 gram), DM water (13.2 gram) and sodium bicarbonate (0.0245 gram). This mixture was added to 1 gram of bamboo fiber while mixing and heated to 70 °C for 4 hours for bleaching. These particles are used for further modification and formulation study.
  • Quaternary ammonium samples from Example 3 A was diluted with water with active concentration of 0.0536%, i.e. 100 g of an aqueous solution of the quat containing 0.0536 g of the quat (0.0536 weight-%) were prepared. In a 100 ml two-necked bottle, 9.5 g of the diluted quat solution (with 0.053% active), and 7g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture bring the pH to 3-4. 0.1 g cellulose powder Vivapur ® CS4 FM (microcrystalline cellulose having a D50 average particle size of 4 pm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h.
  • Quaternary ammonium samples from Example 3 A was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat.
  • 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added.
  • the mixture was mixed at room temperature.
  • 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4.
  • 20 g Cellulose powder Vivapur ® CS4 FM was added very slowly to the above mixture.
  • the mixture was allowed to mix for 4-5 h.
  • the resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT).
  • the quat-modified sample was analyzed using FTIR technique to confirm the presence of ester peak resulting from the quat.
  • Quaternary ammonium samples from Example 3 A was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat.
  • 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added.
  • the mixture was mixed at room temperature.
  • 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4.
  • 20 g cellulose powder Vivapur ® CS Sensory 5 was added very slowly to the above mixture.
  • the mixture was allowed to mix for 4-5 h.
  • the resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT).
  • Quaternary ammonium samples from Example 3B was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat.
  • 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added.
  • the mixture was mixed at room temperature.
  • 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4.
  • 20 g spherical hydrophilic cellulose beads CELLULOBEAD D-10 (median diameter ⁇ 15 pm) were added very slowly to the above mixture.
  • the mixture was allowed to mix for 4-5 h.
  • the resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature.
  • Vivapur CS5 microcrystalline cellulose having an average particle size of 5 pm
  • STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat.
  • 80 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature.
  • Tri ethanol amine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h.
  • STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat.
  • a 500 ml two-necked bottle 125 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Triethanolamine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To the above mixture, 50 g of above described 0.1% quat solution in water was added to the above mixture.
  • STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat.
  • a 500 ml two-necked bottle 125 g of water were placed, and 5 gm of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Triethanolamine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To the above mixture, 50 g of above described 0.1% quat solution in water was added to the above mixture.
  • STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with in order to prepare a solution containing 0.1 weight-% of the quat.
  • 80 g of water were placed, and 5 g of com starch as described above were added. It was mixed at room temperature.
  • Triethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10- 11. The mixture was stirred at room temperature for 1 hr.
  • Sample preparation required digesting the sample in a microwave (Anton Paar, Multiwave7000 An acid vessel blank was prepared during the sample digestion. An acid mixture of 3 mL HF, 1 mL HNCh, and 1 mL HC1 were added to ⁇ 0.3 g sample in a 30 mL Teflon vessel. The Teflon vessels with acid and sample could pre-digestion and then transferred to the microwave for complete digestion. After a microwave digestion, diluted to 50 mL with deionized water (Millipore, Milli-Q). Diluted solution was analyzed by ICP-OES (Agilent 720). Mg calibration standards are prepared using certified stock solution from Inorganic ventures. Example 17 Physisorption of quaternary ammonium compounds and magnesium stearate on cellulose particles
  • STEPANTEX® VK 90 (Methyl bi s[ethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat.
  • 80 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature.
  • Tri ethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h.
  • Evonik VARISOFT® EQ 100 was diluted with water in order to prepare a solution containing 0.0573 weight-% of the quat.
  • 10 g of the aqueous quat solution (quat content 0.0573 weight-%) and 15 g of water were placed.
  • the mixture was mixed at room temperature.
  • Acetic acid was added to this mixture to bring the pH to 3-4.
  • 0.5 g Vivapur CS5 microcrystalline cellulose having an average particle size of 5 pm
  • the mixture was allowed to mix for 4-5 h.
  • the resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature.
  • the quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
  • Tetranyl L-12 (Dialkylester Ammonium Methylsulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat.
  • a solution containing 0.1 weight-% of the quat In a 2000 ml two-necked bottle, 250 g of water were placed, and 10 g of Vivapur CS 12 were added. The mjxture was mixed at room temperature. Triethanol amine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h.
  • TEA Triethanol amine
  • Tetranyl quat content that was determined by this method was 0.7 weight-%.
  • Tetranyl quat content was 2 weight-%.
  • Example 20 Acetylation of Camelia Sinensis (Green Tea) Leaf Powder Vitacel CSS (particle size 8 pm)
  • Example 23 Acetylation of bamboo fiber powder using Acetic Anhydride
  • Example 24 Acetylation of bamboo fiber powder using vinyl acetate
  • Example 29 Esterification of microcrystalline cellulose powder with succinic acid
  • 0.75g succinic acid and 0.05g p-toluene sulfonic acid were dissolved in 37.5g deionized (DI) water. This mixture was placed in a 100ml two necked bottle with nitrogen inlet and nitrogen outlet. 15g microcrystalline cellulose Vivapur CS Sensory 12 were added and mixed with the liquid phase. Finally, 4g DI water were added. The obtained slurry was heated to 110 °C for 15h while nitrogen (approximately 500ml/min) was flushed over the mixture’s surface. At the end of the esterification reaction, a powdery material was obtained.
  • DI deionized
  • the FTIR spectrum of the final product shows an ester signal at 1710-1720 cm-1 which is not present in a mixture of microcrystalline cellulose and succinic acid without reaction.
  • the FTIR spectrum is displayed in Figure 4.
  • Example 30 Esterification of microcrystalline cellulose powder with itaconic acid [0345] 0.75g itaconic acid and 0.05g p-toluene sulfonic acid were dissolved in 42.5g DI water. This mixture was placed in a 100ml two necked bottle with nitrogen inlet and nitrogen outlet. 15g microcrystalline cellulose Vivapur CS Sensory 12 were added and mixed with the liquid phase. The obtained slurry was heated to 110° C for 15h while nitrogen (approximately 500ml/min) was flushed over the mixture’s surface. At the end of the esterification reaction, a powdery material was obtained. The FTIR spectrum of the final product shows an ester signal at 1710-1720 cm-1 which is not present in a mixture of microcrystalline cellulose and itaconic acid without reaction. The FTIR spectrum is displayed in Figure 5.
  • Liquid Lip Color formulation was prepared as indicated in table 1 below with unmodified Vivapur CS12 and Modified Vivapur CS12 (Example-12). The lip colors were tested for tack after drying. The lip color formulations were applied to forearm and were allowed to dry for 30 minutes. The tack was evaluated by the panelists by briefly (1 - 2 seconds) touching the dried films on forearm. The study was performed by 2 panelists and both the panelists reported that the Example 1.1 was more tacky than Example 1.2. Table 1.
  • Powder formulations were prepared with the composition shown below in Table 2 using Modified Vivapur CS12 (Example-12) and unmodified Vivapur CS12. The ingredients were mixed in a 100 g speedmixer container and the powders were mixed for 5 minutes to obtain a uniformly mixed loose powder formulation.
  • Tribometer Tribometer. The powder was rubbed on leather (2 mg/cm 2 ) for 10 s. The friction was measured with 1 cm stainless steel diameter probe with leather (Testfabrics Inc.) attached to the flat surface. The friction was measured at 1 cm/s speed for probe reciprocating 2 cm back in forth for 10 cycles. The friction coefficient was reported as average friction coefficient for 10 cycles.

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Abstract

The invention relates to modified particles, wherein (A) said particles are selected from cellulose-based particles, natural fiber particles, starch-based particles, and plant-based particles different from natural fiber particles, said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 μm, (B) said particles being modified by one or more primary modifications selected from the group consisting of esterification, esterification and silication, physisorption of C4 to C29 alkyl derived quaternary ammonium compounds, physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and (C) said particles being optionally modified by one or more secondaiy modifications selected from the group consisting of modification by physisorption of primary, secondary or tertiary amines, preferably of triethanol amine (TEA), modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides, modification by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in particular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B), and that the acetylation of the particles (A) cannot be the only modification performed.

Description

MODIFIED NATURAL AND GREEN PARTICLES FOR COSMETIC APPLICATION
[0001] The present invention relates to modified natural and green particles which are particularly useful for personal care and cosmetic applications, the use of such particles in personal care products, and personal care products comprising the same.
[0002] For better feel and look, different types of skin care products are used and one such example is to have a line-blurring effect on the skin with enhanced sensory benefits. Currently synthetic particles are predominately used to achieve this kind of effect on the skin, in particular spherical polymer powders, for example micro-fine silicone resins, such as Tospearls. Contrary, a very limited number of particles derived from natural and sustainable sources is available for this kind of line-blurring applications. Embedded into the megatrend towards sustainable raw materials and products for PC applications (customer’s expectations and in parallel tighter regulations, such as EU’s microplastics regulation) there is a clear need for the development of natural /natural derived and finally bio degradable particles for this personal care applications.
[0003] The use of natural and natural derived particles in complex PC formulations is challenging. Typically, they tend to absorb moisture and oils, hence changing size and refractive index (the inertness towards almost all types of solvents is the key success factor of Tospearls). Further, microbes start to grow even with the use of preservatives. To guarantee a certain performance, stability and shelf life of final PC formulations natural or natural derived particles have to be modified in a way that interactions with other formulation components are reduced or at least controlled.
[0004] In order to achieve this goal a chemical and physical modification of natural materials is described. It improves the stability of the particles by reducing the water absorption. As a consequence, the antimicrobial properties are improved too. Further, these modified particles yield a line-blurring, soft-focus and anti-wrinkle, sensory and soft feel effect on the skin.
[0005] Sub-micron particles as well as particles in the micron range are used to improve the line blurring, soft focus properties on the skin. BACKGROUND ART
[0006] US 20180078484 describes microfibri Hated celluloses having a length of 0.1 to 50 microns and a diameter from 0.001 to 0.5 microns, in particular, modified microfibrillated cellulose (MFC) with fibril length from 100 nm to 50 pm, fibril diameter from 1 nm to 500 nm as an anti -wrinkle-agent. These long and thin fibers can be used without or after chemical modification for line blurring applications.
[0007] US 2002/0187173 describes cellulose for soft focus applications without sharing any information on the size, geometry or modification.
[0008] There are unmodified celluloses commercially available in the 1 to 10 micron range. They are advertised as ingredients for PC (Personal Care) formulations providing mattifying and viscosity tuning properties (J. Rettenmaier & Sohne GmbH, Rosenberg, Germany). Visible cellulose beads with particle size > 50 microns are used in personal care applications as described in US7410649B2. US 2002/0187173A1 describes the use of water-soluble cellulose as matting agent. WO 2004/024103 Al describes the use of natural polymers such as cellulose particles, covered with cross-linked poly vinyl alcohol shell as optical material for cosmetic composition. US20130243693 describes the use of silk particles for the optical effects and the soft focus of the particles. US9962565 describes the use of different particles including mica particles as the light scattering materials. US10137064B2 describes use of different fillers including inorganic fillers, polyolefin particle, cellulose and bamboo in the personal care compositions. US9446265B2 describes starch particles of particle size of 5 to 30 microns as optical materials to improve the soft-focus effect. However, to our knowledge micronized particles of cellulose and bamboo with particle size < 50 microns and their modification for personal care applications is not studied.
[0009] Further, EP 3081209 Al is directed at microfibrillated cellulose, which is modified by various means including silylation and condensation with glycidyl derivatives, whereas neither esterification nor physisorption modifications of the cellulose particles are addressed.
[0010] CN104358152 discloses cellulose particles that are modified by quaternary ammonium compounds. Therein, the modification takes place by reacting the hydroxyl groups of the cellulose fibers with the epoxy groups of a small molecule quaternary ammonium salt cation modifier or epoxy groups of a high molecular quaternary cation modifier, while modification by physisorption of such compounds is not disclosed, and both the small molecule quaternary ammonium molecules and the high molecular quaternary cation modifiers are different from the C4 to C29 alkyl derived quaternary ammonium compounds applied for the modification of particles by physisorption in the present invention.
[0011] CN109674751 B discloses the modification of small particle size starch particles by esterification by using octenyl succinic anhydride, while modifications of cellulose particles or other fibrous natural particles as defined herein are not addressed.
[0012] WO 2019/151936 Al discloses quinoa starch particles modified by esterification with octenyl succinic anhydride, while modifications of particles different from starch- based particles are not addressed.
[0013] In EP3616682 Al, cosmetic compositions comprising modified starch particles are disclosed, wherein the starch particles are modified chemically, in particular by esterification, or by the provision of a lubricant containing at least a fatty acid, in particular fatty acid metal salts, on the starch particles. The modification of other types of particles than starch particles is not addressed therein.
[0014] In CN103898630, a modified bamboo charcoal polyester fiber, which is prepared with bamboo charcoal powder, PET slices and, inter alia, chitosan, is disclosed, while there is no disclosure of a modification of the material by esterification or physisorption of quaternary ammonium compounds or metal carboxylates in the document.
[0015] CN 109486160 is directed at a green tea powder prepared by pulverizing and grinding green tea leaves, further modified with a surface modifier which is an organopoly siloxane modified by an alkyl group. Therein, there is no indication of an esterification of the tea leaf particles.
[0016] This invention is intended to replace synthetic microplastics (e.g. Tospearls) and focuses on the modification of micronized cellulose and micronized natural fibers in the size range of 1 to 50 microns. The unmodified micronized cellulose samples are either obtained from commercial sources, i.e. the VIVAPUR CS and VITACEL CS series (J. Rettenmaier & Sohne GmbH), alternatively larger natural fibers, in particular bamboo fibers, are grinded into particles in the 1 to 50 micron range for the intended soft focus application and modified afterwards. The modification of these micron sized particles is done by an either chemical or physical treatment, resulting in chemical modifications such as esterification and silication, or in the physisorption of quaternary ammonium compounds, amines or metal carboxylates.
[0017] The preferred chemical modifications are esterifications, such as acetylation, long fatty acid esterification, and parallel modification by acylation, such as acetylation, and silication. Preferred reagents for the modifications are acetic acid anhydride, fatty acid chlorides and silicate esters of carboxylic acids, such as tetraacetoxysilane Si(OAc)4.
[0018] The preferred method for the physical modification of the particles is the treatment with quaternary ammonium compounds. Here, commercial ester quats and poly fatty acid based quats as outlined in WO 2004/093834 and WO 2021/123904 are the most preferred reagents.
[0019] The modification of the particles allows to control and steer the water- and solvent absorbance properties of the particles, to control the hydrophilicity /hydrophobicity properties of the particles and to adjust the sensory properties of the particles and the properties imparted to personal care and cosmetic compositions.
SUMMARY OF THE INVENTION
[0020] The present invention relates to modified particles, wherein
(A) said particles are selected from cellulose-based particles,
- natural fiber particles, starch-based particles, and
- plant-based particles, different from natural fiber particles, said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
(B) said particles being modified by one or more primary modifications selected from the group consisting of esterification, esterification and silication,
- physisorption of C4 to C29 alkyl derived quaternary ammonium compounds, physiorption of of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and
(C) said particles being optionally modified by one or more secondary modifications selected from the group consisting of: modification by physisorption of primary, secondary or tertiary amines, preferably of triethanol amine (TEA), modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides modification by physisorption of fatty acid salts or poly fatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in particular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B), and that the acetylation of the particles (A) cannot be the only modification performed.
[0021] The invention further relates to the use of such modified particles for the manufacture of personal care products, and personal care products comprising such modified particles.
DETAILED DESCRIPTION OF THE INVENTION
[0022] In the following, the invention is described in detail.
[0023] All features and specifi c selections of features and ranges described in the following as being according to the invention may be combined without any restrictions or limitations unless a combination is not possible due to the mere requirements of logic. In the same manner, different embodiments according to the invention described below may be combined, and single features or selections of features and ranges of embodiments of the invention may be combined with other embodiments of the invention. [0024] As stated above, the invention relates to modified particles, wherein
(A) said particles are selected from cellulose-based particles,
- natural fiber particles, starch-based particles, and
- plant-based particles different from natural fiber particles, said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
(B) said particles being modified by one or more primary modifications selected from the group consisting of: esterification, esterification and silication, physisorption of C4 to C29 alkyl derived quaternary ammonium compounds (quats),
- physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and
(C) said particles being optionally modified by one or more secondary modifications selected from the group consisting of: modification by physisorption of primary, secondary and tertiary amines, preferably of triethanol amine (TEA), modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides (quats), preferably of quatemized guar gums, and modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides
- modification by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in particular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B) and that the acetylation of the particles (A) cannot be the only modification performed.
[0025] According to the invention, a modified particle is any particle selected from the group (A) that has been submitted to one or more primary modifications selected from the group (B) and optionally one or more secondary modifications selected from the group (C).
[0026] According to the invention, a particle is a portion of matter defined by its size and the type of matter it consists of.
Size and type of the particles
[0027] The scope of the invention described herein is limited to particles having an average particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20 pm, each as determined by Scanning Electron Microscope (SEM) analysis. It is also preferred that the average particle size is in the range of 2 to 50, more preferably 4 to 40, even more preferably 7 to 30, and still more preferably 10 to 20 pm, as determined by SEM Analysis. It is clarified at this point that the average particle size cited as being according to the invention refers to the size of the particles selected from the group (A) before they are submitted to any primary modification or secondary modification.
[0028] According to the invention, the particle size is preferably determined by Scanning Electron Microscopy (SEM) according to the ASTM Fl 877- 16 Standard Practice for Characterization of Particles. The average particle size is evaluated by Scanning Electron Microscopy.
[0029] In particular, Zeiss EVO-18 Scanning Electron Microscope is used, with test condition SEM: HV, 15 kV Voltage, WD: 8.5-9.5 mm, Probe Current: 100 pa, Detector: SE and BSD. Samples were prepared by smearing the powder on carbon adhesive tape and blowing air to remove excess particles. Samples were sputter coated with gold at 10mA for 90 sec. Smart SEM software from Carl Zeiss software is used for determining the particle size. The particle size range was determined by SEM and the values were reported for particles that were in the average range of 80%.
[0030] The particle size may also be determined by Laser Diffraction Spectrometry Analysis. (Reference: https://www.govinfo.gov/content/pkg/GOVPUB-C13- 765c83e30d67c74a880858fcd261b43e/pdf/GOVPUB-C13- 765c83e30d67c74a880858fcd261b43e.pdf as retrieved on November 15, 2021).
[0031] In this case, the term “average particle size” refers to having such D50 particle size distribution value.
[0032] The term "D50 particle size distribution value” means that 50% (per volume) of the particles have a particle size above or below the defined D50 value expressed in pm.
[0033] According to the invention, in this case the particles selected from the group (A) before they are submitted to any primary modification or secondary modification have a D50 value in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20 pm, and it is also preferred that the D50 value of the particles is in the range of 2 to 50, more preferably 4 to 40, even more preferably 7 to 30, and still more preferably 10 to 20 pm, as determined by Laser Diffraction Analysis.
[0034] These values of the particle size distributions used in the present invention are generally obtained by the Laser diffraction analytical technologies (see for example http://pharmazie-lehrbuch.de/kapitel/3-l.pdf). More specifically the particle size distributions are obtained according to the invention with a LS 13 320 Laser Diffraction Particle Size Analyzer of Beckmann Coulter thereby relying in particular on the corresponding “LS 13 320 Laser Diffraction Particle Size Analyzer Instructions For Use PN B05577AB (October 2011)” using in particular the complete Mie theory. These laser diffraction analytical technologies yield volume weighted distributions. Here the contribution of each particle in the distribution relates to the volume of that particle (equivalent to mass if the density is uniform), i.e. the relative contribution will be proportional to size. More specifically the particle size distribution (PSD) in accordance with the present invention is carried out with a 20 g sample of the particles (A) which is analyzed with a laser particle size analyzer Beckman Coulter LS equipped with a dry powder system. A run length of approx 13” and an obscuration of 4% is applied. The PSD is calculated from the cumulative percentage undersize size distribution using a computer program.
[0035] A summary of the laser diffraction measuring conditi ons is as follows: Particle size have been measured by laser diffraction.
Equipment:
[0036] Measuring device: e.g. LS 13 320 Laser Diffraction Particle Size Analyzer of Beckmann Coulter, Beckman Coulter International S.A. Switzerland
Sample module: Vacuum pressure dispersion system, e.g. Dry Powder System (Tornado), Beckman Coulter International S. A. Switzerland
Conditions:
[0037] Average vacuum : 25-30” H2O; Obscuration approx. 48-10%; Run length approx. 25 seconds’.
Procedure:
[0038] Introduce 20 g of the sample into the Dry Powder dispersion System.
[0039] Measurement: Apply the specified vacuum to transfer the sample and determine the cumulative volume distribution using a laser light diffraction instrument in accordance with the instruction manual. The parameters may be adjusted so that the test dispersion is representative, homogeneous and well dispersed.
[0040] Evaluation/assessment: Determine the particle sizes at the undersize values of 10%, 50% and 90% (dlO, d50, d90), and additional values in question, from the cumulative volume distribution.
[0041] More preferably, the average particle size is determined by SEM, as described above first.
[0042] Further, the particles according to the invention are selected from
- cellulose-based particles,
- natural fiber particles,
- starch-based particles, and
- plant-based particles different from natural fiber particles.
[0043] Therein, the term “cellulose-based particles” in general refers to particles comprising at least 90 percent by weight of cellulose, preferably at least 92 percent by weight, more preferably 93 or more percent by weight and most preferably 95 percent by weight.
[0044] Natural materials containing cellulose include plants, algae and bacteria. While plant-derived cellulose is usually found in a mixture with hemicellulose, lignin, pectin and other substances, bacterial cellulose is of higher purity. Due to the structure of cellulose, cellulose-based particles are characterized by the presence of hydroxyl groups on the surface of the particles, which enable further functionalization by chemical modification, for example by esterification or silication of the hydroxyl groups.
[0045] Specific examples of cellulose-based particles are commercially available microcrystalline cellulose powders produced from wood pulp or cotton linters, as obtainable from many commercial suppliers, such as Sigma Aldrich, J. Rettenmaier & Sbhne GmbH + Co. KG and many more. Specific examples are the materials of the VIVAPUR CS and VITACEL CS series (J. Rettenmaier & Sohne GmbH + Co. KG; https://www.jrs.eu/jrs_en/life-science/cosmetics/skin-care/ as retrieved on November 1 1, 2021).
[0046] In case the particle size of the commercially obtained cellulose particles exceeds the range of the average particle size as determined by SEM Analysis of 1 to 50 pm, the cellulose particles may be submitted to any procedure suitable for micronization, for example milling, grinding and/or sieving.
[0047] The term “natural fiber particles” in general refers to fibers that are produced from plants, in contrast to non-natural fibers made from materials obtained synthetically from chemical processes.
[0048] According to the invention, plant fiber particles are a preferred group of natural fiber particles, generally comprising any particles of seed fiber, leaf fiber, bast fiber, fruit fiber and stalk fiber.
[0049] Specific examples of natural fiber particles are particles of bamboo fiber, coconut fiber, cotton fiber, flax fiber, hemp fiber, jute fiber, kenaf fiber, sisal fiber and wood fiber, in particular bamboo fiber, coton fiber and hemp fiber.
[0050] As the size of natural fibers often exceeds the size of particles of the group (A) according to the invention, natural fibers may be submitted to a pretreatment for micronization such as grinding, milling and/or sieving in order to obtain natural fiber particles displaying an average particle size as determined by SEM Analysis of up to 50 pm, preferably 1 to 50 pm.
[0051] The term “starch-based particles” in general refers to particles comprising at least 90 percent by weight of starch, preferably at least 92 percent by weight, more preferably 93 or more percent by weight and most preferably 95 percent by weight. [0052] Specific examples of starch-based particles are commercially available starch powders, such as corn starch, potato starch, wheat starch, rice starch or manioc starch.
[0053] Typically, the commercially available starch powders are extracted and refined starches, wherein the term “starch powders” according to the invention also comprises unrefined starch powders.
[0054] The starch-based particles according to the invention also comprise particles obtained by drying and/or grinding plant parts which are rich in starch, such as for example potato flour, sweet potato flour, corn flour or rice flour.
[0055] In case the size of the starch-based particles exceeds the size of particles of the group (A) required according to the invention, the starch-based particles may be submitted to grinding, milling and/or sieving in order to obtain starch-based particles displaying an average particle size as determined by Scanning Electron Microscopy (SEM) Analysis of up to 50 pm, preferably 1 to 50 pm.
[0056] The particles described here are plant derived particles not included by the above definition of natural fiber particles.
[0057] According to the invention, said particles comprise in particular particles obtained by grinding or milling dry or dried plant parts, for example dried leaves, seeds, blossoms, fruits, branches, twigs and roots.
[0058] Specific examples of plant-based particles are green tea leave powder, orange peel powder, and bamboo particles obtained from processed bamboo pole.
[0059] It is noted that particles may fall under more than one of the above-cited typed of particles from which the particles according to the invention are selected. For example, many plant fiber particles may also be considered to be cellulose-based particles, as they typically have a high content of cellulose.
Primary modifications of the particles
[0060] The modified particles according to the invention are obtained when the particles as described above have been submitted to one or more primary modifications (B) selected from the group consisting of esterification, esterification and silication, physisorption of C4 to C29 alkyl derived quaternary7 ammonium compounds (quats), physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate
[0061] Therein, the term “primary modification” in general refers to the mandatory modification step or steps to which the particles are submitted, whereas the secondary modificati on steps (C) are optional and may be applied for further modification of the particles.
[0062] The terms “primary” and “secondary”, however, do not determine any order in which the steps have to be performed. Preferably, however, the primary modification step is performed prior to the secondary modification step or at the same time.
[0063] In case more than one of the above-listed primary modifications is performed, or more than one modification of one type of the above-listed modifications is performed, or one or more further secondary' modification steps (C) are performed in addition to one or more primary modifications, this may be performed in a one-step procedure if it is technically feasible, or in a sequential manner.
[0064] Preferably, when secondary modification steps are performed, the primary and secondary modification steps are performed at the same time, for example in one reaction set-up.
[0065] If several primary modification steps or several primary and modification steps are performed, this may also take place in a sequential manner, including the isolation of intermediate modified particles before one or more further modification steps are performed.
[0066] An example in which more than one modification of one type of the primary modifications (B) is performed is the case when several esterification reactions using different esterification reagents are performed by simultaneous or sequential reaction of the particles with two or more acyl donor reagents, for example with a long-chained, i.e. CIO or more, acyl chloride and a short-chained, i.e. C2-C5, acyl chloride.
[0067] According to the invention, in a step of primary’ modification of the particles by esterification, a part of or all of the free hydroxyl groups of the particles are esterified by a reaction with an acyl donor reagent.
[0068] In general, the invention comprises esterification reactions using any type of organic compound having one, two, three or more carboxylic acid groups or derivatives thereof, such as the corresponding acyl halides, anhydrides or esters. Therein, reference is made specifically to esterification using monocarboxylic acids or derivatives thereof as acyl donor reagents, and to compounds having two, three or more carboxylic acid groups or derivatives thereof, which are referred to as di- and higher carboxylic acids and derivatives thereof.
[0069] The acyl donor reagents applied in the esterification of the particles are not restricted in any way and may be selected from carboxylic acid anhydrides, acyl chlorides, carboxylic acids, carboxylic acid esters, and carboxylic acid thioesters, or carboxylic acid amides, wherein carboxylic acid anhydrides and acyl chlorides are preferred due to their high reactivity.
[0070] According to the invention, the acyl donor reagents for esterification are preferably selected from C2-C18 n-alkyl monocarboxylic acid chlorides and non-mixed C2-C18 n-alkyl monocarboxylic acid anhydrides, as well as fZ)-9-Octadecenoic acid chloride or (Zj-9-Octadecenoic acid anhydride, more preferably from C2, C4, C6, CIO, C12, C14, C16 and C18 n-alkyl monocarboxylic acid chlorides and non-mixed C2, C4, C6, CIO, C12, C14, C16 and C18 n-alkyl monocarboxylic acid anhydrides, as well as (ZJ- 9-Octadecenoic acid chloride or fZl-9-Octadecenoic acid anhydride.
[0071] Specific examples of the acyl donor reagents derived from monocarboxylic acids according to the invention are selected from C2 to C18 monocarboxylic acid anhydrides and oleic acid anhydride, preferably C6 to C18 monocarboxylic acid anhydrides and oleic acid anhydrides, more preferably C6 to C12 monocarboxylic acid anhydrides and oleic acid anhydride.
[0072] Most preferably, the acyl donor reagents derived from monocarboxylic acids are selected from acetic anhydride, hexanoyl chloride, vinyl acetate, isopropenyl acetate, acetic acid and palmitoyl chloride.
[0073] Besides the esterification by monocarboxylic acids and/or their corresponding esters, anhydrides or carboxylic acid halides, in particular acyl chlorides, used as acylating agents as described above, it is also within the scope of the invention that the term esterification specifically refers to a reaction of a part of or all of the free hydroxyl groups of the particles with a di- or higher carboxylic acid or a corresponding acyl donor reagent, for example, in the case of dicarboxylic acids, the corresponding dicarboxylic halides, e.g. diacylchlorides. [0074] Esterification using dicarboxylic acids, higher carboxylic acids or acyl donor reagents corresponding thereto enables cross-linking of the particles by an esterification reaction of a dicarboxylic acid or higher carboxylic acid with hydroxyl groups of two or more particles.
[0075] By such esterification reactions, it is possible to influence and steer the water- and solvent adsorption capability of the modified particles according to the invention.
[0076] Considered from another viewpoint, such esterification reactions may be used as a further option for tuning the hydrophilicity /hydrophobicity properties of the particles, and also allows to aggregate the particles (A) in a controlled manner, preferably in addition to further modification steps.
[0077] Preferably, the carboxylate groups of the di- and higher carboxylic acids or the analogous ester, anhydride or acyl halide groups of the corresponding acylating reagents are linked by a single bond, aliphatic or aromatic groups.
[0078] The two carboxylic groups or the analogous acyl donor functional groups of dicarboxylic acids and acyl donor reagents derived thereof are preferably linked by a single bond, Cl -Cl 8 alkylene groups, C2-C18 alkenylene groups, C4-C18 aromatic or heteroaromatic groups, even more preferably a single bond, linear unbranched Cl -Cl 8 alkylene groups, C2-C18 alkenylene groups, in particular monounsaturated C2-C18 alkenylene groups, phenylene groups, benzylene groups, xylylene groups, or naphtalenyl groups.
[0079] The group of C 1 -C 12 linear unbranched alkylene groups and C2-C 12 monounsaturated alkenylene groups is particularly preferred as linker group.
[0080] Examples of preferred dicarboxylic acids selected from the group of linear saturated dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanoic acid, preferred dicarboxylic acids selected from monounsaturated alkenylene dicarboxylic acids are maleic acid, fumaric acid, glutaconic acid, citraconic acid, mesaconic acid and itaconic acid.
[0081] Particularly preferred dicarboxylic acids are succinic acid and itaconic acid.
[0082] The corresponding acyl chlorides, mono- and diesters formed with C1-C6 alcohols, internal anhydrides and mixed anhydrides formed with C1-C6 monocarboxylic acids thereof are likewise preferred. [0083] Preferred higher carboxylic acids are citric acid, isocitric acid, aconitic acid, propane-1, 2, 3 -tricarboxylic acid, agaric acid, trimesic acid, pyromellitic acid, and compounds having three or more terminal carboxylic acid groups formally obtained by the esterification of polyols having three or more hydroxyl groups with dicarboxylic acids.
[0084] The corresponding acyl chlorides, esters formed with C1-C6 alcohols, internal anhydrides and mixed anhydrides formed with C1-C6 monocarboxylic acids thereof are likewise preferred.
[0085] According to the invention, it is also possible to combine esterification by monocarboxylic acids or derivatives thereof and di- or higher carboxylic acids or derivatives thereof, resulting in a modification of the surface by the particles by esterification in particular by the monoacyl reagents and cross-linking of the particles by the two- or higher acyl reagents at the same time.
[0086] The conditions for modification by esterification are not limited in any way, as long as the modification step results in the esterification of at least a part of the hydroxyl groups of the starting material.
[0087] Preferred conditions for modification by esterification is the suspension of the particles in a solvent and the addition of one or more acyl chlorides and/or carboxylic acid anhydrides, and of a tertiary amine, for example triethyl amine or 4- (dimethylamino)pyridine. The reaction may also be performed neat in an excess of the acylation reagent if it is a liquid at reaction temperature or may be used as a melt.
[0088] Further preferred conditions for esterification are Lewis- or Bronsted-acid catalyzed esterification, which are achieved by the conversion of the particles in the presence of a carboxylic acid or carboxylic acid ester acting as the acyl donor reagent, preferably added in excess, and a Lewis acid or Brbnsted acid acting as catalyst.
[0089] Esterification may also be achieved under mild conditions using mono-, di- or higher carboxylic acids or the corresponding carboxylic acid esters as acylation reagents in the presence of enzymes effecting esterification and transesterification reactions, in particular of hydrolases, for example lipases and esterases.
[0090] The acyl donors and the reaction conditions may be chosen by the skilled artisan in view of the technical, environmental and economical requirements of the production of the modified particles according to the invention. [0091] Preferably, in the modification by esterification the hydroxyl groups on the surface of the particles are completely or partially converted to groups of the structure OC(O)R1 , wherein R1 is independently selected from C1-C17 alkyl and alkylene groups. Specific examples of R1 are methyl, pentyl, tetradecyl. Residues derived from acetyl, butanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tetradecanoy I, hadecanoyl and octadecanoyl acid chlorides and the respective C2, C4, C6, CIO, C12, C14, C16, C18 anhydrides or from oleyl chloride or oleic acid anhydride are particularly preferred. Accordingly, further preferred examples of R1’ are methyl, propyl, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl and (Z)-heptadec-8-enyl.
[0092] According to the invention, in a step of primary modification the particles can be modified by esterification and simultaneous silication. Preferred reagents for this type of primary modification are acylated silanes, preferred acetoxysilanes, i.e tetraacetoxy si lane and methyltriacetoxysilane. When acylated silanes are used as reagent, the free hydroxyl groups of the particles are esterified by reaction with the acyl group, i.e. acetyl group in case of acetoxy silanes. In parallel, the siloxy portion of the silanes by condensation forms a silicate polymer within the particles or on their surface. The basic reaction mechanism is outlined in US2014/0127523 and M. Pries et. al., Wood Sci. Technol. 47, 2013, 685 to 699.
[0093] According to the invention, in a step of primary modification by physisorption of C4 to C29 alkyl derived quaternary ammonium compounds (quats) the particles are contacted with one or more quaternary ammonium compounds (quats) in such way that an amount of the one or more quaternary ammonium compound is adsorbed on the particles acting as adsorbent by intermol ecular forces which do not involve a significant change in the electronic orbital patterns of the species involved, i.e. without the formation of chemical bonds or ionic structures. Physisorption thus refers to the accumulation of molecules or ions on the surface of a material, creating a film of the adsorbate, i.e. the molecules or ions being accumulated on the adsorbent's surface.
[0094] The term C4 to C29 alkyl derived means that the quat structures contain CHs and CH2 based moieties of the chain length C4 to C29, as for example typically found in fatty acids and fatty alcohols as hydrophobic moieties. It is within the scope of the invention that the hydrophobic chains in the quats used for the primary modification contain more than one of these C4 to C29 alkyl derived moieties. Therein, while it is mandatory that the quats comprise at least one, more preferably two or more CH3 and CH2 based moieties of the chain length C4 to C29, the quats may also contain CH?, and CH2 based moieties consisting of or comprising shorter alkyl and alkylene groups , i.e. C1-C3 alkyl and alkylene groups, and also moieties comprising 30 or more carbon atoms.
[0095] This definition explicitly includes quats containing poly fatty acid-based estolide moieties.
[0096] Details on respective poly fatty acid quat structures are outlined in WO 2021/123904. Preferred examples for fatty acids and alcohols bearing these C4 to C29 alkyl derived moieties are the C5 to C30 fatty acids, such as hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecenoic acid, octadecanoic acid, behenic acid, oleic acid, ricinoleic acid, lesquerolic acid and 1 -ethylhexanoic acid and the respective alcohols.
[0097] According to the invention, a quaternary7 ammonium compound, herein also referred to as quat, is defined as any organic compound comprising one or more ammonium groups in which all four hydrogen atoms bonded to the nitrogen have been replaced by organyl groups, i.e. by any organic substituent groups, which are bonded to the nitrogen atom via a free valence at a carbon atom. According to this definition, quaternary ammonium compounds are the salts of quaternary ammonium cations, which are permanently charged independent of the pH of their solution.
[0098] According to the invention, a C4 to C29 alkyl derived quaternary ammonium compound is a quaternary ammonium compound comprising one or more C4 to C29 alkyl or alkylene groups.
[0099] The physisorption of the one or more quaternary ammonium compounds used may be effected in the absence or in the presence of a solvent.
[0100] Preferably, one or more quaternary ammonium compounds are contacted with the particles selected from the group of (A) in a suspension of the particles, wherein the quaternary ammonium compound may be added to the suspension, or the suspension of the particles may be prepared in a solution or suspension containing the quaternary ammonium compound.
[0101] In general, the load of the material adsorbed on the modified particles submitted to physisorption as modification treatment, for example the physisorption of quaternary ammonium compounds, can be determined by quantitative FTIR, wherein the modified particles are submitted to an extraction protocol, and the content of material in the solution of the adsorbed material can be determined by comparison to a standard solution of the respective material. Usually, the load is indicated by the weight ratio of the weight of the adsorbed material on the modified particles, for example the quaternary ammonium compound, to the total weight of the modified particles including any compounds adsorbed thereon. The load “1” may be indicated as the ratio obtained following the equation
1 = weight of the adsorbed material/total weight of the modified particles, wherein it is also common to indicate the load in weight-% on the basis of the total weight of the modified particles, which is 1*100 [%].
[0102] The load may further be determined by comparison of the weight of the particles submitted to the modification procedure by physisorption and the modified particles obtained.
[0103] In case metal carboxylates, in particular Al- and Mg carboxylates are used for the modification of the particles by physisorption, the load of said carboxylates can be determined by determination of the metal ion content of a sample by inductively coupled plasma optical emission spectrometry (ICP-OES) upon digestion of the sample.
[0104] Preferably, the load of quaternary ammonium salts on the modified particles is in the range of from 0.01 to 10 weight-%, preferably from 0.05 to 5 weight-%, more preferably from 0.1 to 2 weight-% and most preferably from 0.5 to 1 weight-%.
[0105] According to the invention, there are several preferred groups of C4 to C29 alkyl derived quaternary ammonium compounds.
[0106] The first group of these preferred quat compounds are quats containing poly fatty acid-based estolide moieties, i.e. compounds as described in WO2021/123904 Al, having the general formula
R1(~F)x (I) wherein x is 1 to 50,
R1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups
— hl- sel ected from -O-, -NH-, -C(O)~, -C(S)-, tertiary amino groups ( ),and can be substituted by one or more groups selected from OH groups and halide groups, and F can be the same or different and is represented by the general formula (II)
Figure imgf000020_0001
wherein the groups F bind to a carbon atom of R1, and n is independently 0 to 100,
R2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from O -, -NH -,
— N—
— C(O)— , — C(S)— , tertiary amino groups ( ),and can be substituted with one or more groups selected from OH groups and halide groups,
R3, R4, R5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)--, -C(S)--, tertiary amino groups
— N—
( ), quaternary ammonium groups
Figure imgf000020_0002
can be substituted with one or more groups selected from OH groups and halide groups, wherein R3, R4, R5 each bind with a carbon atom to the nitrogen atom, and preferably R3, R4, R5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R1, R2, R3, R4, R5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV ): (~X-C(O)-R6)m-X--C(O)- (III) or
(-C(O)-X-R6)m--C(O)-X- (IV), wherein m = 1 to 20,
X is O or NR11, and
R11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from
— N—
-O-, -NH-, -C(O)~, -C(S)~, tertiary amino groups ( ), and can be substituted with one or more hydroxyl and halide groups,
R6 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, with the proviso that at least one R6 has more than 6 carbon atoms, and that for x = 1
R1, R3, R4, R5 do not bind through OCH2CH2 to the nitrogen atom of the group
Figure imgf000021_0001
[0107] Accordingly, these quat compounds are characterized by containing at least one estolide group, i.e. a poly carboxylic acid group formed by the condensation of at least two hydroxy or amino carboxylic acid units.
[0108] The disclosure of WO2021/123904 Al is hereby incorporated by reference, as the above-specific group of preferred quats is described therein in detail.
[0109] Particularly preferred are the compounds characterized by having 1 to 4 quaternary ammonium groups and with at least one ester bond yielding an estolide moiety in the hydrophobic back bone.
[0110] Estolide groups containing quats having the specific structures outlined in examples 6, 7, 8, 9, 10, 11, Ha, l ib, 11c, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29b, 29c, Synthesis Example 30, Synthesis Example 30a, Synthesis Example 30b, Synthesis Example 32, Synthesis Example 32a, Synthesis Example 32b, 33, Synthesis Example 33a, Synthesis Example 33b, 34, Synthesis Example 34a, Synthesis Example 34b, 35, Synthesis Example 35a, Synthesis Example 35b, 36b, 37b of WO 2021/123904 are particularly preferred. These specific structures of the Examples of WO2021/123904 are hereby incorporated by reference as being particularly preferred C4 to C29 alkyl derived quaternary ammonium compounds for physisorption on the particles as a primary modification according to the present invention.
[0111] Further, another preferred group of C4 to C29 alkyl derived quats according to the invention are C4 to C29 alkyl derived ester quats.
[0112] Ester quats according to the invention are characterized by containing an ester group in at least one of the organyl substituents of one or more quaternary ammonium moieties of the quats.
[0113] In particular preferred are C7-C29 tetra alkyl- or alkenyl-substituted ammonium compounds containing ester moieties and having preferably Cl", Br", CFE-O-SCh" counter ions.
[0114] Further preferred are cationic saturated or unsaturated fatty acid based mono-ester and di-ester quats having 7 to 21, preferred 7 to 17 carbon atoms in each of the fatty acid- derived alkyl chains, in particular monoester compounds, such as dimethylethanolamine-, methyldiethanolamine- and triethanolamine-derived C8-C18 saturated and unsaturated mono-ester quats, for example
Figure imgf000022_0001
Figure imgf000023_0001
wherein each R is a C7-C17 saturated or unsaturated hydrocarbyl group, preferably a linear C7-C17 alkenyl or alkyl group, more preferably a C7 or C17 alkyl group, ethoxylated C8-C18 saturated and unsaturated mono-ester quats, such as cocoyl pentaethoxy methyl ammonium metho-sulfate (Rewoquat® CPEM), triethanolamine-derived C8-C18, preferably C16 - Cl 8 saturated and unsaturated di -ester quats, for example
Figure imgf000023_0002
TEAQ, wherein each R independently is a C7-C17, preferably a C7 or C17 alkyl or alkenyl group, N-methyl-diethanolamine-derived C8-C18, preferred C16-C18 saturated and unsaturated ester quats, for example
Figure imgf000023_0003
DEEDMAC wherein each R independently is a C7-C17, preferably a C7 or C17 alkyl or alkenyl group, N, N-dimethyl-3 -aminopropane- 1 ,2-diol derived C8-C18, preferred C16 - C18 saturated and unsaturated ester quats, for example
Figure imgf000024_0002
HEQ wherein each R independently is a C7-C17 alkyl or alkenyl group,
N-dimethyl -diisopropanolamine derived C16 - C18 saturated and unsaturated ester quats, for exampl e
Figure imgf000024_0001
wherein each R independently is a C7-C17 alkyl or alkenyl group, and A' is a Cl', Br‘ or CHs-O-SCh" counter ion, such as dioleoylisopropyl dimethylammonium methosulfate, dioleoylisopropyl dimethylammonium chloride, dipalmitoylisopropyl dimethylammonium methosulfate, dipalmitoylisopropyl dimethylammonium chloride, bis-(isostearoyl/oleoyl isopropyl) dimethylammonium methosulfate, bis- (isostearoyl/oleoyl isopropyl) dimethylammonium chloride.
[0115] Commercially available examples are Arquad PC SV-60 PG and Armocare VGH70 (Akzo Nobel), Varisoft EQ65 (Evonik), Vari soft EQI 00 (Evonik) and the materials of the Rewoquat® series CR 3099, W 222, W 325 PG, W 3690, W 75 H, W 90, WE 15, WE 18, WE 28, WE 38, WE HV 18 (Evonik).
[0116] Further preferred are triethanolamine-derived C8-C18, preferred C16-C18 saturated and unsaturated tri -ester quats, such as
Figure imgf000025_0001
wherein each R is a C7-C17 saturated or unsaturated hydrocarbyl group, preferably a linear C7-C17 alkenyl or alkyl group.
[0117] Also particularly preferred are symmetric or asymmetric, head group bridged or tail bridged, ester-containing di-quatemary ammonium compounds (Gemini quats), i.e. ester-containing di-quatemary compounds, containing at least one, preferred at least two C7-C29, more preferred C7-C21, even more preferred C7-C17 alkyl groups, for example head group-bridged di-quatemary compounds, such as ester brigded, preferably C4-C29 ether and ester bridges containing di-quatemary compounds, such as
Figure imgf000025_0002
R=C7-C23, or
Figure imgf000025_0003
or di-quatemary compounds containing fatty acid or fatty alcohol ester moieties, preferred C8-C29, preferred C10-C29, more preferred C10-C22, even more preferred C7-C17 fatty acid or fatty alcohol ester moieties, for example
Figure imgf000026_0001
decyl esterquat geminis with s = 2-12, preferred 3-10, more preferred 3 and 6
Figure imgf000026_0002
with n independently selected from 2-22, and m independently selected from 2-6,
Figure imgf000026_0003
Figure imgf000027_0001
[0118] Also preferred are ester-containing tri-quaternary ammonium compounds, for example tri-quaternary compounds containing at least one, preferred at least two C10- C29, more preferred three C10-C22, even more preferred C10-C18 alkyl groups, in particular derived from
- monovalent to octadecaval ent, preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from alkyl halogenides having more than one, preferred more than two carbon atoms such as alkyl chlorides, bromides, iodides, e.g. 1,3 -di chloropropane, 1,3-dichlorobutane, 1,4-di chlorobutane, dichloromonohydroxy propane isomers, 1, 2, 3-trichloro propane, 1,2-dichloro hexanediol, 1,2- dichloro hexane, or the respective bromides and iodide derivatives;
- monovalent to octadecavalent, preferably divalent to octadecavalent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetraval ent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from esters of halogenated carboxylic acids, preferred, chloro carboxylic acids, in total (ester) having more than two, preferred more than three carbon atoms such as esters of chloroacetic acid, 3- chloropropionic acid, 4-chlorobutanoic acid or the respective bromo carboxylic acids, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2, -propanediol, 1,3-propanediol, 1,3- butanediol, 1,4-butanediol, 1,2 hexanediol, 1,6-hexanediol, glycerol, diglycerol, triglycerol and higher linear or branched oligoglycerols, trimethylol propane, castor oil (ricinoleic acid triglyceride), pentaerythritol, sorbitol, poly(alkylene oxides), such as (ethylene oxide)-, (propylene oxide)- and/or (butylene oxide)-based polyethers, e.g. derived from polyethylene glycols, like diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol, or derived from polypropylene glycols, like dipropylene glycol (e.g, derived from 2,2'-oxydi-l -propanol, l,l'-oxy di -2-propanol, and 2-(2-hydroxypropoxy)-l -propanol), tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide) and (butylene oxide)-based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copoly ethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers,
- monovalent to octadecaval ent, preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from ethers or esters of epoxy compounds, in total having more than three, preferred more than four carbon atoms, preferred glycidyl ethers, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2, -propanediol, 1,3-propanediol, 1,3- butanediol, 1 ,4-butanediol, 1,2 hexanediol, 1,6-hexanediol, glycerol, diglycerol, triglycerol and higher linear or branched oligoglycerols, trimethylol propane, castor oil (ricinoleic acid triglyceride), pentaerythritol, sorbitol, poly(alkylene oxide)s, such as (ethylene oxide)-, (propylene oxide)- and/or (butylene oxide)-based polyethers, e.g. derived from polyethylene glycols, like di ethylene glycol, tri ethylene glycol, tetraethylene glycol, and pentaethylene glycol , or derived from polypropylene glycols, like di propylene glycol (e.g, derived from 2,2'-oxydi-l -propanol, l,l'-oxy di -2-propanol, and 2-(2-hydroxypropoxy)-l -propanol), tri propylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide)- and (butylene oxide)- based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copolyethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers, or preferred glycidyl esters, with acids, in particular neodecanoic acid,
- monovalent to octadecaval ent, preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent optionally OH, amino or amido substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, formed from esters of halogenated carboxylic acids, preferred chloro carboxylic acids, in total having more than two, preferably more than three carbon atoms, such as chloroacetic acid, 3 -chloropropionic acid, 4-chlorobutanoic acid or the respective bromo carboxylic acids, with ethers or esters of epoxy compounds, preferred glycidyl ethers, with alcohols, in particular methanol, ethanol, 2-propanol, 1 -butanol, t-butanol, undec- 10-en-ol, oleyl alcohol, stearyl alcohol, 1,2-propanediol, 1,3 -propanediol, 1,3 -butanediol, 1,4-butanediol, 1,2- hexanediol, 1,6-hexanediol, glycerol, di glycerol, triglycerol, and higher linear or branched oligoglycerols, trimethylol propane, castor oil (ricinoleic acid triglyceride), pentaerythritol, sorbitol, poly(alkylene oxide)s, such as (ethylene oxide)-, (propylene oxide)- and/or (butylene oxide)-based polyethers, in particular derived from polyethylene glycols, like diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol, or derived from polypropylene glycols, like dipropylene glycol (in particular, derived from 2,2'-oxydi-l -propanol, l,l'-oxy di -2-propanol, and 2-(2- hydroxypropoxy)-! -propanol), tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, derived from mixed (ethylene oxide)- and (butylene oxide)- based copolyethers, derived from mixed (propylene oxide)- and (butylene oxide)-based copoly ethers, and derived from mixed (ethylene oxide)- and (propylene oxide)- and (butylene oxide)-based copolyethers, or preferred glycidyl esters, with acids, in particular neodecanoic acid,
- monovalent to octadecavalent, preferably divalent to octadecaval ent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent, optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, formed from ethers of epoxy compounds, in total having more than seven, preferred more than eight carbon atoms, preferred glycidyl ethers, with di- to hexavalent carboxylic acids, in particular maleic acid, succinic acid, adipic acid, sebacic acid, itaconic acid, tartaric acid, trimellitic acid, fatty dimer acids, carboxyl (-C(O)OH) functionalized polyesters, in particular preferably formed by the condensation of di- to hexavalent carboxylic acids, e g. maleic acid, succinic acid, adipic acid, sebacic acid, itaconic acid, tartaric acid, trimellitic acid, fatty dimer acids, with di- to hexavalent alcohols as outlined above or alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and compounds comprising at least one glycidoxy group, such as glycidol, diglycidyl ether, glycerol digly cidyl ether, glycerol triglycidyl ether and oligomeric glycerol glycidyl ethers, butanediol diglycidylether, in particular the condensation products of succinic acid, maleic acid and tartaric acid, fatty dimer acids with glycerol diglycidyl ether, polyesters, in particular preferably derived from oligomerized hydroxycarboxylic acids, in particular oligomerized lactic acid, 12- hydroxy stearic acid, lesquerolic acid, ricinoleic acid,
- monovalent to octadecaval ent, preferably divalent to octadecavalent, more preferably divalent to hexavalent, even more preferably divalent, trivalent and tetravalent, optionally OH substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon groups, derived from esters of halogenated carboxylic acids, preferably chloro carboxylic acids, in total having more than five, preferred more than six carbon atoms such as esters of chloroacetic acid, 3 -chloropropionic acid, 4- chlorobutanoic acid or the respective bromo carboxylic acids, with OH functionalized polyesters, in particular preferably formed by the condensation of di- to hexavalent carboxylic acids, e.g. maleic acid, succinic acid, adipic acid, sebacic acid, itaconic acid, tartaric acid, trimellitic acid, fatty dimer acids, with di- to hexavalent alcohols as outlined above or alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and compounds comprising at least one glycidoxy group, such as glycidol, diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether and oligomeric glycerol glycidyl ethers, butanediol diglycidylether, in particular the condensation products of succinic acid, maleic acid and tartaric acid or fatty dimer acids with glycerol diglycidyl ether.
[0119] According to the invention, in a step of primary modification by physisorption of metal carboxylates of divalent or trivalent metals, the particles (A) are contacted with metal carboxylates of divalent and trivalent metals, in particular of Mg and Al, in such way that an amount of the one or more metal carboxylates of divalent and trivalent metals is adsorbed on the particular adsorbent by intermolecular forces which do not involve a significant change in the electronic orbital patterns of the species involved, i.e. without the formation of chemical bonds or ionic structures. The term physisorption is thus understood in the same way as described above for the physisorption of quats.
[0120] The divalent metal cations are preferably selected from the group of the alkaline earth metal cations, in particular from magnesium and calcium.
[0121] The trivalent metals cations are preferably Al cations. [0122] The carboxylate anions are preferably derived from fatty acids, more preferably from C12-C18 saturated or unsaturated unbranched aliphatic monocarboxylic acids, in particular C12, C14, C16 and C18 saturated or unsaturated unbranched aliphatic monocarboxylic acids.
[0123] Even more preferably, the carboxylate anions are derived from capric acid, lauric acid, myristic acid, palmitic acid and stearic acid , specifically from stearic acid.
[0124] A preferred example of divalent metal carboxylates is thus Mg stearate, a preferred example of trivalent metal carboxylates is thus Al stearate.
[0125] Also preferably, the carboxylate anions are derived from linear, branched or dendritic poly fatty acids as outlined in WO 2021/123904 and WO 2021/123911, which in the sense of this invention are compounds characterized by at least one ester or amide linkage, more preferably ester linkage, of a fatty acid acyl structure to the alkyl or alkenyl backbone of another fatty acid compound or fragment.
[0126] Accordingly, the poly fatty acid-derived carboxylate anions comprise estolide structures formed by carboxylic acids as described above, preferably from the fatty acid compounds typically obtainable by hydrolysis of natural oils and fats.
[0127] The estolide structure is identified by the secondary ester linkage of one fatty acyl molecule to the hydrocarbyl backbone of another fatty acid fragment. The terms “fatty acid” and “fatty acyl molecule” seem to imply that the individual residue needs to be derived from a component of a fat, which is not the case.
[0128] The term “fatty acid” herein generally refers to carboxylic acids with chain-shaped organyl groups, in particular unbranched aliphatic monocarboxylic acids. Fatty acids differ from each other by their number of carbon atoms (chain length) and, when referring to unsaturated fatty acids, the number and position of double bonds. Fatty acids may be classified as short chain fatty acids with up to 7 carbons atoms, middle chain fatty acids with 8 to 12 carbon atoms, long chain fatty acids with 13 to 21 carbon atoms, and very long chain fatty acids with more than 22 carbon atoms.
[0129] Poly fatty acids are obtained by condensation of the carboxyl group of one carboxylic acid molecule with a hydroxyl group or amino group, more preferably a hydroxyl group, of another carboxylic acid molecule. If such condensation is performed once, a carboxylic acid dimer is obtained, repeating the condensation reaction sequentially results in the formation of trimers, tetramers, pentamers and so on. Therein, the poly fatty acid structure may comprise several types of carboxylic acids, and the properties of the poly fatty acids may be controlled by the number, type and sequence order of the carboxylic acids and hydroxyl -substituted carboxylic acids constituting the poly fatty acid structure.
[0130] The poly fatty acid anions of the poly fatty acid metal carboxylates are preferably selected from the group consisting of anions of the formulae (V), (VII), and (X): formula (V):
R7(-X-C(O)-G)P (V) wherein
R7 in formula (V) is selected from a p-valent, optionally substituted hydrocarbon radical and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-,
— N —
— C(S)— , tertiary amino groups ( ), and quaternary ammonium groups, and can be optionally substituted by one or more substituent groups selected from a carboxyl group
(-COOH) group, a carboxylate anion (-COO") group and a hydroxyl (-OH) group, p > 1, more preferably 2-811,
X can be the same or different and is selected from -O-, or -NR10-, wherein R10 is selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-,
— N —
-NH-, -C(O)-, -C(S)-, tertiary amino groups ( ), or in formula (V) R10 may form a bond to R7 to form a cyclic structure,
G can be the same or different and is selected from optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1005 carbon atoms, which optionally contain one or more groups selected from
— N —
-O-, -NH-, — C(O)— , — C(S)— , and tertiary amino groups ( ) and can be optionally substituted by one or more substituent groups selected from a carboxyl (-COOH) group, a carboxylate anion (-COO") group, a hydroxyl (-OH) group and a halide (-halogen) group, with the proviso that at least one of the radicals G contains at least one moiety of the formula (VI) or (VI*): -R8(-X-C(O)-R8)m-X-C(O)-R9 (VI)
-R8(-X-C(O)-R8)m-X-C(O)-R9* (VI*) wherein X is as defined above for formula (V), m = 0 to 20, preferably 1 to 20, R8 is independently selected from a divalent optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radical which have up to 36 carbon atoms, R9 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 1000 carbon atoms, optionally containing one or more groups selected from -O-, -NH-, -C(O)-,
— N— — N—
— C(S)— , tertiary amino groups ( ), quaternary ammonium groups ( ), and which can be substituted with one or more substituent groups selected from a carboxyl (-COOH) group, carboxylate anion (-COO") group, a hydroxyl (-OH) group, and a halide (-halogen) group, wherein the radical R9 cannot contain an internal carboxy (—COO—) group or (-CON(R’)-, R’ being hydrogen or organic group) amide group, i.e. R9 cannot contain a combination of a -C(O)- group and a -O- group or a combination of a — C(O)— group and a -NH- or tertiary amino group, and with the proviso that in at least one moiety of the formula (VI) R9 has at least 2, preferably at least 6 carbon atoms, and that in the same moiety of the formula (VI) at least one R8 has at least 6, preferably at least 8 carbon atoms, with the proviso, that at least one of R7 and G comprises one or more carboxylate anion (-COO") groups,
R9* is independently selected from optionally substituted branched or dendrimeric hydrocarbon radicals which have 1 to 1000 carbon atoms, optionally containing one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N— — N—
( ), quaternary ammonium groups ( ), and which can be substituted with carboxyl, hydroxyl, or halide groups, wherein the radical R9* is terminated by two or more groups of the general structure
-X-C(O)-T wherein X is as defined above for formula (V), (VI) or (VI*), and
T is a monovalent straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radical optionally substituted with carboxyl, hydroxyl, or halide groups with up to 36 carbon atoms, with the proviso that in at least one moiety of the formula (VI*) R9* is terminated by one or more groups T having at least 2, preferably at least 6 carbon atoms, and in the same moiety of the formula (VI*) at least one R8 has at least 6, preferably at least 8 carbon atoms, and with the proviso, that at least one of R7 and G in formula (V) comprises one or more carboxylate anion (-COO") groups, formula (VII):
R7(-C(O)-X-Y)q (VII), wherein
R7 and X are as defined above for formula (V), (VI) or (VI*), q = 1 to 55, preferably 1 to 40, more preferably 2 to 4, and
Y can be the same or different and is selected from optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1005 carbon atoms, which optionally contain one or more groups selected from
— N —
-O-, -NH-, — C(O)~ , — C(S)— , and tertiary amino groups ( ), and can be substituted by one or more substituent groups selected from a carboxyl (-COOH) group, a carboxylate anion (-COO") group and a hydroxyl group, with the proviso that at least one of the radicals Y contains at least one moiety of the formula (VIII) or (VIII*):
Figure imgf000034_0001
wherein X, m, R8, and R9 in formula (VIII) are each as defined above for formula (VI), and X, m, R8, and R9* in formula (VIII*) are each as defined above for formula (VI*), and with the proviso that at least one of R7 and Y in formula (VII) comprises one or more carboxylate anion (-COO-) groups, formula (X):
R7(-C(O)-X-R8-COO')q (X) wherein X, R7, R8, and q in formula (X) are each as defined above for formula (VII) and (VIII). [0131] Even more preferably, the poly fatty acid-based carboxylate anions of the poly fatty acid metal carboxylates are selected from a group consisting of polymeric fatty acid carboxylates of the type R7[(-C(O)-X-R8)m+i-C(O)-X-R9]q or R7[(X-C(O)-R8)m+i-X-C(O)-R9]P, wherein X, R7, R8,R9, m, p and q are as defined above for the formulas (V), (VI), (VII) and (VIII) and wherein either R7 or at least one of R9, or both R7 and at least one of R9 bear one or more carboxylate groups, preferably with X = O, in particular linear polymeric fatty acid carboxylates of the type 'O-C(O)-R7(-X-C(O)-R8)m+i-X-C(O)-R9, preferably 'O-C(O)-R7-(O-C(O)-R8)m+i-O-C(O)-R9 , wherein R9 is selected from monovalent optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have up to 36 carbon atoms, branched linear polymeric fatty acid carboxylates, or branched linear polymeric fatty acid carboxylates derived from partial esters of polyfunctional carboxylic acids, in particular of the dicarboxylic acids succinic acid and maleic acid, with castor oil or lesquerella oil, dendritic polymeric fatty acid carboxylates, or of the types R7[(-C(O)-X-R8)m+i-C(O)-X-R9C(O)O‘]q or fOC(O))q-i-R7-(C(O)-X- R8)m+i-C(O)-X-R9C(O)O' , wherein X, R', R8,R9, m, p and q are as defined above for the formulas (V), (VI), (VII) and (VIII), preferably with X = O, and wherein the carboxylate anion (COO") group-comprising anion or anions of the types
R7[(-C(O)-X- R8)m+i-C(O)-X-R9C(O)O']q or COC(O))q-i-R7-(C(O)-X- R8)m+i-C(O)-X-R9C(O)O‘ are preferably mono- to pentacontavalent, more preferably mono- to decavalent, even more preferably mono- to pentavalent, most preferably pentavalent, tetravalent, trivalent, divalent or monovalent anions.
[0132] In the above-described poly fatty carboxylate anions, it is preferred when at least one group R9 radical is selected from linear alkyl groups and linear alkenyl groups, in particular from linear C6-C24 alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylene, nonadecyl, eicosyl, henicosyl, doicosyl, tricosyl, and tetraicosyl, or linear C6-C24 alkenyl groups such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, henicosenyl, doicosenyl, tricosenyl, and tetraicosenyl, wherein the groups are most preferably bonded to the adjacent X group or -C(O)- group by a terminal C-atom, and it is likewise preferred when at least one group R9 is derived from a carboxylic acid or a hydroxy carboxylic acid bearing one or more hydroxylic groups, more preferably from a carboxylic acid or monohydroxy carboxylic acid, most preferably from a C7-C25 fatty acid bearing no hydroxyl group as substituent.
[0133] It is also preferred when at least one R9 represents the alkyl or alkenyl chain of a carboxylic acid or hydroxyl carboxylic acid obtained by abstraction of the carboxylate group, and wherein preferably the carboxylic acid is selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, linoleic acid, a-linolenic acid, y-linolenic acid, oleic acid, nonadecylic acid, arachidic acid, mead’s acid, arachidonic acid, heneicosanoic acid, docosanoic acid, tricosylic acid and lignoceric acid, from hydroxyl carboxylic acid such as lesquerolic acid, ricinoleic acid, 10-hydroxy octadecanoic acid, 12-hydroxy octadecanoic acid, 14-hydroxy tetradecanoic acid, 10-hydroxy stearic acid, 12-hydroxy stearic acid, or from dihydroxy carboxylic acids, in particular 2,2’-di- hydroxymethyl propanoic acid, 9,10-dihydroxy stearic acid, or polyhydroxy carboxylic acids, in particular gluconic acid, more preferably at least one R9 radical is derived from palmitic acid, margaric acid, stearic acid, linoleic acid, a-linolenic acid, y-linolenic acid, oleic acid, nonadecylic acid, arachidic acid, 10-hydroxy stearic acid, 12-hydroxy stearic acid, ricinoleic acid, lesquerolic aci d or from 2,2’-di-hydroxymethyl propanoic acid, and most preferably at least one R9 radical is derived from oleic acid, stearic acid, lesquerolic acid and ricinoleic acid.
[0134] Further, it is preferred with regard to the poly fatty anions of the general formulas (V), (VII) and (X) when
X=O,
R8 is independently selected from optionally hydroxyl -substituted hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, henicosylene, doicosylene, tricosylene, and tetraicosylene, or hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, eicosenylene, henicosenylene, doicosenylene, tricosenylene, and tetraicosenylene, wherein the groups are most preferably bonded to the adjacent C(O) group or O group by a terminal C-atom,
R9 is independently selected from optionally hydroxyl -substituted hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, doicosyl, tricosyl, and tetraicosyl, or hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, henicosenyl, doicosenyl, tricosenyl, and tetraicosenyl, wherein the groups are most preferably bonded to the adjacent C(O) or O group by a terminal C-atom, and m is 0-10, preferably 1-10, more preferably 1, 2, 3, 4 or 5.
[0135] More preferably, the poly fatty acid-based carboxylate anions have the structure as outlined in WO 2021/123904 pages 13 line 34 to page 19 line 2.
[0136] It is thus preferred that the poly fatty acid-based carboxylate anions of the divalent or trivalent metal salts are polymeric fatty acid carboxylates of the type R1[(-C(O)-X-R6)m-C(O)-X-R7]x or
R1[(X-C(O)-R6)m-X-C(O)-R7]x, wherein either R1 or at least one of R7, or both R1 and at least one of R7 bear one or more carboxylate groups, preferably with X = O, in particular linear polymeric fatty acid carboxylates of the type ■O-C(O)-R6(-X-C(O)-R6)m-i-X-C(O)-R7, preferably 'O-C(O)-R6-(O-C(O)-R6)m-O-C(O)-R7 , i.e. derived from linear poly fatty acid structures, such as
Figure imgf000038_0001
Figure imgf000039_0001
branched linear polymeric fatty acid carboxylates, i.e. derived from branched poly fatty acid structures, such as
Figure imgf000039_0002
or with R =
Figure imgf000040_0001
Figure imgf000041_0001
or branched linear polymeric fatty acid carboxylates derived from partial esters of polyfunctional carboxylic acids, in particular of the dicarboxylic acids succinic acid and maleic acid, with castor oil or lesquerella oil, such as
Figure imgf000041_0002
and the remaining two R groups =
Figure imgf000041_0003
dendritic polymeric fatty acid carboxylates, i.e. derived from dendritic poly fatty acid structures, such as
Figure imgf000042_0001
or of the types
X-R6(-C(O)-X-R6)m-i-C(O)-X-R7 or
R6(-C(O)-X-R6)m-i-C(O)-X-R7 , wherein in the two latter types the R7 group bears at least one anionic carboxylate group, or of the type
R1[(-C(O)-X-R6)m-C(O)O']x , such as
Figure imgf000043_0001
wherein X, R1, R6, m and x are as defined above and
R7 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, optionally containing one or more groups selected from -O-, -NH-, -C(O)-,
— N— — N—
— C(S)— , tertiary amino groups ( ), quaternary ammonium groups ( ), and which can be substituted with OH groups groups or halide groups, wherein the radical R7 cannot contain an internal carboxy group or amide, i.e. R7 cannot contain a combination of a -C(O)- group and a -O- group or a combination of a -C(O)- group and a -NH- or tertiary amino group.
[0137] The most preferred carboxylate metal salts used in the primary modification method of physisorption of metal carboxylates of divalent metals or trivalent metals are magnesium stearate and aluminum stearate.
[0138] As the physisorption of the quaternary ammonium compounds, the physisorption of the metal carboxylates of divalent metals used may be effected in the absence or presence of a solvent.
[0139] Preferably, one or more metal carboxylates of divalent metals are contacted with the particles selected from the group of (A) in a suspension of the particles, wherein the metal carboxylates of divalent metals may be added to the suspension, or the suspension of the particles may be prepared in a solution or suspension containing the metal carboxylates of divalent metals.
[0140] Preferably, the load of metal carboxylate salts on the modified particles is in the range of from 0.1 to 10 weight-%, preferably from 0.5 to 5 weight-%, more preferably from 1 to 3 weight-% and most preferably from 1 to 2 weight-%.
Secondary modifications of the particles
[0141] The particles according to the invention are optionally submitted to one or more additional secondary modifications (C) selected from the group consisting of
- modification by physisorption of primary, secondary or tertiary amines, preferably of triethanol amine (TEA),
- modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides (quats), preferably of quaternized guar gums,
- modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides, and
- modification by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in particular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B).
[0142] Preferably, the particles are submitted to at least one primary modification selected from physisorption of quaternary compounds as mentioned under (B), and at least one secondary modification as mentioned under (C).
[0143] The modification of the particles by the physisorption of primary, secondary and tertiary amines is effected by contacting the particles with such an amine in the presence or absence of a solvent. By such treatment, the amine is adsorbed on the particle.
[0144] Preferably, the amine is selected from the following groups of organic amines:
[0145] Preferred primary amines are C12-C18 fatty amines e.g. stearyl amines, oleyl amines; OH functionalized amines such as ethanol amine and glucosamine; preferred secondary amines are N-methyl C12-C18 fatty amines, OH functionalized amines, diethanol amine and N-methyl glucosamine, N-octyl glucosamine. [0146] Preferred tertiary amines are: Cl to C18 with at least total C-number of 6. C1-C18 herein refers to the number of carbon atoms of the amine substituents. In one preferred embodiment N,N dimethyl C8-C18 amines are used. In another preferred embodiment the C8-C18 tertiary amines are derived from amidation of C8-18 fatty acids with n,n dimethyl propylene diamine. In another preferred embodiment, the tertiary amines are alkanol amines such as triethanol amine, ethyl diethanol amine and diethyl monoethanol amine. One preferred commercially available example of tertiary amines is Schercodine-C supplied by Lubrizol, i.e. cocamidopropyl dimethylamine.
[0147] Further preferably, the amine is selected from of triethanol amine.
[0148] The secondary modification of the particles by an amine as described above improves the sensory properties of the particles and the formulations comprising the same, in particular the friction coefficient, the tackiness of the formulations as well as the hydrophobicity /hydrophilicity properties of the particles.
[0149] In the same manner, the modification of the particles by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides,, preferably of quaternized guar gums, is effected by contacting the particles with the quaternary ammonium compounds (quats) derived from mono-, oligo- and polysaccharides in the presence or absence of a solvent as described above for the primary modification by physisorption of C4 to C29 alkyl derived quaternary ammonium compounds.
[0150] Particularly preferred, the saccharide derived quaternary ammonium compound is selected from cationic guar polymers, for example cationic and hydroxypropyl-modified guar polymers such as the Jaguar® guar polymers provided by Solvay, for example guar hydroxypropyltrimonium chloride.
[0151] The quaternary ammonium compounds used in the second modification are derived from mono-, oligo- and polysaccharides. Quaternized cellulose, quaternized crosslinked cellulose, quaternized hydroxyl ethyl celluloses and ethoxylated celluloses, quaternized guar gum, quaternized chitins, and quaternized chitosans represent a preferred group of quaternary ammonium compounds for the second modification by physisorption.
[0152] The quaternary ammonium compounds derived from polysaccharides are preferably based on cellulose, guar gum, chitin and chitosan, more preferably quaternized celluloses and crosslinked quatemized celluloses (hydrogels), such as quatemized cellulose according to the following structure
Figure imgf000046_0001
or - H wherein the structure displays a repeating unit of the corresponding polymer, quatemized cel lulose of the following structure
Figure imgf000046_0002
with n > 1, hydrogel of the following structure
Figure imgf000047_0001
with n > 1, or
Figure imgf000047_0002
which displays the structure of a repeating unit of the corresponding polymer, i.e.quatemized hydroxy ethyl celluloses and ethoxylated celluloses, such as
Figure imgf000048_0001
with n > 2, or
Figure imgf000049_0001
quatemized guar gums, for example of the formula
Figure imgf000049_0002
or as obtained in the following reaction scheme
Figure imgf000050_0001
and in particular commercially available guar gum based products such as guar hydroxypropyltrimonium chlorides, quaternized chitins, such as the products (1) and (2) as obtained in the reaction schemes displayed below,
Figure imgf000050_0002
and quaternized chitosans, in particular N-quaternized chitosans, O-quaternized chitosans, N,O-quatemized chitosans, for example (N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride (HTCC), Q-chitosan or TMCTPCHT as obtained in the reaction schemes displayed below
Figure imgf000051_0001
Figure imgf000052_0001
Chitosan (CHI) N,N,N-trimethyi chitosan free of O-methyiation
Figure imgf000052_0002
Q.N quaiemized chitosan derivative fWCTPCHT) or the structures obtained in the reactions displayed below:
Figure imgf000052_0003
Figure imgf000053_0001
[0153] A particularly preferred group of quats are quaternary ammonium compounds derived from guar gums, so-called guar quats.
[0154] The terms “guar polymers” and “guar gums” may be used interchangeably with regard to the present invention. Guar gum is a galactomannan polysaccharide extracted from guar beans composed of the sugars galactose and mannose. The backbone is a linear chain of P-l,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches. Cationic guar gum quats are cationic polymers obtained by quaternization of guar gum, i.e. by functionalization with residues comprising quaternary ammonium groups. For example, hydroxypropyl guar hydroxypropyltrimonium chloride is prepared by the etherification of free hydroxyl groups of the guar gum polysaccharide with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride under substitution of the chloro substituent.
[0155] Preferred cationic guar gums for the secondary modification (C) of the particles according to the invention are guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.
[0156] The secondary modification of the particles by cationic guar gums as described above improves the stability of the absorption of the primary modification onto the particle surface.
[0157] It is within the scope of the invention to carry out primary modifications and secondary modifications in a sequential or simultaneous mode.
[0158] A further secondary modification of the particles according to the invention is modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides. [0159] Herein, from the group of monosaccharides, the aminosugars glucosamine, mannosamine and galactosamine may be used, or monosaccharides bearing primary, secondary and tertiary amino groups obtained from monosaccharides such as glucose, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose or sorbose by reaction with a compound bearing a primary, secondary or tertiary amino group.
[0160] Particularly preferred are such compounds obtained from glucose, mannose, or fructose.
[0161] The oligosaccharides and polysaccharides may either be saccharides comprising aminosugars as building blocks, such as for example chitosan, or oligo- and polysaccharides such as starch, cellulose, chitin, pectin, and guaran that have been modified to bear primary, secondary or tertiary amino groups.
[0162] Modification by physisorption of chitosan is particularly preferred.
[0163] The physisorption of the C4-C29 alkyl derived quats (primary modification) and mono-, oligo- and polysaccharide derived quats (secondary modification) can be carried out sequentially. The C4-C29 alkyl derived quats and mono-, oligo- and polysaccharide derived quats are dissolved separately in water or water/organic solvent mixtures. Afterwards, the calculated quantities of the quat solutions are mixed with the particles in a sequential mode (primary modification first, secondary modification afterwards) yielding a sequential physisorption.
[0164] In the same manner, the physisorption of the C4-C29 alkyl derived quats (primary modification) and mono-, oligo- and polysaccharide derived quats (secondary modification) can be carried out simultaneously. The C4-C29 alkyl derived quats and mono-, oligo- and polysaccharide derived quats are dissolved separately in water or water/organic solvent mixtures. Afterwards, the calculated quantities of both quat solutions are mixed with the particles yielding a simultaneous physisorption.
[0165] As a further means of secondary modification, the particles may be modified by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent and trivalent metals, in particular of Mg stearate and Al stearate.
[0166] The methods for modifying a particle by physisorption of fatty acid salts or polyfatty acid salts, are as described above with regard to the primary modification by physisorption of metal carboxylates of divalent and trivalent metals wherein the modification may be performed in one step or sequentially.
[0167] It is preferred that the secondary modification is performed by physisorption of fatty acid or poly fatty acid metal carboxylates of divalent and trivalent metals, in particular of Mg stearate and Al stearate.
[0168] According to the invention, a secondary modification (C) is required to be different from the primary modification or primary modifications (B) performed in order to modify the particles.
[0169] Further, the acetylation of the particles (A) cannot be the only modification of the modified particles according to the invention.
[0170] According to the invention, it is generally preferred when the load of adsorbate or several adsorbates on the modified particles based on the total weight of the modified particles as defined above is in the range of 0.1 to 10 weight-%, more preferably 0.5 to 5 weight-%, even more preferably 0.7 to 3 weight-%, and most preferably 1 to 2 weight-%.
[0171] In a preferred embodiment of the invention, the modified particles according to the invention are selected from cellulose-based particles.
[0172] Therein, it is preferred when the cellulose-based particles, in particular particles of pure microcrystalline cellulose, have an average particle size of 1 to 50, more preferably 2 to 40, most preferably 3 to 20 pm as determined by SEM Analysis as described above. The average particle size may also be the D50 average particle size determined by Laser Diffraction Analysis as described above.
[0173] According to this embodiment, it is preferred that the cellulose-based particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, more preferably using a carboxylic acid anhydride or an acyl chloride reagent as primary modification.
[0174] According to the invention, the acetylation of cellulose-based particles without performing a different further primary modification (B) or a secondary modification (C) is excluded from the scope of the invention.
[0175] Preferred acylation reagents for esterification of cellulose-based particles according to this embodiment are for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride, vinyl acetate, isopropenyl acetate and palmitoyl chloride.
[0176] It is also preferred to use vinyl acetate or isopropenyl acetate as acetylation reagents according to this embodiment. [0177] It is further also preferred according to this embodiment that the cellulose-based particles are modified by physisorption of quaternary ammonium compounds, wherein the quat compounds are preferably selected from the group consisting of poly fatty acidbased quats as described above, STEPANTEX® VK 90 as supplied by Stepan Company, i.e. ethyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate, or ester quats as described above, for example Tetranyl L 12-90
Structure
Figure imgf000056_0001
Anion: Methylsulfate and Evonik VARISOFT® EQ 100, i.e. bis-(isostearoyl/oleoyl isopropyl) dimonium methosulfate.
[0178] In case the cellulose-based particles are modified by physisorption of quaternary ammonium compounds as primary modification, it is preferred that a secondary modification by physisorption of a quaternized guar gum is performed.
[0179] Likewise, in said case that physisorption of quaternary ammonium compounds is performed as primary modification, it is preferred according to this embodiment that a secondary modification by the physisorption of a divalent metal or trivalent metal carboxylate, even more preferably of a stearic acid salt, most preferably of Mg stearate is performed.
[0180] According to this embodiment, it is preferred that the load of the adsorbate or the adsorbates on the modified particle is in the range of 0.1 to 10 weight %, preferably 0.5 to 10 weight %, more preferably 0.7 to 3 weight % and most preferably 1 to 2 weight %.
[0181] According to this embodiment, it is particularly preferred that the cellulose-based particles are modified by a primary step of physisorption of a C4-C29 alkyl derived quaternary ammonium compound, preferably being an ester quat, in particular having the structure as displayed above for the Tetranyl L12-90 quat, and it is even more preferred when the particles are additionally modified by the physisorption of a triorganoamine compound, most preferably by the physisorption of triethanol amine. [0182] Further, according to this embodiment, it is preferred when the cellulose particles are esterified, preferably acetylated, and modified by the additional physisorption of a C4- C29 alkyl derived quat, preferably an ester quat, more preferably of the Tetranyl type displayed above.
[0183] Both for the modification by a C4-C29 alkyl derived quat, preferably an ester quat, more preferably of the Tetranyl L12-90 type combined with the modification by either physisorption of a tertiary amine, preferably triethanol amine, or an esterification reaction, preferably acetylation, it is particularly preferred when the cellulose particles are additionally modified by the physisorption of a quaternary ammonium compound based on mono-, oligo- or polysaccharides, in particular by the physisorption of guar hydroxypropyltrimonium chloride.
[0184] In another preferred embodiment of the invention, the modified particles according to the invention are selected from natural fiber particles.
[0185] Preferred natural fiber particles according to this embodiment, in particular bamboo fiber particles, have an average particle size of 1 to 50 pm, more preferably 2 to 45 pm, most preferably 10 to 40 pm, preferably as determined by Scanning electron microscope (SEM) Analysis as described above. The average particle size may also refer to the D50 value determined by Laser Diffraction Analysis as described above.
[0186] According to this embodiment, it is preferred that the natural fiber particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, as primary modification. Preferred acylation reagents for esterification of cellulose-based particles are carboxylic acid anhydrides or acyl chloride reagent, for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride and palmitoyl chloride, or carboxylic acids, for example acetic acid, or carboxylic acid esters, such as vinyl acetate or isopropenyl acetate.
[0187] According to this embodiment, it is also preferred that besides the esterification of a part of the hydroxy groups of the natural fiber particles, the natural fiber particles are modified by silication, wherein the silication is preferably achieved by the use of tetraacetoxy silane as silication reagent.
[0188] In a further preferred embodiment of the invention, the modified particles according to the invention are selected from starch-based particles. [0189] Preferred starch-based particles according to this embodiment, for example potato starch and com starch particles, have an average particle size of 1 to 50, more preferably 2 to 40, most preferably 3 to 20 pm as determined by SEM Analysis. The average particle size may also refer to the D50 average particle size as determined by Laser Diffraction analysis as described above.
[0190] According to this embodiment, it is preferred that the starch-based particles are modified by physisorption of quaternary ammonium compounds, wherein the quat compounds are preferably selected from the group consisting of poly fatty acid-based quats, or ester quats, for example STEPANTEX® VK 90 as supplied by Stepan company, i.e. ethyl bis[ethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate, and Evonik VARISOFT® EQ 100.
[0191] In case the starch-based particles are modified by physisorption of quaternary ammonium compounds as primary modification, it is preferred that a secondary modification by physisorption of a divalent or trivalent metal carboxylate, even more preferably of a stearic acid salt, most preferably of Mg stearate or AL stearate is performed.
[0192] According to this embodiment, it is also particularly preferred that the starch- based particles are modified by a primary step of physisorption of a C4-C29 alkyl derived quaternary ammonium compound, preferably being an ester quat, in particular having the structure as displayed above for the Tetranyl L12-90 quat, and it is even more preferred when the starch-based particles are additionally modified by the physisorption of a triorganoamine compound, most preferably by the physisorption of triethanol amine.
[0193] Also preferably, the starch particles according to this embodiment are submitted to a primary modification step (B) of physisorption of a C4-C29 alkyl derived quat, preferably of an ester quat as described above, more preferably of an ester quat, and a secondary modification step (C) of physisorption of a quaternary ammonium compound derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, most preferably of guar hydroxypropyltrimonium chloride.
[0194] According to this embodiment, it is preferred that the load of the adsorbate or the adsorbates on the modified particle is in the range of 0.1 to 10 weight-% to , preferably 1 to 5 weight% , more preferably 0.5 to 3 weight-%, and most preferably 1 to 2 weight-%.
[0195] In still a further preferred embodiment of the invention, the modified particles according to the invention are selected from plant-based particles. [0196] Preferred plant-based particles according to this embodiment are leaf powder particles, for example green tea leave powder.
[0197] Preferably, the plant-based particles according to this embodiment, have an average particle size as determined by SEM Analysis, of 1 to 50 pm , more preferably 12 to 40 pm, most preferably 3 to 20 pm. The average particle size may also refer to the D50 average particle size as determined by Laser Diffraction analysis as described above.
[0198] According to this embodiment, it is preferred that the plant-based particles are modified by esterification, preferably with at least one acyl donor reagent selected from a mono- or dicarboxylic acid or a derivative thereof, as primary modification. Preferred acylation reagents for esterification of the plant-based particles are carboxylic acid anhydrides or acyl chloride reagent, for example acetic anhydride, acetyl chloride, propionyl chloride, hexanoyl chloride, and palmitoyl chloride, or carboxylic acids, for example acetic acid, or carboxylic acid esters, such as vinyl acetate or isopropenyl acetate.
[0199] According to this embodiment, it is also preferred that besides the esterification of a part of the hydroxy groups of the plant-based particles, the plant-based particles are modified by silication. Therein, it is preferred that the silication is achieved by the use of tetraacetoxy silane as silication reagent.
[0200] In a preferred embodiment of the invention, the modified particles according to the invention are plant-based particles which are selected from particles made from tea leaves.
[0201] Preferably, the modified particles are based on green tea leaf powders.
[0202] Further preferably, the modified particles based on green tea leaf powders are submitted to a primary modification by esterification of a part or all OH groups present on the surface of the green tea leaf powder particles, most preferably by acetylation.
[0203] In a further preferred embodiment according to the invention, the modified particles according to the invention are cellulose-based particles which are selected from micronized cellulose particles, such as microcrystalline cellulose particles.
[0204] According to the invention, micronized cellulose particles are particles of cellulose which have been submitted to a process for the reduction of the average diameter, such as milling, grinding and sieving.
[0205] Microcrystalline cellulose is generally obtained from cellulose by the isolation of the crystalline regions from cellulose chain microfibrils. The isolation of microcrystalline cellulose may be effected by destroying the amorphous regions with appropriate reagents, leaving the crystalline domains termed microcrystalline cellulose.
[0206] In another preferred embodiment of the invention, the modified particles according to the invention are starch-based particles selected from natural starch particles, such as com starch particles or potato starch particles.
[0207] The term “natural starch-based particles” comprises particles obtained from grains and root vegetables rich in starch without further processing for extraction and/or refining the starch, or for chemical modifications.
[0208] Examples of such natural starch-based particles according to the invention are corn starch particles or potato starch particles obtained by drying and milling of the grains or tubers.
[0209] In a further preferred embodiment according of the invention, the modified particles according to the invention are natural fiber particles that are selected from bamboo fiber particles.
[0210] Bamboo fiber particles are obtained from bamboo fiber, which is cellulose fiber extracted or fabricated from natural bamboo.
[0211] Preferably, bamboo pole is cut into chips, the chips are dried, for example in a hot air oven, and then pulverized. Bamboo fiber particles having the average particle size as required by the invention are then obtained by sieving the bamboo fiber powder using a 25 um sieve three times.
[0212] In a preferred embodiment of the invention, the modified particles according to the invention are modified particles obtained by physisorption of quaternary ammonium compounds by the particles of any of the previ ous embodi m ents, and wherein preferably the weight ratio of the particles to said quaternary ammonium compounds is from 99.9 : 0. 1 to 90 : 10.
[0213] As defined above, in such embodiment the load 1 of the quaternary ammonium compounds based on the total weight of the modified particles is preferably 0.1 weight-% to 10 weight-%, more preferably 0.5 weight-% to 8 weight-%, even more preferably 1.0 weight-% to 5 weight-%, further more preferably 1.5 weight-% to 4.5 weight-%, and most preferably 2.0 weight-% to 4 weight-%.
[0214] The weight ratio of the particles to said quaternary ammonium compounds, which is preferably in the range from 99.9 : 0. 1 to 90 : 10, refers to the ratio by weight, which is determined by quantitative IR analysis. [0215] According to this embodiment, any type of the particles (A) may be submitted to the modification (B) of physisorption of C4 to C29 quaternary ammonium compounds.
[0216] Likewise, according to this embodiment, any type of the particles (A) may be submitted to a primary modification (B) and in addition to the modification (C) of physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums.
[0217] Preferably, the physisorption of quaternary ammonium compounds is achieved by contacting particles with the quaternary ammonium compounds in the presence of a solvent, more preferably the particles are dissolved or suspended in a solvent and the quaternary ammonium compounds or a solution thereof are added.
[0218] As a solvent for the dissolution or suspension of the particles (A), preferably a solvent selected from water, alcohols, i.e. ethanol, propanol, iso propanol, C4 mono alcohols, ethylene glycols, propylene glycols, butylene glycols, ester alcohols i.e. propylene glycol mono acetic acid ester, ether alcohols i.e. propylene glycol mono butyl ether, or mixtures thereof, is used.
[0219] In another preferred embodiment of the invention, the modified particles according to the invention consist of the particles (A) and the quaternary ammonium compounds adsorbed by said particles.
[0220] According to the this embodiment, the modified particles consist exclusively of particles (A) selected from cellulose-based particles,
- natural fiber particles starch-based particles, and
- plant-based particles, different from natural fiber particles, and the quaternary ammonium compounds absorbed thereon.
[0221] The quaternary ammonium compound or compounds are absorbed physically to the particles (A), i.e. there are no covalent bonds linking the quaternary ammonium group-containing structures to the particles (A).
[0222] As stated above with regard to the previous embodiment, the weight to weight ratio (w/w) of primary articles (A) to quaternary ammonium compound absorbed thereon is in the range of 99.9 : 0.1 to 90 : 10, preferably 99.5: 0.5 to 95: 5, more preferably 99.3 : 0.7 to 92 : 3, even more preferably 99 : 1 to 98 : 2. [0223] It is also preferred according to this embodiment when the modified particles consisting of particles selected from (A) and a quaternary ammonium compound from a primary modification step (B) are further modified by a secondary modification (C) being the physisorption of a quaternary ammonium compound derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, in particular guar hydroxypropyltrimonium chloride.
[0224] In a particularly preferred embodiment of the invention, the C4 to C29 alkyl derived quaternary ammonium compounds of the primary modification (B)contained in the modified particles according to the invention are selected from the group consisting of ester quats or poly fatty acid based quats.
[0225] From the group of ester quats, it is preferred when the quats are selected from the group of Stepan VK-90, Tetranyl L12-90, Vari soft EQ 100, TEAQ, DEEDMAC, HEQ, more preferably Stepan VK-90, Tetranyl L12-90, and Vari soft EQ 100.
[0226] It is most preferred when the particles (A) are selected from starch particles or cellulose particles, in particular particles of microcrystalline cellulose or spherical cellulose beads, and the ester quat for modification is selected from Stepan VK-90. From the group of poly fatty acid quats, it is preferred when the quats are selected from the group of poly fatty acid quats having the structure
Figure imgf000062_0001
with n = 0 to 4, wherein preferably n = 1 or 4. It is most preferred when the particles (A) are selected from microcrystalline cellulose particles having an average particle size below 10 pm or spherical cellulose beads having an average particle size below 20 pm, and the poly fatty acid quats for modification are selected from poly fatty acid quats having the structure
Figure imgf000063_0001
with n = 1 or 4.
[0227] In a further preferred embodiment of the invention, the particles according to the invention are modified by the physisorption of C4 to C29 alkyl derived quaternary ammonium compounds selected from compounds of the general formula (I): R1(-F)x (I), wherein x is 1 to 50,
R1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ),and can be substituted by one or more groups selected from OH groups and halide groups, and F can be the same or different and is represented by the general formula (II)
Figure imgf000064_0001
wherein the groups F bind to a carbon atom of R1, and n is independently 0 to 100,
R2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), and can be substituted with one or more groups selected from OH groups and halide groups,
R3, R4, R5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), quaternary ammonium groups
Figure imgf000064_0002
can be substituted with one or more groups selected from OH groups and halide groups, wherein R3, R4, R5 each bind with a carbon atom to the nitrogen atom, and preferably R3, R4, R5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R1, R2, R3, R4, R5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV): (-X-C(O)-R6)m-X-C(O)- (III) or
(-C(O)-X-R6)m-C(O)-X- (IV), wherein m = 1 to 20,
X is O or NR11, R11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), and can be substituted with one or more hydroxyl and halide groups,
R6 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, with the proviso that at least one R6 has more than 6 carbon atoms, and that for x = 1
R1, R3, R4, R5 do not bind through -OCH2CH2- to the nitrogen atom of the group
Figure imgf000065_0001
[0228] In another preferred embodiment according to the invention, the quaternary ammonium compounds for the preparation of the modified particles according to any of the previous embodiments in the primary or secondary modification step are selected from the group consisting of the ester quats, Stepan VK-90, STEPANQUAT® Helia, Kao Tetranyl L 12, and Fentacare TEP 90, in particular Tetranyl LI 2, estolide-based quats, or guar-gum based quats, in particular Jaguar Excel.
Tetranyl L12 is an ester quat commercially available from the Kao company having the structure Structure
Figure imgf000066_0001
Anion: Methylsulfate a compound formally derived from triethanol amine by methylation of the amine group to obtain a quaternary ammonium compound, and R1 and R2 result from the esterification of two of the hydroxyl groups with the carboxylic acids selected from palmitic acid, stearic acid, myristic acid, oleic acid, palmitoleic acid, linoleic acid and linolenic acid, wherein oleic acid is found most frequently in the ester groups comprising R1 and R2.
[0229] The anion of the structure may be selected from chloride, bromide, fluoride, and methosulfate, wherein methosulfate is preferred and also used in the commercially available product.
[0230] Stepan VK-90 is the commercially available ester quat methyl bis[ethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate, i.e. having the structure
Figure imgf000066_0002
STEPANQUAT®Helia is a commercially available naturally-derived cationic surfactant having the INCI name di sunfl oweroyl ethyl dimonium chloride (and) sunflower seed oil glycerides (and) lauryl lactyl lactate, and
Fentacare TEP 90 is an agent having the chemical nam Ethanaminium, 2-hydroxy-N,N- bis(2-hydroxyethyl)-N-methyl-, esters with Cl 6- 18 and C18-unsaturated fatty acids, methyl sulfates (salts), having the CAS-number 157905-74-3.
Jaguar® is a brand of cationic guar derivatives supplied by the Solvay company; the term Jaguar Excel refers to guar hydroxypropyltrimonium chloride, which may be used interchangeably according to the invention. [0231] According to the invention, the number of repeating units in the galactomannan polysaccharide chain constituting the guar is not limited.
[0232] In a further preferred embodiment of the invention, a primary modification (B) of the modified particles according to the invention is an esterification step carried out with one or more esterification agents selected from carboxylic acids, carboxylic acid anhydrides, acyl halides and alkenyl acetates.
[0233] The esterification agents listed above are used for the esterification of a part or all hydroxyl groups present on the particles selected from the group of (A).
[0234] The conditions used for esterification of substrates applying the esterification agents of this embodiment are known to the skilled person, for example from the compendium “Esterification: Methods, Reactions, and Applications”, Second Edition 2009, Wiley-VCH Verlag GmbH & Co. KGaA, by J. Otera and J. Nishikido, and are applied to the particles (A).
[0235] As acyl donor agents serving as esterification agents, acyl halides and carboxylic acid anhydrides, are preferred due to their high reactivity.
[0236] In a particularly preferred embodiment according to the invention, the primary modification (B) by esterification for the production of the modified particles according to the previous embodiments of the invention is carried out with acetic acid, acetic acid anhydride, alkanoyl chlorides derived from C3-C28 saturated or unsaturated, linear or branched chain fatty acids which are monocarboxylic acids, preferably with an even number of carbon atoms of from 4 to 28, more preferably of from 6 to 24 carbon atoms, such as the acyl chlorides derived from hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid.
[0237] In order to increase the hydrophobic properties of the modified particles, it is preferred to select esterification agents derived from carboxylic acids having a higher number of carbon acids.
[0238] Accordingly, it is preferred that C6-C28 acyl halides, more preferably C10-C28 acyl halides, most preferably C14-C28 acyl halides are used for the esterification of the particles.
[0239] In another preferred embodiment according to the invention, a primary modification (B) by esterification for the production of the modified particles according to the invention as described by any of the previous embodiments is carried out with at least one di- or higher carboxylic acid or a derivative thereof selected from a corresponding ester, acyl chloride or carboxylic acid anhydride, preferably with a dicarboxylic acid or a derivative thereof, even more preferably with a Cl -Cl 8 linear alkylene dicarboxylic acid or C2-C18 linear monounsaturated alkenylene dicarboxylic acids or derivatives thereof.
[0240] Esterification of the particles by di- and higher carboxylic acids enables crosslinking of the particles, which occurs when at least one acyl donor group of the agent reacts with an hydroxyl group of one particle and at least one acyl donor group of the agent reacts with an hydroxyl group of another particle.
[0241] It is also possible that the molecules of the di- and higher carboxylic acids and their derivatives bind to a single particle only at two or more sites, wherein either all available acyl donor groups bind to said particle, or one or more acyl donor groups, e.g. carboxylic acid groups, remain unreacted as terminal groups linked to the particle.
[0242] Accordingly, the use of di- and higher carboxylic acids and their derivatives allows to influence and steer the water- and solvent adsorption capability of the particles in different ways.
[0243] The ratio of di- and higher carboxylic acid compound molecules reacting with one or more hydroxyl groups of only one single particle and di- and higher carboxylic acid compound molecules reacting with one or more hydroxyl groups of two or more individual particles, resulting in the cross-linking of the particles, can be controlled by the selection of the reaction conditions, in particular of the ratio of the amount of acylating agent to the amount of particles, and of the amount of solvent used in the esterification reaction.
[0244] In another preferred embodiment, the modified particles according to the invention are modified by a primary modification (B) of esterification and silication, wherein the silication is preferably carried out with alkanoyloxy silanes, such as tetraacetoxy silane or methy 1 tri acetoxy sil ane .
[0245] Therein, it is particularly preferred when the reagent tetraacetoxysilane isused for silication.
[0246] In general, according to the invention in addition to substances used for primary and secondary modification as described above, any actives well known in the context of personal care formulations, can be added as well optionally. Such examples are buffer substances i.e. tertiary amine, such as fatty acid amino amide like Schercodine™ C amido-amine, antioxidants, or preservatives.
[0247] A further aspect of the present invention is the use of any of the modified particles as described above for the manufacture of personal care products, such as cosmetic compositions.
[0248] According to the invention, personal care products are products used in personal hygiene, personal grooming or for beautification, and more specifically cosmetics are products intended to be applied to the human body for cleansing, beautifying, promoting attractiveness, or altering the appearance without affecting the body's structure or functions.
[0249] The use of the modified particles according to the invention has beneficial effects with regard to formulation stability, texture, spreadability, absorption, smoothness, soft- focus and brightness of various formulations.
[0250] The present invention further relates to personal care products comprising the modified particles as defined in any of the previous embodiments.
[0251] The personal care products comprising the particles according to the invention as described in one or more of the embodiments above comprise at least one additional cosmetic active ingredient.
[0252] According to the invention, a cosmetic ingredient is any compound which may be used in the formulation of products that are used to care for the face and body or to enhance or change the appearance of the face or body.
[0253] Therein, oils, waxes, thickeners, humectants, sunscreens, emollients, fats obtained from animals, or minerals, in particular metal oxides, organic compounds acting as colorants, fragrances or preservatives, pigments, natural products and mixtures thereof obtained by extraction of plants, processed plant parts or polymers, emulsifiers and surfactants are preferred.
[0254] According to this embodiment, it is preferred that the personal care products comprises 0.1 to 99 weight-% of the particles according to the invention. The weight-% value indicates the ratio of the weight of the modified particles relative to the overall weight of the personal care product composition.
[0255] More preferably the personal care product comprises 0.2 to 50 weight-% of the particles, further preferred 0.5 to 30 weight-% of the modified particles, even more preferred 1.0 to 20 weight-% of the modified particles, even further preferred 2 to 15 weight-% of the modified particles, and most preferred 5 to 10 weight-% of the modified particles according to the previous embodiments.
[0256] According to the embodiment, the modified particles comprised by the personal care product according to the invention may fall under two or more of the embodiments as described above, unless this is impossible by mere logic. Further, the personal care product according to the invention may also comprise two or more different types of modified particles according to the invention, each displaying different features and adding different properties to the personal care product.
[0257] According to the invention, a personal care product can be any kind of product used in personal hygiene, personal grooming or for beautification.
[0258] The modified particles according to the invention can render personal care products more smooth, improve formulation stability, texture, spreadability, absorption, soft-focus and brightness of the formulations, or prevent undesired high tackiness.
[0259] In a preferred embodiment of the invention, the personal care products comprising the modified particles according to the previous embodiments are selected from: a. topical compositions to be applied to keratinous substrate such as skin, lip, hair, nail; b. antiperspirant and deodorant compositions in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, selffoaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories; c. skin care compositions such as lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti-acne products, day-creams, night-cream, under eye-cream, face mask, face lotion, body lotion, after-shave lotions, cleaning milk, toners; d. color cosmetic compositions such as lip-stick, pencils, lip-color, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer; e. hair care compositions such as hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams; f. sun care compositions such as sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products. g. bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash.
[0260] Therein, a topical composition is defined as a composition that is applied directly to a part of the body, in this case to the keratinous substrates such as skin, lip, hair and nail.
[0261] A antiperspirant according to the invention is any kind of substance or composition that is put on the skin, especially under the arms, in order to prevent or to reduce sweating. Such antiperspirant according to the invention may be any kind of composition comprising at least one of the volatile compounds according to the invention, however, it is preferably in the form of a spray, stick, multiphase stick, paste, powder, aerosol, cream, cream foam, lotion, self-foaming, foam-like, after-foaming or foamable emulsion, gel, roll-on preparation, foam or depilatories; a deodorant according to the invention is defined as any kind of substance or composition that is applied to the body to prevent or mask body odor due to bacterial breakdown of perspiration in the armpits, groin, and feet, and according to the invention such deodorant may be any kind of composition comprising at least one of the volatile compounds according to the invention, and is preferably in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, self-foaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories. The typical formulations for such products are known to the person skilled in the art.
[0262] According to the invention, a skin care composition is defined any composition which may be applied to the skin in order to support skin integrity, enhance its appearance and relieve skin conditions. According to the invention, such skin care composition may be any composition containing at least one of the volatile compounds according to the invention and are typically in the form of lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti -acne products, day-creams, night-cream, under eye-cream, face mask, face lotion, body lotion, after-shave lotions, cleaning milk, toners
[0263] According to the invention, a color cosmetic composition denotes any cosmetic composition, i.e. any composition intended to be placed in contact with the various external parts of the human body (epidermis, hair system, nails, lips and external genital organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them, perfuming them, changing their appearance and/or correcting body odors and/or protecting them or keeping them in good condition which is primarily directed at the aim of changing the appearance by the provision of color. Typically, these compositions according to the invention containing at least one of the volatile compounds according to the invention are in the form of lip-stick, pencils, lipcolor, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer.
[0264] According to the invention, a hair care composition is any cosmetic composition applied for care and treatment of hair, in particular on the head.
[0265] According to the invention, such hair care composition may be any composition containing at least one of the volatile compounds according to the invention and are typically in the form of hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams.
[0266] A sun care composition according to the invention is any kind of skin care, hair care product and nail care product directed at the protection against the effect of sunlight, wherein both the lowering of the amount of radiation interacting with the keratinous parts of the body and alteration of effects of the absorption of radiation, in particular the reduction of skin damage and skin aging, is included. According to the invention, such hair sun care composition may be any such composition containing at least one of the volatile compounds according to the invention and are typically in the form of sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products.
[0267] According to the invention, bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash are product which are applied to the skin for the removal of dirt, dust, grease and other undesired substances and particles adherent to the skin and/or hair, which are used either in a pure form, for example make up remover for the removal of make up residues, or in combination with water, for instance bathing soap or bath gel.
[0268] In an even further preferred embodiment of the invention, the personal care products according to the previous embodiments are aqueous compositions.
[0269] According to the invention, a personal care product comprising the modified particles of the invention is considered to be an aqueous composition when it contains at least 10 weight-% of water based on the total weight of the composition.
[0270] Typically lotions, creams, emulsions are aqueous compositions. [0271] It is preferred when the water content of the personal care products as defined above is in the range of 10 to 80 weight-%, more preferably 15 to 70 weight-% of the composition, most preferably 20 to 60 weight-% based on the total weight of the composition.
[0272] In another embodiment, the personal care product comprising the particles according to the embodiments according to the embodiment described above has a water content of less than 10 weight-%, preferably less than 8 weight-%, even more preferably less than 5 weight-% and most preferably less than 3 weight-% on the basis of the overall weight of the personal care product. This is the case when the personal care product is an application as a compact in powder form.
[0273] In a particularly preferred embodiment of the invention, personal care products according to the invention comprise from 0.5 to 95 weight-% of one or more types of modified particles according to the invention as described above.
[0274] When the personal care product is selected from the group of skin care formulation, it is preferred when the composition comprises 0.1 to 90 weight-%, more preferably 2 to 80 weight-%, even more preferably 5 to 70 weight-%, and most preferably 10 to 60 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition.
[0275] When the personal care product is selected from the group of color cosmetics, it is preferred when the composition comprises 1 to 90 weight-%, more preferably 2 to 80 weight-%, even more preferably 3 to 70 weight-%, and most preferably 5 to 60 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition.
[0276] When the personal care product is selected from the group of hair care formulations, it is preferred when the composition comprises 0.01 to 99 weight-%, more preferably 0.5 to 95 weight-%, even more preferably 1 to 92 weight-%, and most preferably 2 to 90 weight-% of the one or more types of modified particles according to the invention as described above based on the total weight of the personal care product composition. Summary of preferred embodiments according to the invention
[0277] In the following, the preferred embodiments according to the invention are summarized:
1. Modified particles, wherein
(A) said particles are selected from cellulose-based particles,
- natural fiber particles, starch-based particles, and
- plant-based particles different from natural fiber particles, said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
(B) said particles being modified by one or more primary modifications selected from the group consisting of: esterification, esterification and silication,
- physisorption of C4 to C29 alkyl derived quaternary ammonium compounds,
- physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in parti cular of Mg stearate, and
(C) said particles being optionally modified by one or more secondary modifications selected from the group consisting of:
- modification by physisorption of primary, secondary or tertiary amines, preferably of triethanol amine (TEA),
- modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quaternized guar gums, and modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides
- modification by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in parti cular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B), and that the acetylation of the particles (A) cannot be the only modification performed. Modified particles according to embodiment 1, wherein the particles are selected from cellulose-based particles. Modified particles according to embodiment 1, wherein the particles are selected from natural fiber particles. Modified particles according to embodiment 1, wherein the particles are selected from starch-based particles. Modified particles according to embodiment 1, wherein the particles are selected from plant-based particles. Modified particles according to the previous embodiment, wherein the plant-based particles are selected from particles made from tea leaves, preferably green tea leaf powders. Modified particles according to embodiments 1 or 2, wherein the cellulose-based particles are selected from micronized cellulose particles, such as microcrystalline cellulose particles. Modified particles according to embodiments 1 or 4, wherein the starch particles are selected from natural starch particles, such as corn starch particles or potato starch particles. Modified particles according to embodiments 1 or 3, wherein the natural fiber particles are selected from bamboo fiber particles. Modified particles according to any of embodiments 1 to 9, wherein the modified particles are obtained by physisorption of quaternary ammonium compounds by said particles, and wherein preferably the weight ratio of the particles to said quaternary ammonium compounds is from 99.9 : 0.1 to 90 : 10. Modified particles according to any of embodiments 1 to 10, wherein the modified particles are consisting of the particles and the quaternary ammonium compounds adsorbed by said particles. Modified particles according to any of embodiments 1 to 11, wherein the C4 to C29 alkyl derived quaternary ammonium compounds of the primary modification (B) are selected from the group consisting of ester quats or poly fatty acid based quats. 13. Modified particles according to any of embodiments 1 to 12, wherein the particles are modified by the physisorption of C4 to C29 alkyl derived quaternary ammonium compounds selected from compounds of the general formula (I): R1(-F)X (I), wherein x is 1 to 50,
R1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ),and can be substituted by one or more groups selected from OH groups and halide groups, and
F can be the same or different and is represented by the general formula (II)
Figure imgf000076_0001
wherein the groups F bind to a carbon atom of R1, and n is independently 0 to 100,
R2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), and can be substituted with one or more groups selected from OH groups and halide groups,
R3, R4, R5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N— — N—
( ), quaternary ammonium groups ( ), and can be substituted with one or more groups selected from OH groups and halide groups, wherein R3, R4, R5 each bind with a carbon atom to the nitrogen atom, and preferably R3, R4, R5 are not hydrogen, the counter ions A" of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R1, R2, R3, R4, R5 present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV):
(— X—C(O)—R6)m— X~C(O)~ (III) or
(-C(O)-X-R6)m-C(O)-X-- (IV), wherein m = 1 to 20, X is O or NR11, R11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), and can be substituted with one or more hydroxyl and halide groups,
R6 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, with the proviso that at least one R6 has more than 6 carbon atoms, and that for x = 1
R1, R3, R4, R5 do not bind through -OCH2CH2- to the nitrogen atom of the group
Figure imgf000077_0001
Modified particles according to any of embodiments 1 to 13, wherein the quaternary ammonium compounds for the preparation of the modified particles according to any of the previous embodiments in the primary or secondary modification step are selected from the group consisting of the ester quats Stepan VK-90,
STEPANQUAT® Helia, Kao Tetranyl L 12, and Fentacare TEP 90, in particular Kao Tetranyl L 12, estolide-based quats, or guar-gum based quats, in particular Jaguar Excel. Modified particles according to any of embodiments 1-10 and 12-14, wherein a primary modification (B) of the particles is an esterification step carried out with one or more esterification agents selected from carboxylic acids, carboxylic acid anhydrides, acyl halides or alkenyl acetates. Modified particles according to the previous embodiment, wherein the esterification is carried out with acetic acid, acetic acid anhydride, alkanoyl chlorides derived from C3-C28 saturated or unsaturated, linear or branched chain fatty acids which are monocarboxylic acids, more preferably with an even number of carbon atoms of from 4 to 28, even more preferably of from 6 to 24 carbon atoms, such as the acyl chlorides derived from hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid. Modified particles according to the previous embodiments 1-10 and 12-16, wherein a primary modification (B) by esterification is is carried out with at least one di- or higher carboxylic acid or a derivative thereof selected from a corresponding ester, acyl chloride or carboxylic acid anhydride. Modified particles according to any of embodiments 1-10 and 12-17, wherein a primary modification (B) of esterification and silication is carried out, preferably with alkanoyloxy silanes, such as tetraacetoxy silane or methyltriacetoxysilane. Use of the modified particles according to any of embodiments 1 to 18 for the manufacture of personal care products, such as cosmetic compositions. 20. Personal care products comprising the modified particles as defined in any of the previous embodiments 1 to 18, and at least one further additional cosmetic active ingredient.
21. Personal care products according to the previous embodiment 20, which are selected from: a. topical compositions to be applied to keratinous substrate such as skin, lip, hair, nail; b. antiperspirant and deodorant compositions in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, selffoaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories; c. skin care compositions such as lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti-acne products, day- creams, night-cream, under eye-cream, face mask, face lotion, body lotion, aftershave lotions, cleaning milk, toners; d. color cosmetic compositions such as lip-stick, pencils, lip-color, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer; e. hair care compositions such as hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams; f. sun care compositions such as sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products. g. bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash.
22. Personal care products according to the previous embodiments 20 to 21, wherein the personal care product is an aqueous composition.
23. Personal care products according to the previous embodiments 20 to 22, wherein the personal care product comprises from 0.5 to 95 wt.-% of one or more types of modified particles as defined in any of the previous embodiments.
THE WEIGHT
[0278] The grinding protocols for natural fibers larger than covered by the invention are outlined in the experimental section. Further, chemical as well as physical modification protocols for the micronized particles are described in the example section. The example section also outlines the incorporation of these particles in personal care formulations and the determination of the overall likeabilitiy based on the sensory properties of the particles.
EXAMPLES
Materials
[0279] Vivapur ® CS 4 FM (microcrystalline cellulose having average particle size of 4 pm as determined by laser diffraction method according to the supplier JRS), Vivapur ® CS 5 (microcrystalline cellulose having an average particle size of 5 pm), Vivapur ® CS 12 (microcrystalline cellulose having an average particle size of 12 pm), Vitacel ® CS8 Green Tea powders ( 0.16mol OH with Mw 324.28 for cellobiose (particle size 8 pm)) were procured from J.Rettenmaier &Sbhne GmbH, Germany.
[0280] Bamboo fiber was supplied by Institute of Wood Science and Technology, Bengaluru, India. Sigmacell cellulose Type 20: 20 pm, Com Starch, Acetic anhydride, dimethyl formamide, potassium carbonate, isopropenyl acetate, vinyl acetate, hexanoyl chloride, palmitic acid and oxalyl chloride were procured from Sigma Aldrich chemicals, India.
[0281] Iodine was procured from TCI chemicals, India. All reagents were used as received.
[0282] Stepantex VK-90 was procured from the Stepan Company, Jaguar Excel was procured from Solvay, Tetranyl L12 was procured from Kao Industrial (Thailand) Co., Ltd., Varisoft EQ100 was procured from Evonik Industries AG, and Cellulobeads D- 10 was procured from Kobo Products, Inc.
Preparation of materials
1. Processing of Bamboo
[0283] Dendrocalamus stocksii species of bamboo was obtained from Institute of Wood Science and Technology (Parent Institution: Indian Council of Forestry Research and Education), Bengaluru, India. It contains cellulose (45 weight-%), hemicellulose (25 weight-%), lignin (23 weight-%), extractives (5 weight-%), ash content (2 weight-%). [0284] Bamboo pulverization and sieving was done at Institute of Wood Science and Technology, Bengaluru, India. The bamboo pole was converted into chips using a small scale wood chipper. The chips were dried in a hot air oven at 90 °C for 24 hours and then pulverized. The pulverized wood powder was further sieved using a gyrator sieve shaker and segregated into different particle size. The bamboo particles were further micronized using cryogrinding using Retsch Cryogrinder and sieved through 25 microns sieve.
[0285] Width of the particle was below 50 microns as per SEM image analysis.
[0286] 1% H2O2 solution mixture was prepared from 3% H2O2 peroxide solution (6.6 gram), DM water (13.2 gram) and sodium bicarbonate (0.0245 gram). This mixture was added to 1 gram of bamboo fiber while mixing and heated to 70 °C for 4 hours for bleaching. These particles are used for further modification and formulation study.
[0287] To verify the desired particle size, SEM was used to study the particle size.
Figure imgf000081_0001
(Particle size study of bamboo fibers after sieved through 25 um sieve by SEM) 2. Modification of micronized particles - Examples Example 1 (not according to the invention)
Acetylation of microcrystalline cellulose (Vivapur ® CS4 FM)
[0288] In a 250ml two neck bottle equipped with magnetic stirrer and reflux condenser 11 gram of Vivapure® CS4 FM powder (microcrystalline cellulose having average particle size of 4 pm as determined by laser diffraction method according to the supplier JRS), 61 gram of acetic anhydride (0.056 mmol) and 1.1 gram of potassium carbonate (0.072 mmol) were placed. The reaction was carried out in dimethyl formamide (100ml) as solvent at 100 °C for 3 hours. After reaction completion, the final product was centrifuged to remove unreacted chemicals. The final product is centrifuged 3 times with mixture of 2-propanol and acetone (1 : 1) and oven-dried at 80 °C for 24 h. Example 2
Esterification of microcrystalline cellulose (Vivapur ® CS4 FM) with hexanoyl chloride [0289] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser taken 1g of Vivapur® CS4 FM powder (microcrystalline cellulose having D50 average particle size of 4 pm as determined by laser diffraction method according to the supplier JRS)) was dispersed in 1 : 1 ratio of dimethylformamide and triethyl amine as solvents (total volume 20 ml). The reaction mixture was heated to 70°C for 2 hours. To this 5 ml of hexanoyl chloride were added dropwise. The reaction was continued for 12h at 115°C. After completion of the reaction, the product was filtered and washed several times with a mixture of isopropanol and acetone in the ratio of 1 : 1 to remove unreacted chemicals. The final material was oven-dried at 85°C overnight. The schematic representation of the reaction is described below.
Figure imgf000082_0001
FTIR Spectra of esterified microcrystalline cellulose (Vivapur® CS4 FM)
[0290] Modified samples were characterized by FTIR spectroscopy. Esterified samples were easily identified in the FTIR spectra. The emergence of a carbonyl stretching vibration at 1745 cm'1 (u C=O) and reduced intensity of the characteristic hydroxyl group absorption bands in the spectra confirmed the formation of ester bonds after reactions. Example 3A Synthesis of a glycerol based quat (quaternary ammonium compound) for the modification of natural particles
[0291] The synthesis of quaternary ammonium samples is carried out in a three-step process:
A. Synthesis of the poly fatty acid
B. Synthesis of an amine salt
C. Synthesis of the final quat
A. Synthesis of the poly fatty acid hexamer
[0292] Synthesis of a (ricinoleic acid)s-oleic acid estolide hexamer and the corresponding (ricinoleic acid)s-oleic acid hexamer chloride:
[0293] (ricinoleic acid)s-oleic acid estolide hexamer (“[(rici)5-oleic acid]”), the corresponding (ricinoleic acid)s-oleic acid hexamer chloride and the intermediates [(rici)i-oleic acid], [(rici)2-oleic acid], [(rici)3-oleic acid] and [(rici)4-oleic acid] as well as the carboxylic acid chlorides obtained during synthesis of the title compounds have been prepared according to Synthesis Example 3 of WO2021/123904.
[0294] A brownish, transparent oil essentially having the following structure of ((rici)s-oleyl acid) is obtained:
Figure imgf000083_0001
B. Synthesis of an amine salt
[0296] Synthesis of an amine salt of a tertiary amino alcohol ester of the (ricinoleic acid)2-oleic acid estolide
[0297] Following the procedure of Example 1 of WO2021/123904, a brownish wax having the following structure is obtained:
Figure imgf000083_0002
with R =
Figure imgf000084_0001
C. Synthesis of the final quat
[0298] Synthesis of a glycerol based quat using the amine salt of a tertiary amino alcohol ester of the (ricinoleic acid)2-oleic acid estolide
[0299] Following the procedure of Example 6 of WO2021/123904, a brownish viscous oil having the following approximate structure is obtained:
Figure imgf000084_0002
Example 3B
[0300] A. The synthesis of a [(ricinoleic acid)s-oleic acid] estolide hexamer and the corresponding [(ricinoleic acid)s-oleic acid] chloride hexamer was carried out as described in the Synthesis Example 3 of WO2021/123904 as noted above. [0301] B. Synthesis of an amine salt of a tertiary amino alcohol ester of the [(ricinoleic acid)s-oleic acid] estolide
[0302] Following the procedure of Example 2 of WO2021/123904, a brownish wax having the following structure was obtained:
Figure imgf000085_0001
[0303] C. Synthesis of a glycerol diglycidyl ether based quat using the amine salt of a tertiary amino alcohol ester of the [(ricinoleic acid)s-oleic acid] estolide
[0304] Following the procedure of Example 10 of WO2021/123904„a brownish viscous oil having the following structure was obtained:
Figure imgf000085_0002
with R =
Figure imgf000086_0001
Example 4
Physisorption of quaternary ammonium compounds on Vivapur® CS4 FM powder (microcrystalline cellulose having an average particle size of 4 pm)
[0305] Quaternary ammonium samples from Example 3 A was diluted with water with active concentration of 0.0536%, i.e. 100 g of an aqueous solution of the quat containing 0.0536 g of the quat (0.0536 weight-%) were prepared. In a 100 ml two-necked bottle, 9.5 g of the diluted quat solution (with 0.053% active), and 7g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture bring the pH to 3-4. 0.1 g cellulose powder Vivapur ® CS4 FM (microcrystalline cellulose having a D50 average particle size of 4 pm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through the filter paper and the solid samples were collected and was dried at room temperature (RT). The quat-modified sample was analysed using FTIR technique to confirm the presence of ester peak resulting from the quat. Example 5 Physisorption of quaternary ammonium compounds on Vivapur® CS4 FM powder (microcrystalline cellulose having a particle size of 4 pm)
[0306] Quaternary ammonium samples from Example 3 A was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 2 liter two-necked bottle, 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added. The mixture was mixed at room temperature. 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4. 20 g Cellulose powder Vivapur ® CS4 FM was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was analyzed using FTIR technique to confirm the presence of ester peak resulting from the quat.
Example 6
Physisorption of quaternary ammonium compounds on Vivapur® CS5 powder (microcrystalline cellulose having an average particle size of 5 pm)
[0307] Quaternary ammonium samples from Example 3 A was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 2 liter two-necked bottle, 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added. The mixture was mixed at room temperature. 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4. 20 g cellulose powder Vivapur ® CS Sensory 5 was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was analysed using FTIR technique to confirm the presence of an ester peak resulting from the quat. Example 7 Physisorption of quaternary ammonium compounds on Spherical Cellulose Beads (CELLULOBEADS D-10)
[0308] Quaternary ammonium samples from Example 3B was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 2 liter two-necked bottle, 400 g of aqueous quat solution (quat content 0.053 weight-%) and 600g of water were added. The mixture was mixed at room temperature. 1.6 g of acetic acid was added to the above mixture to bring the pH to 3-4. 20 g spherical hydrophilic cellulose beads CELLULOBEAD D-10 (median diameter < 15 pm) were added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature. The quat-modified sample was analyzed using FTIR technique to confirm the presence of ester peak resulting from the quat. FTIR confirms the modification of cellulose particle with the quat. Example 8 Physisorption of quaternary ammonium compounds on Spherical Cellulose Beads (CELLULOBEADS D-10)
[0309] STEPANTEX® VK 90 (Methyl bi s[ethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat.. In a 100 ml two-necked bottle, 10 g of aqueous quat solution (quat content 0.05 weight-% ), and 15 g of water were added. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g cellulose beads CELLULOBEAD D-10 (median diameter < 15pm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through the filtered paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was submitted to analysis using FTIR technique to confirm the presence of an ester peak.
Example 9
Physisorption of quaternary ammonium compounds on cellulose particles [0310] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 50 ml two-necked bottle, 5.1 g of aqueous quat solution (quat content 0.05 weight-% ), and 20 g of water were added. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g cellulose powder Sigmacell cellulose Type 20 (particle size 20 pm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
Example 9A
Physisorption of quaternary ammonium compounds on cellulose particles
[0311] Quaternary ammonium samples from Example 3 A was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 50 ml two-necked bottle, 10 g of aqueous quat solution (quat content 0.05 weight-% ), and 15 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g cellulose powder Sigmacell cellulose Type 20 (particle size 20 mm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of ester peak. Example 9B
Physisorption of quaternary ammonium compounds on cellulose particles
[0312] Asample of the quaternary ammonium compound STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0536 weight-% of the quat. In a 50 ml twonecked bottle and 5.1 g of aqueous quat solution (quat content 0.0573 weight-%) and 20 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g cellulose powder Sigmacell cellulose Type 20 (particle size 20 mm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through the filter paper and the solid samples were collected and dried at room temperature (RT). The quat- modified sample was submitted for analysis using FTIR technique to confirm the presence of ester peak.
Example 9C
Physisorption of quaternary ammonium compounds on cellulose particles [0313] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0573 weight-% of the quat. In a 50 ml two-necked bottle 10 g of aqueous quat solution (quat content 0.0573 weight-%) and 15 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g of Vivapur ® CS Sensory 5 was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature RT. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
Example 10
Physisorption of quaternary ammonium compounds on corn starch particles [0314] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0573 weight-% of the quat. In a 50 ml two-necked bottle, 10 g of the aqueous quat solution (quat content 0.0573 weight-%) and 15 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 0.5 g corn starch (Sigma Aldrich, particle size 4-21 pm according to determination by SEM) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through filter paper and the solid samples were collected and dried at room temperature (RT). The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
Example 11
Physisorption of quaternary ammonium compounds on cellulose particles [0315] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.0573 weight-% of the quat. In a 500 ml two-necked bottle 180 g of aqueous quat solution (quat content 0.0573 weight-%) and 1 g of an aqueous solution of Jaguar Excel (quat content 1 weight-%) and 70 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to the above mixture to bring the pH to 3-4. 5 g Vivapur CS5 (microcrystalline cellulose having an average particle size of 5 pm) was added very slowly to the above mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. Example 12
Physisorption of quaternary ammonium compounds on cellulose particles [0316] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 2000 ml two-necked bottle, 250 g of water were placed, and 10 g of Vivapur CS 12 were added. The mjxture was mixed at room temperature. Triethanol amine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h. After the 1 h of mixing, 100 g of the aqueous quat solution (quat content 0.1 weight-%), 2 g of an aqueous solution of Jaguar Excel (1% active), and 150 g of water were added to the mixture. Triethanol amine (TEA) was added slowly dropwise and pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 8 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. Example 13
Physisorption of quaternary ammonium compounds and aluminum monostearate on cellulose particles
[0317] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 500 ml two-necked bottle, 80 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Tri ethanol amine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To the above mixture, 50 g of above described 0.1% quat solution in water, a mixture of 0.01 g of aluminum monostearate in 125 g of isopropyl alcohol (IP A), were added to the above mixture. Triethanolamine (TEA) was added slowly dropwise and pH of the mixture was maintained between 10-11. This mixture was stirred at room temperature for 30 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. Example 14
Physisorption of quaternary ammonium compounds and aluminum monostearate on cellulose particles
[0318] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 500 ml two-necked bottle, 125 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Triethanolamine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To the above mixture, 50 g of above described 0.1% quat solution in water was added to the above mixture. To this mixture, a mixture of 0.1 g of aluminum monostearate in 125 g of isopropyl alcohol (IP A) were added. Triethanolamine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. This mixture was stirred at room temperature for 30 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. Example 15
Physisorption of quaternary ammonium compounds and aluminum monostearate on cellulose particles
[0319] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 500 ml two-necked bottle, 125 g of water were placed, and 5 gm of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Triethanolamine (TEA) was added slowly drop wise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To the above mixture, 50 g of above described 0.1% quat solution in water was added to the above mixture. To this mixture, a mixture of 0.2 g of aluminum monostearate in 125 g of IPA was added. Triethanolamine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 30 h. The resultant mixture was filtered through a filter paper and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. Example 16
Physisorption of quaternary ammonium compounds and magnesium stearate on corn starch particles
[0320] STEPANTEX® VK 90 (Methyl bisfethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate) was diluted with in order to prepare a solution containing 0.1 weight-% of the quat. In a 500 ml two-necked bottle, 80 g of water were placed, and 5 g of com starch as described above were added. It was mixed at room temperature. Triethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10- 11. The mixture was stirred at room temperature for 1 hr. To this mixture, 50 g of the aqueous quat solution, a mixture of 0.05 g of magnesium stearate in 125 g of IPA, were added to the above mixture. Triethanolamine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 30 h. The resultant mixture was filtered through the filter paper and washed with water three times. The solids were collected and dried at room temperature RT. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak. [0321] For determining Mg content, inductively coupled plasma optical emission spectrometry (ICP-OES) as described below was used. The Mg content was determined to be 102 ppm.
Experimental determination of the Mg content:
[0322] Sample preparation required digesting the sample in a microwave (Anton Paar, Multiwave7000 An acid vessel blank was prepared during the sample digestion. An acid mixture of 3 mL HF, 1 mL HNCh, and 1 mL HC1 were added to ~0.3 g sample in a 30 mL Teflon vessel. The Teflon vessels with acid and sample could pre-digestion and then transferred to the microwave for complete digestion. After a microwave digestion, diluted to 50 mL with deionized water (Millipore, Milli-Q). Diluted solution was analyzed by ICP-OES (Agilent 720). Mg calibration standards are prepared using certified stock solution from Inorganic ventures. Example 17 Physisorption of quaternary ammonium compounds and magnesium stearate on cellulose particles
[0323] STEPANTEX® VK 90 (Methyl bi s[ethyl (tallowate)] -2- hydroxyethyl ammonium methyl sulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 500 ml two-necked bottle, 80 g of water were placed, and 5 g of Vivapur CS Sensory 5 were added. It was mixed at room temperature. Tri ethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. The mixture was stirred at room temperature for 1 h. To this mixture, 50 g of the aqueous quat solution - and a mixture of 0.05 g of magnesium stearate in 125 g of IP A were added. Triethanolamine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. This mixture was stirred at room temperature (RT) for 30 h. The resultant mixture was filtered through the filter paper and washed with water three times. The solids were collected and dried at room temperature (RT). The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
Example 18
Physisorption of quaternary ammonium compounds on cellulose partides [0324] Evonik VARISOFT® EQ 100 was diluted with water in order to prepare a solution containing 0.0573 weight-% of the quat. In a 50 ml two-necked bottle, 10 g of the aqueous quat solution (quat content 0.0573 weight-%) and 15 g of water were placed. The mixture was mixed at room temperature. Acetic acid was added to this mixture to bring the pH to 3-4. 0.5 g Vivapur CS5 (microcrystalline cellulose having an average particle size of 5 pm) were added very slowly to the mixture. The mixture was allowed to mix for 4-5 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
Example 19
Physisorption of quaternary ammonium compounds on cellulose particles
[0325] Tetranyl L-12 (Dialkylester Ammonium Methylsulfate) was diluted with water in order to prepare a solution containing 0.1 weight-% of the quat. In a 2000 ml two-necked bottle, 250 g of water were placed, and 10 g of Vivapur CS 12 were added. The mjxture was mixed at room temperature. Triethanol amine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h. After this 1 h of mixing, 100 g of the aqueous quat solution (quat content 0.1 weight-%), 2 g of an aqueous solution of Jaguar Excel (guar hydroxypropyltrimonium chloride) (1% active), and 150 g of water were added to the mixture. Triethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10- 11. This mixture was stirred at RT for 8 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. The quat-modified sample was submitted for analysis using FTIR technique to confirm the presence of an ester peak.
[0326] Further, the amount of Tetranyl quat on the modified cellulose particles was quantified by quantitative FT-IR.
Experimental Conditions:
Instrument Fourier Transform Infrared (FTIR) Mode: Transmission Cell: KBr Source: MIR (8000- 30 cm'1) Beam splitter: OptKBr (7800-400 cm'1) Detector: MIR TGS Optimum Scan: (4000-400 cm'1) Accumulations: 16 scans Scan speed: 0.5 cm/s
Sample preparation:
[0327] 200 mg of sample was taken in a glass vial. 10 ml of THF was added and kept on the shaker for 10 min, the mixture was allowed to settle for 5 min and the supernatant was injected in the flow cell between KBr plates with 1 mm spacer for FTIR measurement.
[0328] Tetranyl standard: Tetranyl L12-90 0.04% in THF (equivalent to 2 weight-% Tetranyl on cellulose)
[0329] Peak area of carbonyl peaks at 1739 cm'1 and 1723 cm'1 was measured and compared with the peak area in the Tetranyl standard to determine weight-% of quat. Example 19 A Physisorption of quaternary ammonium compounds on cellulose particles
[0330] In a 1000 ml two-necked bottle, 125 g of water were placed, and 10 g of Vivapur CS 12 were added. The mjxture was mixed at room temperature. Triethanolamine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h. 0.2 g of Tetranyl L-12 (Dialkylester Ammonium Methyl sulfate) and 0.02 g of Jaguar Excel were mixed with 125 g of water for 5 min and a solution was prepared. After further 1 h of mixing, the above solution was added to the bottle. Triethanolamine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 8 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature.
[0331] The amount of Tetranyl quat on the modified cellulose particles was quantified by quantitative FT-IR as described above. Tetranyl quat content that was determined by this method was 0.7 weight-%.
Example 19 B
Physisorption of quaternary ammonium compounds on cellulose particles
[0332] In a 1000 ml two-necked bottle, 125 g of water were placed, and 10 g of Vivapur CS 12 were added. The mjxture was mixed at room temperature. Triethanol amine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h. 0.4 g of Tetranyl L-12 (Dialkylester Ammonium Methyl sulfate) and 0.02 g of Jaguar Excel was mixed with 125 g of water for 5 min and a solution was prepared. After further 1 h of mixing, the above solution was added to the bottle. Triethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 8 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature.
[0333] The amount of Tetranyl quat on the modified cellulose particles was quantified by quantitative FT-IR. Tetranyl quat content that was determined by this method was 2 weight-%.
Example 20 (not according to the invention) Acetylation of Camelia Sinensis (Green Tea) Leaf Powder Vitacel CSS (particle size 8 pm)
[0334] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 10g Vitacel CS8 Green Tea (J. Rettenmaier & Sbhne GmbH; 0.18 mol OH with Mw 324.28 for cellobiose, (particle size 8 pm)), 40g acetic acid anhydride (0.392 mol) and 40g acetic acid were mixed at room temperature under N2. The mixture was heated to 115 °C for 5 h. Afterwards, volatiles were removed at 70°C /20mmHg. 40ml 2-propanol were added to the viscous product and the stripping repeated. In total four 2-propanol addition and stripping cycles were carried out. Finally, a solid, dark green material was obtained which was subjected to a manual grinding and yielding a powdery acetylated green tea derivative, and the isolated yield thereof was 12.97g. FTIR was used to prove the acetylation reaction. The FTIR spectrum is shown in Figure 1.
Example 21
Acetylation and silication of Camelia Sinensis (Green Tea) Leaf Powder Vitacel CSS (particle size 8 pm) using acetic acid anhydride and tetraacetoxysilane
[0335] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 8.65g Vitacel CS8 Green Tea (J. Rettenmaier & Sbhne GmbH; 0.16mol OH with Mw 324.28 for cellobiose (particle size 8 pm)), 8.16g acetic acid anhydride (0.08 mol), 5.57g tetraacetoxysilane (0.08 mol acetoxy) and 50g acetic acid were mixed at room temperature under N2. The mixture was heated to 115°C for 12 h. Afterwards, volatiles were removed at 45°C /20mmHg. 40ml 2-propanol were added to the viscous product and the stripping repeated. In total seven 2-propanol addition and stripping cycles were carried out. Finally, a solid, dark green material was obtained which was subjected to a manual grinding and yielding a powdery acetylated green tea derivative. Isolated yield 13.05g. FTIR was used to prove the acetylation reaction. The FTIR spectrum is shown in Figure 2. Example 22
Acetylation and silication of Camelia Sinensis (Green Tea) Leaf Powder Vitacel CSS (particle size 8 pm) using tetraacetoxy silane
[0336] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 8.65g Vitacel CS8 Green Tea (J. Rettenmaier & Sbhne GmbH; 0.16mol OH with Mw 324.28 for cellobiose (particle size 8 pm)), 10.57g tetraacetoxysilane (0.16 mol acetoxy) and 43g acetic acid were mixed at room temperature under N2. The mixture was heated to 115°C for 17 h. Afterwards, volatiles were removed at 48°C /20mmHg. 40ml 2-propanol were added to the viscous product and the stripping was repeated. In total four 2-propanol addition and stripping cycles were carried out. Finally, a solid, dark green material was obtained which was subjected to a manual grinding, yielding a powdery acetylated green tea derivative. Isolated yield 10.95g. FTIR was used to prove the acetylation reaction. The FTIR spectrum is shown in Figure 3.
Example 23 (not according to the invention) Acetylation of Bamboo fiber powder using Acetic Anhydride
Figure imgf000097_0001
[0337] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 1 g of bamboo powder, 5.71 g of acetic anhydride (0.056 mmol) and 0.1 g of potassium carbonate (0.072 mmol) were placed. The reaction was carried out in dimethyl formamide (20 ml) as solvent at 100 °C for 3 h. After completion of the reaction, the final product was filtered. The filtered product was washed repeatedly with a mixture of acetone and 2- propanol (volume ratio 1 : 1) and oven-dried at 80 °C overnight. The reaction product was characterized by FTIR to prove the acetylation reaction.
Example 24 (riot according to the invention) Acetylation of Bamboo fiber powder using vinyl acetate
Ba txx 0H
Figure imgf000097_0002
[0338] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 1 g of bamboo fiber powder, 4.8 g vinyl acetate (0.056 mmol) and 0.1 g of potassium carbonate (0.072 mmol) and 0.01 g of I2 were placed. The reaction was carried out in dimethyl formamide (20 ml) as solvent at 100 °C for 3 h. After completion of reaction, the final product was filtered. The filtered product was repeatedly washed with mixture of acetone and 2-propanol (volume ratio 1 : 1) and oven-dried at 80°C overnight. The reaction product was characterized by FTIR to prove the acetylation reaction.
Example 25
Acetylation of Bamboo fiber powder using acetic anhydride (not according to the invention)
[0339] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 1 g of bamboo fiber powder and 5.71 g of acetic anhydride (0.056 mmol) were placed with a concentration of 0.035 mol/1 of iodine used as catalyst. The reaction was carried out in dimethyl formamide as solvent at 95 °C for 3-5 h. After completion of the reaction, the final product was filtered. The filtered product was washed repeatedly with a mixture of acetone and 2-propanol (volume ratio 1 : 1) and oven-dried at 80 °C overnight. The reaction product was characterized by FTIR to prove the acetylation reaction.
Example 26
Acetylation and silication of Bamboo fiber powder using acetic acid anhydride and tetraacetoxy silane
[0340] In a 250 ml three neck bottle equipped with magnetic stirrer and reflux condenser 15.52 g bamboo fiber powder, 14.64 g acetic acid anhydride (0.08 mol), 10 g tetraacetoxy silane (0.08 mol acetoxy) and 90g acetic acid were mixed at room temperature under N2. The mixture was heated to 115 °C for 12 h. Afterwards, volatiles were removed at 45 °C /20mmHg. The filtered product was washed five times with a mixture of acetone and 2- propanol (volume ratio 1 : 1) and oven-dried at 80 °C overnight. The reaction product was characterized by FTIR to prove the acetylation reaction.
Example 27
Esterification of Bamboo fiber powder with hexanoyl chloride
9 DMF:TEA n , _ n , , I Bamboo-0 x/\/\/ + HC
Bamboo-OH + /X/X , ¥
' - ' Cl 115°C, 12hrs II
0
[0341] In a 100ml three neck bottle equipped with magnetic stirrer and reflux condenser 1g of bamboo fiber powder dispersed in 1 : 1 ratio of dimethylformamide and triethyl amine as solvents (total volume 20 ml) was placed. The reaction mixture was heated to 70°C for 2 h. To this 5 ml of hexanoyl chloride were added dropwise. The reaction continued for 12h at 115°C. After the completion of the reaction, the product was filtered and washed several times with a mixture of isopropanol and acetone in the volume ratio of 1 : 1 to remove unreacted chemicals. The final material was oven-dried at 85°C overnight. The schematic representation of the reaction is provided above. The product was characterized by FTIR spectroscopy. Esterified samples were easily identified in the FTIR spectra. The emergence of a carbonyl stretching vibration at 1745cm'1 (u C=O) in the spectra confirmed the formation of ester bonds after reactions and reduced intensity of hydroxyl groups.
Example 28
Esterification of Bamboo fiber powder with palmitoyl chloride Step 1: Conversion of palmitic acid to palmitoyl chloride:
Figure imgf000099_0001
[0342] In a 100ml three necked roundbottomed flask 5 g (0.025 mole) of palmitic acid were placed. The fatty acid was melted at 65°C and 3.8 g (0.03 mole) of oxalyl chloride were added dropwise. After the addition of the chlorinating agent to the fatty acid, the mixtures were heated and stirred at 70°C for two hours.
Step 2: Esterification of bamboo fibers with palmitoyl chloride: D
Bamboo-OH Bamboo-
Figure imgf000099_0002
Figure imgf000099_0003
1g of bamboo fiber powder was dispersed in 1 : 1 wt.-ratio of dimethylformamide and triethyl amine as solvents (total volume 20 ml). The reaction mixture was heated at 70°C for 2 h. To this added 5ml of palmitoyl chloride dropwise (prepared in step 1 without further purification). The reaction was continued for 12h at 115°C. After the reaction was completed, the product was filtered and washed several times with a mixture of isopropanol and acetone in the volume ratio of 1 : 1 to remove unreacted chemicals. The final material was oven-dried at 85°C overnight. The schematic representation of the reaction is described above. The product was characterized by FTIR spectroscopy. Example 29: Esterification of microcrystalline cellulose powder with succinic acid [0343] 0.75g succinic acid and 0.05g p-toluene sulfonic acid were dissolved in 37.5g deionized (DI) water. This mixture was placed in a 100ml two necked bottle with nitrogen inlet and nitrogen outlet. 15g microcrystalline cellulose Vivapur CS Sensory 12 were added and mixed with the liquid phase. Finally, 4g DI water were added. The obtained slurry was heated to 110 °C for 15h while nitrogen (approximately 500ml/min) was flushed over the mixture’s surface. At the end of the esterification reaction, a powdery material was obtained.
[0344] The FTIR spectrum of the final product shows an ester signal at 1710-1720 cm-1 which is not present in a mixture of microcrystalline cellulose and succinic acid without reaction. The FTIR spectrum is displayed in Figure 4.
Example 30: Esterification of microcrystalline cellulose powder with itaconic acid [0345] 0.75g itaconic acid and 0.05g p-toluene sulfonic acid were dissolved in 42.5g DI water. This mixture was placed in a 100ml two necked bottle with nitrogen inlet and nitrogen outlet. 15g microcrystalline cellulose Vivapur CS Sensory 12 were added and mixed with the liquid phase. The obtained slurry was heated to 110° C for 15h while nitrogen (approximately 500ml/min) was flushed over the mixture’s surface. At the end of the esterification reaction, a powdery material was obtained. The FTIR spectrum of the final product shows an ester signal at 1710-1720 cm-1 which is not present in a mixture of microcrystalline cellulose and itaconic acid without reaction. The FTIR spectrum is displayed in Figure 5.
Example 30 A (+quat modification)
[0346] In a 1000 ml two-necked bottle, 125 g of water were placed, and 10 g of modified Vivapur CS 12 from example 30 were added. The mjxture was mixed at room temperature. Triethanol amine (TEA) was added slowly dropwise and the pH of the mixture was maintained between 10-11. The mixture was stirred at room temp for 1 h. 0.4 g of Tetranyl L-12 (Dialkylester Ammonium Methyl sulfate) and 0.02 g of Jaguar Excel was mixed with 125gm of water for 5 min and a solution was prepared. After further 1 h of mixing, the above solution was added to the bottle. Triethanol amine (TEA) was added slowly drop wise and pH of the mixture was maintained between 10-11. This mixture was stirred at RT for 8 h. The resultant mixture was filtered through the filter paper, and washed with water three times. The solids were collected and dried at room temperature. 3. Evaluation of Properties of Material Evaluation of sensory properties of neat particles [0347] Sensory properties of the particles are evaluated by 10 panelists. lOpg of neat sample is applied on the panelists forearm and asked them to evaluate as per the sensory properites such as smoothness, texture, spread ability, absorption, soft-focus, and brightness, skin adhesion, soft feel, fineness, matte, residue. The average values of these properties as evaluated by the panelists were determined. Also the overall sensory ranking of the properties of the material is evaluated from bad to excellent with numbering from 1 to 10. The below table summarizes the overall sensory rating of the materials.
Figure imgf000101_0002
Figure imgf000101_0001
Evaluation of sensory properties of formulations comprising modified particles
Application Example 1: Liquid Lip Color [0348] A Liquid Lip Color formulation was prepared as indicated in table 1 below with unmodified Vivapur CS12 and Modified Vivapur CS12 (Example-12). The lip colors were tested for tack after drying. The lip color formulations were applied to forearm and were allowed to dry for 30 minutes. The tack was evaluated by the panelists by briefly (1 - 2 seconds) touching the dried films on forearm. The study was performed by 2 panelists and both the panelists reported that the Example 1.1 was more tacky than Example 1.2. Table 1.
Figure imgf000102_0001
Application Example 2: Powder Foundation
[0349] Powder formulations were prepared with the composition shown below in Table 2 using Modified Vivapur CS12 (Example-12) and unmodified Vivapur CS12. The ingredients were mixed in a 100 g speedmixer container and the powders were mixed for 5 minutes to obtain a uniformly mixed loose powder formulation.
[0350] The friction coefficient of the powder formulation were measured with CSM
Tribometer. The powder was rubbed on leather (2 mg/cm2) for 10 s. The friction was measured with 1 cm stainless steel diameter probe with leather (Testfabrics Inc.) attached to the flat surface. The friction was measured at 1 cm/s speed for probe reciprocating 2 cm back in forth for 10 cycles. The friction coefficient was reported as average friction coefficient for 10 cycles.
[0351] As indicated in the Table 2, the friction coefficient of the formulation with Modified Vivapur CS12 (Example-12) was observed to be lower than that of Vivapur CS12.
Table 2.
Figure imgf000103_0001

Claims

CLAIMS:
1. Modified particles, wherein
(A) said particles are selected from
- particles comprising at least 90 percent by weight of cellulose,
- natural fiber particles, said particles have a particle size in the range of 1 to 50, preferably 1 to 40, more preferably 1 to 30 and still more preferably 1 to 20 pm,
(B) said particles being modified by one or more primary modifications selected from the group consisting of: esterification, esterification and silication, physisorption of quaternary ammonium compounds comprising one or more C4 to C29 alkyl or alkylene groups, physisorption of metal carboxylates of divalent metals or trivalent metals, preferably fatty acid or poly fatty acid metal carboxylates of divalent metals and of trivalent metals, more preferably fatty acid or poly fatty acid metal carboxylates of Al or Mg, in particular of Mg stearate, and
(C) said particles being optionally modified by one or more secondary modifications selected from the group consisting of
- modification by physisorption of primary, secondary or tertiary amines, preferably of triethanol amine (TEA),
- modification by physisorption of quaternary ammonium compounds derived from mono-, oligo- and polysaccharides, preferably of quatemized guar gums, and modification by physisorption of primary, secondary and tertiary amino compounds derived from mono-, oligo- and polysaccharides
- modification by physisorption of fatty acid salts or polyfatty acid salts, preferably of fatty acid or poly fatty acid metal carboxylates of divalent or trivalent metals, in particular of Mg and Al, preferably Mg stearate and Al stearate, provided that the secondary modification (C) is different from the primary modification (B), and that the acetylation of the particles (A) cannot be the only modification performed. Modified particles according to claim 1, wherein the particles are selected from particles comprising at least 90 percent by weight of cellulose. Modified particles according to claim 1 or 2, wherein the particles are selected from micronized cellulose particles, such as microcrystalline cellulose particles. Modified particles according to claim 1, wherein the particles are selected from natural fiber particles. Modified particles according to claim 4, wherein the natural fiber particles are selected from bamboo fiber particles. Modified particles according to any of claims 1 to 5, wherein the modified particles are obtained by physisorption of quaternary ammonium compounds by said particles, and wherein preferably the weight ratio of the particles to said quaternary ammonium compounds is from 99.9 : 0.1 to 90 : 10. Modified particles according to any of claims 1 to 6, wherein the modified particles are consisting of the particles and the quaternary ammonium compounds adsorbed by said particles. Modified particles according to any of claims 1 to 7, wherein the quaternary ammonium compounds comprising one or more C4 to C29 alkyl or alkylene groups of the primary modification (B) are selected from poly fatty acid based quats selected from compounds of the general formula (I):
R1(-F)x (I), wherein x is 1 to 50,
R1 is selected from x-valent, optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, preferred 2 to 300 carbon atoms, more preferred 3 to 200 carbon atoms, even more preferred 3 to and 150 carbon atoms, specifically 3 to 50 carbon atoms, more specifically 3 to 20 carbon atoms, and may contain optionally one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ), and can be substituted by one or more groups selected from OH groups and halide groups, and
F can be the same or different and is represented by the general formula (II)
Figure imgf000106_0001
wherein the groups F bind to a carbon atom of R1, and n is independently 0 to 100,
R2 can be the same or different and is selected from divalent optionally substituted hydrocarbon radicals which have up to 1000 carbon atoms, and optionally contain one or more groups selected from -O-, -NFI-, -C(O)--, ~C(S)~, tertiary amino groups
— N—
( ' ), and can be substituted with one or more groups selected from OH groups and halide groups,
R3, R4, R5 can be the same or different and are selected from hydrogen and optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 1000 carbon atoms, which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N— — N—
( ), quaternary ammonium groups ( ), and can be substituted with one or more groups selected from OH groups and halide groups, wherein R3, R4, R5 each bind with a carbon atom to the nitrogen atom, and preferably R3, R4, R3 are not hydrogen, the counter ions A‘ of the ammonium ions are selected from mono to trivalent inorganic and mono- to 30000-valent, preferably mono- to kiliavalent organic anions, and at least one of R1, R2, R3, R4, R’ present in the cationic structure of the general formulas (I) and (II) contains at least one moiety of the formulas (III) or (IV):
(_X-C(O)-R6)m-X-C(O)- (III) or
(-C(O)-X~R6)m-C(O)-X-- (IV), wherein m = 1 to 20,
X is O or NR11,
R11 is independently selected from the group consisting of hydrogen, or optionally substituted straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals which have up to 100 carbon atoms which optionally contain one or more groups selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amino groups
— N—
( ' ), and can be substituted with one or more hydroxyl and halide groups,
R6 is independently selected from optionally substituted straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radicals which have 1 to 36 carbon atoms, with the proviso that at least one R6 has more than 6 carbon atoms, and that for x :=: 1
R1, R3, R4, R5 do not bind through -OCH2CH2-- to the nitrogen atom of the group
Figure imgf000107_0001
Modified particles according to any of claims 1 to 7, wherein the quaternary ammonium compounds comprising one or more C4 to C29 alkyl or alkylene groups of the primary modification (B) are selected from ester quats, and/or wherein preferably the quaternary ammonium compounds for the preparation of the modified particles in the primary or secondary modification step are selected from the group consisting of the ester quats
Stepan VK-90, STEPANQUAT® Helia, Kao Tetranyl L 12, and Fentacare TEP 90, in particular Kao Tetranyl L 12, or quaternized guar gums, in particular Jaguar Excel. Modified particles according to any of claims 1 to 9, wherein a primary modification (B) of the particles is an esterification step carried out with one or more esterification agents selected from carboxylic acids, carboxylic acid anhydrides, acyl halides or alkenyl acetates, wherein the esterification is carried out with acetic acid, acetic acid anhydride, alkanoyl chlorides derived from C3-C28 saturated or unsaturated, linear or branched chain fatty acids which are monocarboxylic acids, more preferably with an even number of carbon atoms of from 4 to 28, even more preferably of from 6 to 24 carbon atoms, such as the acyl chlorides derived from hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid. Modified particles according to the previous claims 1 to 10, wherein a primary modification (B) by esterification is carried out with at least one di- or higher carboxylic acid or a derivative thereof selected from a corresponding ester, acyl chloride or carboxylic acid anhydride. Modified particles according to any of claims 1 to 11, wherein a primary modification (B) of esterification and silication is carried out, preferably with alkanoyloxy silanes, such as tetraacetoxy silane or methyltriacetoxysilane. Use of the modified particles according to any of claims 1 to 12 for the manufacture of personal care products, such as cosmetic compositions. Personal care products comprising the modified particles as defined in any of the previous claims 1 to 12, and at least one further additional cosmetic active ingredient, wherein preferably the personal care products are selected from: a. topical compositions to be applied to keratinous substrate such as skin, lip, hair, nail; b. antiperspirant and deodorant compositions in the form of spray, pencils, sticks, multiphase sticks, pastes, powder, aerosols, creams, cream foams, lotions, selffoaming, foam-like, after-foaming or foamable emulsions, gels, roll-on preparations, foams or depilatories; c. skin care compositions such as lotions, creams, emulsions and microemulsions, moisturizers, anti-aging products, skin tightening lotions, anti-acne products, day- creams, night-cream, under eye-cream, face mask, face lotion, body lotion, aftershave lotions, cleaning milk, toners; d. color cosmetic compositions such as lip-stick, pencils, lip-color, liquid lip color, lip stain, lip balm, lip-gloss, mascara, eye liner, eye-shadow, foundation, face powder, blush, peel cream, bb cream, cc cream, tinted moisturizer; e. hair care compositions such as hair treatments, damage repair compositions, hair waxes, hair gels, hair foam, hair styling fluids, hair sprays, hair oil, mousse, shampoo, conditioner, hair remover creams; f. sun care compositions such as sunscreens, after sun lotions, sun tanner, sunscreen oils, self-tanning products. g. bath products such as bath soap, bath gel, cleansing milk, cleansing solution, make up remover, face wash, and preferably the personal care product comprises from 0.5 to 95
Figure imgf000109_0001
of one or more types of modified particles as defined in any of the previous claims. Personal care products according to the previous claim 14, wherein the personal care product is an aqueous composition.
PCT/US2023/017603 2022-04-05 2023-04-05 Modified natural and green particles for cosmetic application WO2023196410A1 (en)

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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020187173A1 (en) 2001-01-15 2002-12-12 L'alloret Florence Compositions with an optical effect, especially cosmetic compositions
WO2004024103A1 (en) 2002-09-13 2004-03-25 Lipo Chemicals, Inc. Optically activated particles for use in cosmetic compositions
WO2004093834A1 (en) 2003-04-17 2004-11-04 Croda, Inc. Personal care product containing diester quat
US7410649B2 (en) 2004-10-15 2008-08-12 The Procter & Gamble Company Personal care compositions comprising visible beads, cationic polymer, and surfactant
US20130243693A1 (en) 2010-06-17 2013-09-19 Tufts University Silk optical particles and uses thereof
US20140127523A1 (en) 2011-04-18 2014-05-08 Momentive Performance Materials Gmbh Functionalized Polyorganosiloxanes Or Silanes For The Treatment Of Lignocellulosic Materials
CN103898630A (en) 2014-04-13 2014-07-02 临沂市裕成纺织有限公司 Modified bamboo charcoal polyester fiber with health function
CN104358152A (en) 2014-11-26 2015-02-18 四川省宜宾惠美线业有限责任公司 Modified cellulose fibers
US9446265B2 (en) 2014-01-14 2016-09-20 The Procter & Gamble Company Cosmetic composition
EP3081209A1 (en) 2015-04-13 2016-10-19 Borregaard AS Skin care compositions comprising microfibrillated cellulose
US9962565B2 (en) 2015-03-20 2018-05-08 Elc Management Llc Optically-activated system for reducing the appearance of skin imperfections
US10137064B2 (en) 2014-05-30 2018-11-27 L'oreal Foaming cleanser
CN109486160A (en) 2018-12-29 2019-03-19 上海普利特复合材料股份有限公司 A kind of preparation method of smell faint scent, the PC/ABS functional agglomerate of imitative flocking effect and its composite material
CN109674751A (en) 2019-01-15 2019-04-26 华南理工大学 A kind of preparation method of high embedding rate anthocyanin lotion
WO2019151936A1 (en) 2018-02-02 2019-08-08 Speximo Ab Use of non-dissolved starch based particles
EP3616682A1 (en) 2017-12-26 2020-03-04 Japan Corn Starch Co., Ltd. Cosmetic composition, cosmetic product, and method for producing cosmetic composition
WO2021123911A2 (en) 2019-12-17 2021-06-24 Momentive Performance Materials Gmbh Nonionic polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair
WO2021123904A1 (en) 2019-12-17 2021-06-24 Momentive Performance Materials Gmbh Polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020187173A1 (en) 2001-01-15 2002-12-12 L'alloret Florence Compositions with an optical effect, especially cosmetic compositions
WO2004024103A1 (en) 2002-09-13 2004-03-25 Lipo Chemicals, Inc. Optically activated particles for use in cosmetic compositions
WO2004093834A1 (en) 2003-04-17 2004-11-04 Croda, Inc. Personal care product containing diester quat
US7410649B2 (en) 2004-10-15 2008-08-12 The Procter & Gamble Company Personal care compositions comprising visible beads, cationic polymer, and surfactant
US20130243693A1 (en) 2010-06-17 2013-09-19 Tufts University Silk optical particles and uses thereof
US20140127523A1 (en) 2011-04-18 2014-05-08 Momentive Performance Materials Gmbh Functionalized Polyorganosiloxanes Or Silanes For The Treatment Of Lignocellulosic Materials
US9446265B2 (en) 2014-01-14 2016-09-20 The Procter & Gamble Company Cosmetic composition
CN103898630A (en) 2014-04-13 2014-07-02 临沂市裕成纺织有限公司 Modified bamboo charcoal polyester fiber with health function
US10137064B2 (en) 2014-05-30 2018-11-27 L'oreal Foaming cleanser
CN104358152A (en) 2014-11-26 2015-02-18 四川省宜宾惠美线业有限责任公司 Modified cellulose fibers
US9962565B2 (en) 2015-03-20 2018-05-08 Elc Management Llc Optically-activated system for reducing the appearance of skin imperfections
EP3081209A1 (en) 2015-04-13 2016-10-19 Borregaard AS Skin care compositions comprising microfibrillated cellulose
US20180078484A1 (en) 2015-04-13 2018-03-22 Borregaard As Skin care compositions comprising microfibrillated cellulose
EP3616682A1 (en) 2017-12-26 2020-03-04 Japan Corn Starch Co., Ltd. Cosmetic composition, cosmetic product, and method for producing cosmetic composition
WO2019151936A1 (en) 2018-02-02 2019-08-08 Speximo Ab Use of non-dissolved starch based particles
CN109486160A (en) 2018-12-29 2019-03-19 上海普利特复合材料股份有限公司 A kind of preparation method of smell faint scent, the PC/ABS functional agglomerate of imitative flocking effect and its composite material
CN109674751A (en) 2019-01-15 2019-04-26 华南理工大学 A kind of preparation method of high embedding rate anthocyanin lotion
WO2021123911A2 (en) 2019-12-17 2021-06-24 Momentive Performance Materials Gmbh Nonionic polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair
WO2021123904A1 (en) 2019-12-17 2021-06-24 Momentive Performance Materials Gmbh Polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. OTERAJ. NISHIKIDO: "Esterification: Methods, Reactions, and Applications", 2009, WILEY-VCH VERLAG GMBH & CO. KGAA
M. PRIES, WOOD SCI. TECHNOL., vol. 47, 2013, pages 685 - 699

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